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Title: Synthetic resins and their raw materials, report no. 131, second series: A survey of the types and uses of synthetic resins, the organization of the industry, and the trade in resins and raw materials, with particular references to factors essential to tariff consideration
Author: United States Tariff Commission
Language: English
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RAW MATERIALS, REPORT NO. 131, SECOND SERIES ***
UNITED STATES TARIFF COMMISSION
SYNTHETIC RESINS
AND THEIR RAW MATERIALS
REPORT No. 131
SECOND SERIES
[Illustration]
RECENT REPORTS OF THE UNITED STATES TARIFF COMMISSION
REPORTS TO THE PRESIDENT
_Under the Rate Adjustment Provisions (Sec. 336) of the
Tariff Act of 1930_
Dressed or Dyed Furs, Report No. 122, Second Series, 1937 $0.05
Slide Fasteners (Zippers), Report No. 113, Second Series, 1936 .10
_Under the Unfair Practices Provisions (Sec. 337) of the
Tariff Act of 1930_
Coilable Metal Rules, Report No. 106, Second Series, 1936 .05
REPORTS TO THE UNITED STATES SENATE
_Under the General Powers Provision (Sec. 332) of the
Tariff Act of 1930_
Nets and Netting and Other Fishing Gear, Report No. 117, Second
Series, 1937 .10
Salmon and Other Fish, Report No. 121, Second Series, 1937 .15
Subsidies and Bounties to Fisheries Enterprises by Foreign
Countries, Report No. 116, Second Series, 1936 .15
Tuna Fish, Report No. 109, Second Series, 1936 .10
Wood Pulp and Pulpwood, Report No. 126, Second Series, 1938 .30
OTHER REPORTS UNDER THE GENERAL POWERS PROVISION OF THE
TARIFF ACT OF 1930
Dominion and Colonial Statistics, Report No. 127, Second
Series, 1938 .10
Dyes and Other Synthetic Organic Chemicals in the United
States, 1937, Report No. 132, Second Series, 1938 .10
Extent of Equal Tariff Treatment in Foreign Countries,
Report No. 119, Second Series, 1937 .15
The Mica Industry, Report No. 130, Second Series, 1938 .25
Chemical Nitrogen, Report No. 114, Second Series, 1937 .25
Flat Glass and Related Glass Products, Report No. 123,
Second Series, 1937 .35
Iron and Steel, Report No. 128, Second Series, 1938 .60
Cutlery Products, Report No. 129, Second Series, 1937 .15
TRADE AGREEMENTS INFORMATION
Trade Agreement With Canada (a summary of the provisions of
this agreement), Report No. 111, Second Series, 1936 .15
_Miscellaneous Reports_
Changes in Import Duties Since the Passage of the Tariff Act
of 1930, Miscellaneous Series, 1937 .10
Rules of Practice and Procedure (Sixth Revision) and Laws
Relating to the United States Tariff Commission, Miscellaneous
Series, 1938 .10
For sale by the Superintendent of Documents, Government Printing Office,
Washington, D. C., at the prices indicated
UNITED STATES TARIFF COMMISSION
Washington
ERRATA
Since publication of the report on Synthetic Resins the Commission’s
attention has been called to certain necessary corrections.
Page 37—2d line under heading “Production in the United States”
_Strike out_ “The Resinous Products and Chemical Co., Inc.,” and
_insert_ “Rohm and Haas,”
Page 154—Last item under “Vinyl Resins”
_Transfer_ the name of E. I. du Pont de Nemours and Co., Wilmington,
Del. to line below so that it will not be opposite a trade name. This
company manufactures Vinyl Resins but not “Koroseal”.
December 1938
Transcriber’s Note: The errata have been corrected for this e-text,
together with a number of sundry typos.
UNITED STATES TARIFF COMMISSION
SYNTHETIC RESINS
AND THEIR RAW MATERIALS
A SURVEY OF THE TYPES AND USES OF SYNTHETIC
RESINS, THE ORGANIZATION OF THE INDUSTRY,
AND THE TRADE IN RESINS AND RAW
MATERIALS, WITH PARTICULAR
REFERENCE TO FACTORS
ESSENTIAL TO TARIFF
CONSIDERATION
UNDER THE GENERAL PROVISIONS OF SECTION 332, TITLE III,
PART II, TARIFF ACT OF 1930
REPORT No. 131
SECOND SERIES
[Illustration]
UNITED STATES
GOVERNMENT PRINTING OFFICE
WASHINGTON: 1938
For sale by the Superintendent of Documents, Washington, D. C.
Price 25 cents
UNITED STATES TARIFF COMMISSION
_RAYMOND B. STEVENS, Chairman_
_HENRY F. GRADY, Vice Chairman_
_EDGAR B. BROSSARD_
_OSCAR B. RYDER_
_E. DANA DURAND_
_A. MANUEL FOX_
_SIDNEY MORGAN, Secretary_
Address All Communications
UNITED STATES TARIFF COMMISSION
WASHINGTON, D. C.
TABLE OF CONTENTS
Page
Acknowledgment XI
1. Introduction 1
Scope and purpose 2
Fundamental definitions 2
Tariff history 3
Broadening use of synthetic resins 4
Relation of synthetic resins to their raw materials 5
Sources of information 7
2. Summary:
Growth of the industry 7
Raw materials 8
Resins 9
The industry abroad 10
International trade 10
3. Tar-acid resins 11
The three stages of a tar-acid resin 13
Classification of tar-acid resins 13
Processes of resin manufacture 14
Production in the United States 15
Imports into the United States 16
Exports from the United States 17
Tar-acid resins for molding:
Molding powders and pellets 18
The molding of tar-acid resins 19
Production of tar-acid molding resins 19
Cast phenolic resins:
Process of manufacture 20
Uses 20
Patents and licensing 21
Production of cast phenolic resins 21
Imports and exports 21
Tar-acid resins for laminating 21
Uses of tar-acid resin laminated products 22
Production of tar-acid resins for laminating 23
Imports into the United States 24
Exports from the United States 24
Tar-acid resins for surface coatings:
Types of resin used and the resultant coatings 24
Production in the United States 25
Imports into and exports from the United States 25
Tar-acid resins in adhesives 25
Tar-acid resins for other uses 26
4. Alkyd resins:
Description and uses 26
Development and patents 27
Classification of alkyd resins:
Unmodified drying alkyd resins 28
Drying alkyd resins, modified with natural materials 29
Drying alkyd resins, modified with other synthetic resins 29
Drying alkyd resins, modified with other synthetic resins
and oil extended 29
Semidrying alkyd resins 29
Nondrying alkyd resins 30
Miscellaneous modified alkyd resins 30
Alkyd resins in water dispersion 30
Alkyd resins in molding compositions and other uses 30
Pigments and solvents in alkyd resins 31
Production in the United States 31
Imports into and exports from the United States 32
5. Urea resins:
Description and uses 32
Production in the United States 34
United States imports and exports 35
6. Acrylate resins:
Properties and uses 35
Production in the United States 37
Imports into and exports from the United States 38
7. Coumarone and indene resins:
Description and uses 38
Production in the United States 39
Imports into and exports from the United States 39
8. Petroleum resins:
Properties and uses 39
Production 41
Imports and exports 41
9. Polystyrene resins:
Properties and uses 41
Production in the United States 42
Imports into and exports from the United States 42
10. Vinyl resins 43
Description and uses:
Polyvinyl acetate resins 44
Copolymers of vinyl acetate and vinyl chloride 46
Polyvinyl chloride resins 47
Polyvinyl chloroacetate resins 47
Divinyl acetylene and synthetic rubber 47
Production in the United States 48
Imports into the United States 48
Exports from the United States 50
11. Other synthetic resins:
Adipic acid resins 50
Aniline resins 50
Citric acid resins 50
Diphenyl resins 51
Furfural resins 51
Resins from sugar 51
Sulphonamide resins 51
12. The organization of the synthetic resin industry:
Horizontal relationships between resin producers 52
Vertical relationships between resin producers:
Tar-acid resins for molding 53
Tar-acid resins for laminating 54
Cast phenolic resins 54
Tar-acid resins for coatings 55
Tar-acid resins for miscellaneous uses 55
Alkyd resins made from phthalic anhydride 55
Alkyd resins made from maleic anhydride 55
Urea resins for molding 56
Urea resins for other uses 56
Coumarone and indene resins 56
Other resins 56
Relationship of the resin industry to other industries:
The chemical industry 56
The surface-coating industry 57
The electric industry 57
The auto industry 57
13. The United States tariff and international trade in synthetic
resins 58
Rapid expansion in home markets 59
The effect of patents on international trade 59
The United States tariff on resins and resin products:
Synthetic resins 60
Articles made of synthetic resin 61
14. Synthetic resin prices, properties, and uses:
Synthetic resins as substitutes 62
Motives for substitution 63
Materials displaced by synthetic resins 63
Competition between synthetic resins 63
Resins classified by cost 64
The physical properties of a resin and its uses 65
15. Synthetic resins in other countries:
Germany:
Production 75
Tar-acid resins 75
Alkyd resins 76
Urea resins 76
Polystyrene and vinyl resins 76
Uses of synthetic resins 76
Organization 77
Foreign trade 77
Great Britain:
Production 78
Tar-acid resins 79
Urea resins 79
Acrylate resins 79
Aniline resin 79
Organization 79
Foreign trade 80
France:
Producers 80
Foreign trade 81
Czechoslovakia 82
Italy 82
Japan 83
Production 83
Canada 84
Union of Soviet Socialist Republics 85
Netherlands 85
Denmark 86
Poland 86
16. Raw materials for alkyd resins 86
Naphthalene:
Recovery of naphthalene 87
Description and uses 87
United States production 88
Organization of the industry 89
Trend of production 89
World production 90
Germany 91
Great Britain 92
Belgium 93
Czechoslovakia 93
France 94
Poland 94
Netherlands 94
Canada 94
Union of Soviet Socialist Republics 94
Japan 94
United States imports:
Rates of duty 95
Import statistics 96
United States exports 98
Competitive conditions 98
Phthalic anhydride:
Description and uses 98
United States production 100
Production in other countries 101
United States foreign trade 101
Competitive conditions 101
Polybasic acids other than phthalic anhydride:
Maleic acid and anhydride 102
Malic acid and malomalic acid 102
Adipic acid 102
Succinic acid and anhydride 102
Fumaric acid 102
Glycerin:
Description and uses 103
United States production 103
Production in other countries 104
International trade 104
United States imports 105
United States exports 107
Competitive conditions 108
17. Raw materials for tar-acid resins:
The tar acids 109
Phenol:
Description and uses 110
United States production 111
Grades produced for resins 112
Producers 112
World production 113
United States imports:
Rates of duty 114
Import statistics 114
United States exports 116
Competitive conditions 116
The cresols, xylenols, and cresylic acid:
Description and uses:
The cresols 117
Metacresol 118
Orthocresol 118
Paracresol 118
Metaparacresol 118
Cresol 118
The xylenols 118
Other high-boiling tar acids 119
Cresylic acid 119
United States production:
The cresols 120
The xylenols 120
Other high-boiling tar acids 120
Cresylic acid 120
Foreign production 122
United States imports:
Rates of duty 124
Import statistics 125
United States exports 131
Competitive conditions 131
Synthetic tar acids other than phenol 132
Para tertiary amyl phenol 133
Para tertiary butyl phenol 133
Phenyl phenols 133
Resorcinol 133
Formaldehyde:
Description and uses 133
United States production 134
Production in other countries 134
United States imports and exports 134
Competitive conditions 135
Hexamethylenetetramine:
Description and uses 136
United States production 136
Production in other countries 136
United States imports and exports 136
Competitive conditions 137
Furfural 137
18. Raw materials for urea resins:
Urea 138
Thiourea 139
19. Raw materials for vinyl resins:
Description and uses 140
United States production 140
United States imports 141
Competitive conditions 141
APPENDIXES
Appendix A. Statistical tables on foreign trade in raw material
for synthetic resins 144
Appendix B. Trade names for synthetic resins made in the United
States 153
Appendix C. Trade names for synthetic resins made in Great Britain 155
Appendix D. Trade names for synthetic resins made in Germany 156
Appendix E. List of United States manufacturers of raw materials
for synthetic resins 158
Appendix F. Glossary 160
TABLES
No.
1. Synthetic resins: United States production and sales, 1921-37 8
2. Tar-acid resins: United States production and sales, by type
of raw material, 1933-37 14
3. Tar-acid resins: United States production and sales, 1927-37 15
4. Synthetic resins of coal-tar origin: United States imports for
consumption, 1919-37 16
5. Synthetic resins of coal-tar origin: United States imports for
consumption, by principal sources, in specified years 1929-37 17
6. Cast phenolic resins: United States production and sales,
1934-37 21
7. Alkyd resins from phthalic and maleic anhydride: United States
production and sales, 1933-37 31
8. Urea resins: United States production and sales, 1933-37 35
9. Resoglas and Trolitul: United States imports for consumption,
1933-37 43
10. Synthetic resins classified under paragraph 11: United States
imports for consumption, 1931-37 49
11. Vinyl acetate resins: United States imports for consumption,
1934-37 49
12. Mowilith resins: United States imports for consumption, 1932-37 49
13. Synthetic resins: United States production and imports, 1934-37 58
14. Comparison of the international trade of the United States in
synthetic resins and in certain raw materials for resins,
1934-37 58
15. Tariff classification and rates of duty in Tariff act of 1930
upon certain articles made of synthetic resin 61
16. Manufactured articles n. s. p. f. in which synthetic resin
is the chief binding agent: United States imports for
consumption, 1931-37 62
17. Synthetic resins and other plastics: Properties that affect
appearance 66
18. Synthetic resins and other plastics: Molding properties 68
19. Synthetic resins and other plastics: Strength properties 70
20. Synthetic resins and other plastics: Heat properties 71
21. Synthetic resins and other plastics: Electrical properties 72
22. Synthetic resins and other plastics: Specific gravity,
specific volume, and resistance to other substances 73
23. Synthetic resins: German exports, 1930-37 77
24. Synthetic resins: German exports, by countries, 1934-37 78
25. Synthetic resins: Production in Great Britain, 1934 and 35 78
26. Synthetic resins: Imports into the United Kingdom, 1930-36 80
27. Synthetic resins: Exports from the United Kingdom, 1930-36 80
28. Synthetic resins: French imports, by types, and countries,
1931 and 1933-37 81
29. Synthetic resins: French exports, 1931 and 1933-37 82
30. Manufactures of tar-acid resins: Production in Japan, 1929-35 84
31. Prices of gums and resins in the Netherlands, 1936 86
32. Synthetic resins: Netherland imports by countries 1931
and 1933-37 86
33. Crude naphthalene: United States production, 1918-37 88
34. Refined naphthalene: United States production and sales, 1917-37 89
35. Naphthalene (all grades): World production, by countries,
1933 and 1935 90
36. Naphthalene: German production, imports, exports, and apparent
consumption, 1928-37 92
37. Naphthalene: Production in Great Britain, in specified years 92
38. Naphthalene: Exports from the United Kingdom, 1928-36 93
39. Naphthalene: Belgian production, 1928-35 93
40. Naphthalene: Czechoslovak production, 1928-35 93
41. Crude naphthalene: Polish production, 1928-36 94
42. Naphthalene: Rates of duty upon imports into the United
States, 1916-38 95
43. Crude naphthalene (solidifying at less than 79° C.): United
States imports for consumption, 1919-37 96
44. Refined naphthalene (solidifying at or above 79° C.): United
States imports for consumption, 1919-37 96
45. Crude naphthalene (solidifying under 79° C.): United States
imports for consumption from principal sources, in specified
years 97
46. Crude naphthalene: United States production, imports, and
apparent consumption, in specified years 98
47. Phthalic anhydride: United States production and sales, 1917-37 100
48. Glycerin: United States production, 1919-37 103
49. Glycerin: United States production for sale, 1919-35 104
50. Glycerin: Imports and exports of principal countries, 1931
and 1933-37 105
51. Glycerin: United States imports for consumption, 1919-20
and 1923-37 106
52. Crude glycerin: United States imports for consumption from
Cuba, 1919-37 107
53. Crude glycerin: United States imports for consumption from
Philippine Islands, 1925-37 107
54. Glycerin: United States exports, 1919-37 108
55. Refined glycerin: United States production, imports, exports,
and apparent consumption, in specified years 108
56. Tar acids: Commercial and chemical names, boiling points, and
average percent in coal tar 109
57. Tar acids available in coal tar produced and distilled in 1936 110
58. Phenol: Estimated consumption by industries, 1936-37 111
59. Phenol: United States production and sales, in specified
years, 1918-37 112
60. Phenol: Estimated annual production, by countries, 1933-35 113
61. Phenol: Rates of duty upon imports into the United States,
1916-37 114
62. Phenol: United States imports for consumption, 1910-37 115
63. All distillates of tar yielding below 190° C., an amount of
tar acids equal to or more than 5 percent: United States
imports for consumption, 1918-37 115
64. Phenol: United States exports, 1918-24 116
65. Phenol: United States exports, 1934-36 116
66. Phenol: United States production, imports, exports, and
apparent consumption, in specified years, 1918-37 117
67. Meta, ortho, and para cresols: United States production and
sales, 1934 120
68. Refined cresylic acid: United States production and sales,
1929-37 121
69. Cresol: German production, in specified years 122
70. Cresol: German imports and exports in specified years 122
71. Cresol: Production in Czechoslovakia in specified years 123
72. Cresylic acid: British exports, by countries, 1933-37 123
73. The cresols: Rates of duty upon United States imports, 1916-37 124
74. Cresylic acid: Rates of duty upon United States imports,
1916-37 125
75. Metacresol, orthocresol, and paracresol, 90 percent or
more pure: United States imports for consumption, 1920
and 1923-37 125
76. Metacresol: United States imports for consumption by principal
sources, in specified years 126
77. Orthocresol: United States imports for consumption by principal
sources, in specified years 127
78. Paracresol: United States imports for consumption by principal
sources, in specified years 128
79. Crude cresylic acid: United States imports for consumption,
1924-37 129
80. Refined cresylic acid: United States imports for consumption,
in specified years, 1919-37 129
81. Crude cresylic acid: United States imports for consumption by
principal sources, in specified years, 1929-37 130
82. Refined cresylic acid: United States imports for consumption
by principal countries, in specified years 130
83. The cresols: Comparison of production and imports, 1934 132
84. Formaldehyde: United States production and sales, in specified
years 134
85. Formaldehyde: United States exports to principal markets, in
specified years 135
86. Hexamethylenetetramine: United States production and sales,
1923 and 1925-37 136
87. Hexamethylenetetramine: United States imports for consumption,
1923-37 137
88. Urea: United States imports for consumption, 1919-20 and
1923-37 138
89. Urea: United States imports for consumption, by countries,
1931 and 1933-37 139
90. Thiourea: United States imports through the New York customs
district, 1931-37 140
91. Vinyl acetate, unpolymerized: United States imports for
consumption, 1931-37 141
92. Naphthalene: German imports and exports, by countries, 1929
and 1932-37 144
93. Crude naphthalene: Belgian imports and exports, 1932-37 146
94. Refined naphthalene: Belgian imports and exports, 1932-37 147
95. Crude and refined naphthalene: Netherland imports and exports,
by countries, 1929 and 1932-37 148
96. Refined naphthalene: Canadian imports, by countries, 1928-29
and 1932-37 150
97. Naphthalene: Japanese imports by countries, 1928-29 and 1932-36 150
98. Crude glycerin: United States imports for consumption, by
countries, 1929 and 1931-37 151
99. Refined glycerin: United States imports for consumption,
by countries, 1929 and 1931-37 152
ILLUSTRATIONS
Chart. Derivation of certain synthetic resins 6
Preform press making pellets for use in molding 18
Vacuum cleaner parts of tar-acid resin illustrating the intricate
molded shapes possible 19
Radio cabinet and telephone sets of molded tar-acid resin 19
Cast phenolic resins. Standard shapes and small articles fabricated
from them 20
Laminating sheet press 22
Gears made of laminated tar-acid resin 22
Cocktail lounge using tar-acid laminated decorative materials 23
Thermostat case of molded urea resin 33
Scales case of molded urea resin 33
Airplane cockpit enclosures of cast acrylate resin 36
Spectacle lenses molded to optical prescription from acrylate resin 37
Molded polystyrene resins 42
ACKNOWLEDGMENT
In the preparation of this report, the Commission had the services of
Paul K. Lawrence, Prentice N. Dean, and others of the Commission’s
staff.
1. INTRODUCTION
This survey deals with the several commercially important types of
synthetic resins covered by paragraphs 2, 11, and 28 of the Tariff Act
of 1930 and with the raw materials necessary for their production. It is
made under the general investigatory powers of the Tariff Commission as
provided in section 332 of that act.
The field of synthetic resins is a comparatively new one, most of its
commercial development having occurred within the past 10 years. In 1937
the domestic output was more than 160 million pounds as compared with
slightly more than 10 million pounds in 1927.
The first important patents on synthetic resins were granted about 25
years ago. These patents covered phenolic resins probably intended for
use as substitutes for certain natural resins. It was soon found that
these synthetics offered possibilities of application vastly greater
than the natural materials. At first progress in their application was
slow as is usually the case with new products. During the World War the
shortage of phenol promoted interest in the use of the other tar acids
as raw materials for synthetic resins and intensive research developed
resins from the cresols and higher boiling tar acids. These resins
possessed properties sufficiently different from those made from phenol
to establish them permanently.
In the meantime research on other types of resins was carried on in the
United States and in Europe. The tar-acid resins for molding were the
only commercially important ones on the market until about 1929. About
that time, however, new commercial products began to appear rapidly. Cast
phenolic resins became available as material for novelties of unusual
brilliancy and beauty, the urea resins to meet the requirements for light
colored thermosetting resins in molded articles, and the alkyd resins for
use in new surface coatings which replaced conventional paint materials.
Later there followed a number of thermoplastic materials offering new and
unusual properties. Vinyl resins found application in molded products
and in safety glass. The acrylate resins became the nearest approach to
organic glass yet developed. The polystyrene resins, long in the research
stage, made their commercial appearance in 1937. Resins from petroleum,
from furfural, from adipic acid, and from aniline are on the market. Many
others are under investigation and some of them will undoubtedly become
important.
The versatility of synthetic resins is most unusual. In various uses they
have successfully displaced glass, wood, metal, hard rubber, bone, glue,
cellulose plastics, protein plastics, and conventional paint materials.
They compete with glass in shades and reflectors and offer properties
which will increase their use for this purpose. Cases for scales, radios,
and clocks, formerly of wood and metal, are now made of these synthetic
resins.
Scope and purpose.
This survey deals with the synthetic resins, the nature and trade in the
raw materials necessary for their production, the processes by which they
are made, trade in them in the United States and between nations, and
the nature of the competition which they meet. It does not go into the
details of manufacture of and trade in the multitude of articles made of
synthetic resins but stops at the point where these materials are turned
over to the resin fabricator. The synthetic resins are but one of four
broad groups of organic plastics. The others—natural resins, cellulose
ethers and esters, and protein plastics—are discussed herein only as they
relate to or compete with the synthetic resins.
The purpose of the survey is to bring together in one publication the
available information on synthetic resins so as to provide a basis
for consideration of future tariff problems. Because the industries
involved are comparatively young and are expanding rapidly, their present
day importance is not generally realized. The rapidity with which
the synthetic resin industry is developing causes any comprehensive
report on the subject to be practically out of date before it can be
published. Notwithstanding the progress made each year in the quantity of
production, new applications, and new commercial products, the industry
may be said to be still in the industrial nursery. This circumstance
necessarily limits the period during which any treatment of the subject
will be representative.
Fundamental definitions.
The scope of this report has been stated to include synthetic resins up
to the point where they are further manufactured, and the raw materials
used in producing them. It was also stated that natural resins and
synthetic plastics other than resins, such as the cellulose compounds
and modified rubber compounds, are excluded. The boundaries of these
categories are therefore important.[1]
The term “resin” was formerly applied exclusively to a group of natural
products, principally of vegetable origin, although at least one
important resin, shellac, is of animal origin.[2] These natural resins
are widely used in paints, varnishes, and lacquers for decorative and
protective surface coatings. They also have extensive use in textile
impregnation, adhesives, soap, paper, and in cold-molded articles. In
recent years the natural resins have had to compete with synthetic
products, and each gravitates toward uses which demand the quality or
combination of qualities which it can most completely supply.
A resin may be defined as a semisolid or solid, complex, amorphous
mixture of organic compounds with no definite melting point and no
tendency to crystallize. The resins are characterized by a typical luster
and a conchoidal fracture rather than by definite chemical composition.
The term includes natural resins, such as colophony (ordinary rosin),
copal, damar, lac, mastic, sandarac, shellac, etc., sometimes called gums
or gum resins although none of them are true gums.
A synthetic resin is a resin made by synthesis from nonresinous organic
compounds. The term includes materials ranging from viscous liquids to
hard, infusible, amorphous solids. As a rule synthetic resins possess
properties distinct from those of natural resins. The term “plastics,”
sometimes applied to synthetic resins, also includes many materials which
are not resins.
A plastic is anything possessing plasticity; that is, anything which
can be deformed under mechanical stress without losing its coherence
or its ability to keep its new form. According to this definition the
term includes such materials as putty, cement, clay, glass, and metals,
as well as certain modified natural or semisynthetic products, such
as cellulose acetate, cellulose nitrate, and casein more commonly so
designated. To speak of the plastics industries is almost meaningless
because of their enormous scope, including as they do those producing
cement, ceramics, confectionery and rubber, as well as those producing
the semisynthetic products mentioned.
The resin industry embraces two main types of materials, thermoplastic
and thermosetting. Thermoplastic materials are those which, although
rigid at normal temperatures, may be deformed and molded under heat
and pressure. Among such materials are the cellulose esters, acrylate
resins, vinyl resins, polystyrene resins, etc. The recent development of
injection molding has given thermoplastics a new significance.
Thermosetting substances are thermoplastic at some stage of their
existence, but become hard, rigid, and permanently infusible upon the
application of the proper heat and pressure. They are then irreversible
whereas the thermoplastics are reversible. Outstanding among the
thermosetting resins are tar-acid resins, urea resins, and the alkyd
resins.
Tariff history.
The earliest mention of synthetic resins in the tariff laws of the
United States was the provision in group III of the Emergency Tariff Act
of 1916 for a duty of 30 percent ad valorem and 5 cents per pound on
synthetic phenolic resins. None of the non-coal-tar synthetic resins were
specifically mentioned prior to the Tariff Act of 1930.
The Tariff Act of 1922 (par. 28) provided for synthetic phenolic resin
and all resinlike products, solid, semisolid or liquid, prepared from
phenol, cresol, phthalic anhydride, coumarone, indene, or from any other
article or material provided for in paragraph 27 or 1549. The rate of
duty was 60 percent ad valorem based on American selling price or United
States value and 7 cents per pound, with a provision that the ad valorem
rate should be reduced to 45 percent 2 years after the passage of the act.
The Tariff Commission made two investigations of synthetic resins under
section 316 of the act of 1922. The first was undertaken April 16, 1926,
upon complaints of several domestic manufacturers, of unfair methods of
competition and unfair acts in the importation and sale of synthetic
phenolic resin, Form C, and articles made wholly or in part therefrom, in
infringement of the patent rights of the Bakelite Corporation. Following
the investigation, the Commission recommended on May 25, 1927, that
this material (as described under United States Patents No. 942,809 and
1,424,738) be excluded from entry into the United States. Importers
appealed from the findings of the Commission to the Court of Customs
Appeals, and the judicial proceedings were ended on October 13, 1930, by
denial of a writ of certiorari for the Supreme Court of the United States
to review the judgment of the Court of Customs and Patent Appeals. The
latter court had held, among other things, that there was substantial
evidence in support of each finding of the Commission. On November 26,
1930, the Treasury Department issued an order prohibiting the importation
of synthetic phenolic resin, Form C, with certain exceptions. (T. D.
44411.)
The second investigation by the Tariff Commission was instituted
on December 23, 1927, also under section 316 of the act of 1922.
It concerned unfair methods of competition and unfair acts in the
importation into the United States of laminated products of paper or
other materials and insoluble, infusible condensation products of phenols
and formaldehyde. The Commission recommended to the President that, until
March 4, 1929, inclusive, certain products covered by United States
Letters Patent Nos. 1,018,385, 1,019,406, and 1,037,719 be excluded from
entry into the United States. These products were laminated cloth, paper
or the like, combined with insoluble, infusible condensation products
of phenols and formaldehyde. The order of the President prohibiting the
importation was contained in T. D. 42801 issued June 11, 1928.
Under the Tariff Act of 1930, practically no changes were made in the
provisions of paragraph 28 that concern coal-tar synthetic resins.
Paragraph 2 was extended to include, among other things, the resins
(polymers) of certain organic compounds. The only commercial products
covered by this provision are the vinyl resins. The rate of duty was 30
percent ad valorem on foreign value and 6 cents per pound. Under the
trade agreement with Canada, the duty on vinyl acetate, polymerized or
unpolymerized, and on synthetic resins made in chief value therefrom was
reduced to 15 percent ad valorem and 3 cents per pound (effective Jan. 1,
1936).
The Tariff Act of 1930 contains a provision, in paragraph 11, for
synthetic gums and resins not specially provided for, 4 cents per pound
and 30 percent ad valorem on foreign value.
Broadening use of synthetic resins.
The application of synthetic resins has extended into practically every
branch of industry. This marked expansion is not surprising when the
adaptability of these products is considered. Their uses range from
jewelry and bottle closures to building materials; from adhesives and new
types of surface coatings to light reflectors and shades. They are being
substituted for natural materials, such as wood, metal, and glass at an
increasing rate. They have provided new uses for raw materials formerly
used in antiseptics, disinfectants, explosives, embalming fluids,
fertilizers, moth repellants, and as solvents. The speed of expansion
of their use in resin manufacture has been such as to create a serious
shortage of some of these raw materials.
New applications for synthetic resins appear almost daily. They are used
in furniture, wall panels, builders’ hardware, electrical fixtures, and
in thousands of small appliances. The automobile industry is probably
the largest single user. An interesting application here is in silent
gears and shaft bearings where the use of synthetic resins makes water
lubrication possible. Other automotive uses are in distributor heads,
horn buttons, gear shift knobs, dome light reflectors, control knobs and
the finishing lacquers. Additional uses contemplated for the near future
are in accelerator pedals and instrument panels. A new type of safety
glass in which vinyl resins are used was introduced in 1936.
In decorative uses remarkable progress has been made. Panels of laminated
resins are widely used in store fronts, lobbies of office buildings,
and hotels; doors faced with this material are in use. The liner _Queen
Mary_ is paneled, in part, with laminated resins, as is the annex to the
Library of Congress. Lamp shades of urea resin are used in many Pullman
cars and are available for home and office use.
Other things being equal, the cheaper a synthetic resin, the more widely
it may be applied as a substitute for other materials. As a result many
an apparently useless byproduct, such as oat hulls which yield furfural,
is either already used or being tested as a source of raw material. Other
materials which have already found a place or may do so, are soybean
meal, sugar, and certain petroleum distillates.
Each of the important groups of synthetic resins has been sponsored by
one or more manufacturers of established reputation and large capital
resources. When a product reaches the commercial stage, after heavy
research cost, its future importance is therefore usually assured.
Relation of synthetic resins to their raw materials.
Most of the commercially important synthetic resins are derived directly
or indirectly from coal. The chart (p. 6) shows the derivation of
certain synthetic resins from the principal raw materials used in their
manufacture and the intermediate products back to the original source of
the material.
The polystyrene resins, for example, are made by polymerizing styrene
or vinyl benzene. Although basically from ethylene and benzene, vinyl
benzene may be formed in several ways. Ethylene is found in the gases
from the destructive distillation of coal but is obtained commercially by
cracking natural gas or petroleum. Styrene, found already formed in the
light oil fractions from coal tar, causes gum-forming in motor benzol and
certain industrial gases.
When coke and lime are mixed and heated in an electric furnace to 2,000°
C., calcium carbide is formed. This compound with water yields acetylene,
the starting point for a long list of important products, including
several types of synthetic resins. When acetylene gas is passed through
acetic acid (itself obtained from acetylene) vinyl acetate is obtained.
If hydrochloric acid is used instead of acetic acid, vinyl chloride is
obtained. These compounds, when polymerized, yield the vinyl resins.
The acrylate resins may be obtained from the same basic raw material
by an entirely different procedure. Synthetic rubber is also derived
from acetylene, as are acetic anhydride and acetic acid (used in making
cellulose acetate plastics) and many other chemicals of commercial
importance.
[Illustration: Derivation of certain synthetic resins.]
When naphthalene (from coal tar) is treated with air at elevated
temperatures, phthalic anhydride is formed. Substituting benzene for
naphthalene yields maleic anhydride. Both of these substances when
condensed with glycerin, a byproduct of the soap industry, yield alkyd
resins.
The tar acids from coal tar, either separated or mixed, when condensed
with formaldehyde give the highly important tar-acid resins. Or if
formaldehyde is condensed with urea, obtained from carbon dioxide and
ammonia, the urea resins are formed.
The chart indicates the synthetic resins which are thermoplastic,
that is, which become plastic again upon reheating, and those which
are thermosetting, that is, pass into an infusible stage at a certain
critical temperature and pressure and do not again become plastic upon
subsequent reheating.
Sources of information.
The data used in this report were obtained from a great variety of
sources. The several American and British trade journals were freely
consulted as were the various text books on this subject. Much of the
information on the domestic industry was obtained by personal contact
with producers and by correspondence. Field work included visits to
most of the domestic producers of resins and a representative group
of fabricators. Information of this type which was nonconfidential or
which could be combined so as not to reveal individual operations was
invaluable. Even where it was such that it could not be published it
became part of the general background.
The data pertaining to the industry in foreign countries were, for the
most part, furnished the Tariff Commission by Department of Commerce
representatives stationed abroad, in response to inquiries by the
Commission.
2. SUMMARY
Growth of the industry.
The coal-tar synthetic resin industry in the United States began on a
small scale some years before the World War. The output then was confined
to a few types of tar-acid resins and the applications were quite limited
until 1927, when certain of the basic patents expired. The output of
about 1.5 million pounds in 1921 had increased to more than 13 million
pounds in 1927 and the average unit value of sales had dropped from
81 cents per pound to 47 cents. Production continued to increase and
the unit value to decrease annually until 1932 when general economic
conditions forced a slight curtailment for 1 year. Since then the annual
increase in volume and variety has been rapid. Production of non-coal-tar
synthetic resins was started on a small scale in 1929 when both urea and
vinyl resins entered the picture. Commercial production of the petroleum
resins began in 1936 and of the acrylate resins in 1937. Table 1 shows
the production and sales of coal-tar resins and of non-coal-tar resins,
from 1921 through 1937.
TABLE 1.—_Synthetic resins: United States production and sales, 1921-37_
---------------------+------------+--------------------------------------
| | Sales
Year | Production +------------+------------+------------
| | Quantity | Value | Unit value
---------------------+------------+------------+------------+------------
| _Pounds_ | _Pounds_ | |
Coal-tar resins:[1] | | | |
1921 | 1,643,796 | 1,674,456 | $1,352,166 | $0.81
1922 | 5,944,133 | 6,415,931 | 4,315,196 | .67
1923-26 | ([2]) | | |
1927 | 13,452,230 | 13,084,313 | 6,094,656 | .47
1928 | 20,411,465 | 20,778,856 | 7,211,958 | .35
1929 | 33,036,490 | 30,660,513 | 10,393,397 | .33
1930 | 30,867,752 | 24,014,093 | 7,323,656 | .30
1931 | 34,179,000 | 29,343,000 | 7,862,000 | .27
1932 | 29,039,000 | 23,891,000 | 5,001,000 | .21
1933 | 41,628,485 | 31,657,653 | 7,238,560 | .23
1934 | 56,059,489 | 43,350,876 | 10,126,849 | .23
1935 | 90,913,162 | 65,923,334 | 12,777,195 | .19
1936 |117,301,780 | 86,213,735 | 17,056,099 | .20
1937 |141,098,844 |108,284,175 | 20,165,064 | .19
| | | |
Non-coal-tar resins: | | | |
1932 | 1,898,000 | 1,787,000 | 796,000 | .45
1933 | 3,571,717 | 3,256,411 | 1,745,102 | .54
1934 | ([2]) | 3,500,829 | 1,491,145 | .43
1935 | ([2]) | ([2]) | ([2]) |
1936 | 15,611,041 | 14,766,640 | 3,591,467 | .24
1937 | 21,005,869 | 18,891,277 | 5,680,600 | .30
---------------------+------------+------------+------------+------------
[1] Does not include resins from adipic acid, coumarone and
indene, hydrocarbon, polystyrene, succinic acid and sulfonamides.
With the exception of coumarone and indene resins in recent years
production of the resins not included was small.
[2] Not publishable. Figures would reveal operations of
individual producers.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Many factors have contributed to the growth of the synthetic resin
industry. Among these are the intensive research and development work
carried on by many individuals and firms; their widespread application in
many fields competing with wood, metal, and glass; and the development
of processes for raw materials which have greatly reduced their cost and
made their wider use possible.
_Raw materials._—Although the chief raw materials consumed in the
synthetic resin industry are coal-tar derivatives and formaldehyde, many
others are utilized. The rapid expansion of the industry has created new
demands for materials in increasing quantities and has not only increased
the markets for well-known materials but has resulted in the production
on a huge scale of materials entirely new to commerce. Practically all
the raw materials now used can be derived from a few natural substances,
such as air, water, coal, petroleum crudes, salt, sulphur, and limestone.
The air yields nitrogen which may be converted to ammonia, a raw
material for urea, one of the components of the urea resins. Coal, as
is well known, yields a great variety of substances, many of which are
essential to synthetic resin manufacture. Benzene is the starting point
for synthetic phenol; naphthalene is used to make phthalic anhydride
and maleic anhydride; coke is converted to calcium carbide, which in
turn yields acetylene, acetic acid, and many other synthetics; carbon
monoxide which is converted to methanol and formaldehyde; and the natural
tar acids such as phenol, the cresols, and the xylenols. Limestone is a
component of calcium carbide, and salt yields needed alkalies and acids.
Water is broken down, and the hydrogen is converted to ammonia, methanol,
formaldehyde, and ethylene.
Some idea of the expansion in production of these raw materials whose
principal use is in synthetic resins may be had by comparing the output
in 1923 of tar acids, formaldehyde, phthalic anhydride, maleic anhydride,
urea, vinyl acetate, and vinyl chloride, which amounted to 35 million
pounds, with the output of 270 million pounds in 1936. The manufacture of
these materials is largely by coal-tar distilling companies and makers of
chemicals.
_Resins._—The coal-tar resins are the most important in quantity, value,
and variety of application. This class includes four groups: (_a_) tar
acid, (_b_) alkyd, (_c_) coumarone and indene, and (_d_) polystyrene. Of
these, resins from tar acids (phenol, cresols, and xylenols) are produced
in the largest quantity, the output having increased from about 15
million pounds in 1932 to about 80 million pounds in 1937. In the latter
year about 40 percent of the consumption of tar acid resins was in molded
articles, 25 percent in paint and varnishes, 20 percent in laminated
products, and 15 percent in miscellaneous uses.
The alkyd resins have shown a remarkable increase in output. Production
totaled slightly less than 10 million pounds in 1933; in 1937 it amounted
to about 61 million pounds. Practically all of the alkyds have been
consumed in paints and varnishes.
The coumarone and indene resins have increased steadily over a number of
years and are now one of the most important groups.
The polystyrene resins have been in an experimental stage for a long
time, with the volume of production small. In 1937, however, commercial
production of a water-white product was announced, and it is believed
that the output of these resins will increase sharply in the near future.
The non-coal-tar resins were of little importance prior to 1930 and
production amounted to less than 2 million pounds in 1932. Since then,
however, progress has been rapid, both in types and output. Resins from
urea constitute an important part of this class and the output has
increased practically every year since 1929 when production was started.
Most of the output is used in molded articles where light and pastel
shades are required. In 1936, for the first time, appreciable quantities
were consumed in laminating and in surface coatings.
The vinyl resins have been produced in increasing quantities for the past
8 years. Production reached a new high in 1937, and with the acceptance
of this type of resin for safety glass laminations it is expected that
the output will increase materially in the near future. In 1937 the
application in surface coatings, molded articles, and laminations were of
approximately equal importance.
The acrylate resins are among the newest commercial developments in this
industry. Of the several types now manufactured, one appears valuable in
surface coatings and adhesives and another, in the form of its cast or
molded polymer, in airplane windows, machined articles, and lenses.
Petroleum resins were first produced in commercial quantities in 1936,
but the output in that year was appreciable. These low-priced synthetics
are used in surface coatings, laminations, and miscellaneous uses.
The industry abroad.
World production of synthetic resins at this time is estimated at 300
million pounds annually, of which the United States accounts for 45
percent. Germany produces about 27 percent and Great Britain about 20
percent of the total and a number of countries including France, Italy,
Czechoslovakia, Canada, and Japan produce the remainder. Practically all
types are made in Germany and Great Britain although in lesser quantities
than here. The urea resins originated abroad, as did the acrylates and
polystyrenes.
Commercial development of the synthetic resins abroad has been somewhat
behind that in the United States, although in recent years the increase
there has been so rapid as to seriously affect the international raw
material market. Germany, formerly one of our principal sources of crude
naphthalene, for a time restricted exports of that commodity in order
to conserve the available supply for home consumption, presumably in
alkyd resins. Great Britain, formerly the principal exporter of phenol,
has found it necessary to supplement production of natural phenol with
synthetic phenol. It is possible that in the future similar conditions
may arise in world markets for cresylic acid.
International trade.
International trade in the synthetic resins has been small. Germany has
been the principal exporting country. There are a number of reasons
for the negligible movement of these materials in international trade,
the chief of which are active home markets in the principal producing
countries; the existence of patents of a basic nature which limited
trade to the owners and licencees under them; affiliation of producing
companies in different countries with allocation of the world market; and
high tariff barriers in many countries.
The principal domestic producer of tar-acid resins is affiliated with
firms in Germany, the United Kingdom, France, Italy, Canada, and Japan.
The two principal American makers of urea resins have or have had
agreements as to patents, exchange of technical information, and probably
markets, with producers in Great Britain. Similar conditions exist with
other types of resins.
In 1937 production of all synthetic resins in the United States amounted
to 162 million pounds and imports to less than 674,000 pounds (see table
13, p. 58). Production of tar-acid resins in that year amounted to 79.8
million pounds; alkyd resins to 61.2 million pounds and all coal-tar
resins to 141 million pounds. Imports of all coal-tar synthetic resins
(which would include both tar acid and alkyd as well as others) amounted
to only 19,000 pounds. Coal-tar resins are dutiable at 7 cents per pound
and 45 percent ad valorem based on American selling price. On the small
imports in 1937 the duty collected averaged 54 percent ad valorem on
American selling price and would have averaged much higher had it been
calculated upon foreign value as are most duties.
In 1937 the production of non-coal-tar resins totaled about 21 million
pounds. In that year imports of non-coal-tar resins totaled 65,000
pounds. Imports of non-coal-tar resins, other than vinyl resins, amounted
to less than 2,000 pounds. These were dutiable at 4 cents per pound and
30 percent ad valorem on foreign value, equivalent on the average to 48
percent ad valorem. The vinyl resins have been imported into the United
States in increasing quantities in recent years. The principal foreign
producer, in Canada, developed markets in the United States, but is a
joint owner of a plant now under construction in this country. Imports of
vinyl resins in 1937 were 653,000 pounds. These were dutiable at 3 cents
per pound and 15 percent ad valorem on foreign value, equivalent to 25
percent ad valorem.
It is apparent that foreign competition with United States producers
in the home market has been and is likely to continue insignificant
under existing duties. With a large home market and generally favorable
conditions with respect to the necessary raw materials and the technical
skills, this situation would probably continue even under lower duties.
Moreover, as international trade develops in these materials, this
country is more likely to be a net exporter than a net importer.
3. TAR-ACID RESINS
The tar-acid resins were the first true synthetic resins to appear in
commerce, but they were preceded by two plastics, celluloid and casein.
Probably the first successful attempt to make a semisynthetic or modified
natural product as a substitute for natural materials was the discovery
of celluloid in 1868 by John Wesley Hyatt. By treating cotton with nitric
acid he obtained a material which could be substituted for ivory in
billiard balls. The Celluloid Corporation grew out of this discovery and
the product was widely used to replace amber, ivory, mother-of-pearl,
tortoise shell and other materials.
The discovery of casein plastic took place in 1890. Adolph Spitteler of
Hamburg, Germany, in trying to make a white blackboard, found that casein
(from milk) could be hardened by treating it with formaldehyde. Casein
plastics are now widely used in buttons, buckles, and other ornaments.
As early as 1872 the reactions between coal-tar acids and aldehydes were
being studied, and by 1900 many research workers were investigating
phenol-formaldehyde condensation products. During the period 1900-1910,
the study of these products increased greatly, both with regard to
process of production and to applications, such as its substitution for
shellac and other natural resins. United States Patents Nos. 942,699 and
942,809 issued December 7, 1909, to Dr. L. H. Baekeland and commonly
known as the heat and pressure patents were probably the basic patents on
phenol-formaldehyde resins. Baekeland so modified these resins by methods
of hardening under heat and pressure that rigid molded articles could be
made. The range of uses of tar-acid-formaldehyde molding compositions
has steadily widened. Molded articles such as pencil and pen barrels,
ash trays, bottle closures, parts for automobiles, cameras, precision
instruments, dynamos, motors, and other electrical equipment, cafeteria
trays, table and counter tops are well known to the public.
During the life of these and other basic patents issued about 1909 the
domestic production of phenol-formaldehyde molding compositions was
practically restricted to one company. Since the expiration of these
patents in 1926 a number of other producers have been established. In
1937 there were 36 domestic makers of tar-acid-formaldehyde resins for
molding, laminating, and surface coating applications.
The early work done on phenol-formaldehyde resins gave dark-colored
products which were too hard and brittle to be machined or worked on
a lathe. Investigations by F. Pollak and A. Ostersetzer, in Vienna,
resulted in a process for the manufacture of cast phenolic resin with
a range of color possibilities from water-white transparency through
all shades and degrees of translucency and opaqueness. This product is
cast into sheets, rods, tubes, and special castings, all of which may
be turned or milled on automatic machines. United States Patent No.
1,854,600, issued April 19, 1932, to F. Pollak and A. Ostersetzer and
assigned to Pollopas, Ltd., London, is considered the basic patent for
cast phenolic resins. American rights under this and related patents
are owned by the Catalin Corporation of America who have licensed other
domestic makers. The German equivalent of rights under this patent is
owned by a subsidiary of I. G. Farbenindustrie Aktiengesellschaft and
rights under the French equivalent by Établissements Kuhlmann.
In the early days of the phenol-formaldehyde resin industry (1909-16)
there was considerable uneasiness about the supply of phenol. World
production was not large and Germany and England controlled most of
it. The output of the United States was almost entirely for medicinal
use, although our potential production was large (see p. 111). This
situation caused many research workers to study the resins made from
other tar acids, principally meta and para cresols and the xylenols. The
investigations resulted in many new types of resins and in modifications
of the phenol-formaldehyde type. The World War changed conditions
materially. Imports of phenol were shut off and prices soared. Production
of synthetic phenol was begun, and, although the wartime production
went into explosives, its development had an important bearing on the
synthetic resin industry. Unusual demand for phenol, toluene, and other
coal-tar crudes resulted in a great expansion of production. With the
cessation of hostilities there was an ample supply of cheap phenol and
the expansion of the coal-tar industry continued so that the supply of
tar acids kept pace with the new demand for use in the production of
synthetic resin.
In 1926, the early patents on resins from tar acids began to expire
and the second era of the industry began. Since that year most of
the research work has been for materials that would give different
properties to the resultant resins. The past 10 years have seen a
greater diversification in the manufacture of resins from tar acids and
substantial reductions in their prices. Tar-acid resins averaged $1.29
per pound in 1920, 23 cents per pound in 1934, and 19 cents per pound in
1937. The production of certain resins of this class which are soluble in
drying oils has been an important achievement. They yield varnishes of
improved type that are quick-drying.
The three stages of a tar-acid resin.
About 28 years ago the Journal of Industrial and Engineering Chemistry
published the original paper of Dr. Leo H. Baekeland on the Synthesis,
Constitution, and Uses of Bakelite. According to Baekeland’s theory, the
reaction between phenol and formaldehyde consists of condensation and
polymerization taking place in three stages. The first product formed,
called “initial condensation product A” is usually a liquid or semisolid
which on continued heating is converted to “intermediate condensation
product B.” B is an insoluble solid which can be softened by heat, and is
the material used by molders, laminators, and other fabricators.
The final stage, known as “final condensation product C,” is probably
the result of polymerization of B, by heat and pressure. C product is
infusible, indifferent to all solvents, and cannot be distilled or
melted; hence the tar-acid resins belong to the thermosetting group.
The conversion to C takes place in the presses of the molder or final
fabricator of the resin. This theory is generally accepted and the
designations of the several stages are in universal use in the trade.
Classification of tar-acid resins.
All the synthetic resins obtained by the condensation of a tar acid, or
a mixture of tar acids, with an aldehyde are popularly called phenolic
resins, regardless of whether they are made from phenol, the isomeric
cresols, xylenols, other high boiling tar acids, or any mixture of these
materials. A more accurate designation and that used in this survey is
tar-acid resins, reserving the term phenolic resins for those made from
pure phenol.
The tar-acid resins might be classified in a number of ways; for example,
by composition, physical form, or general application. Each of these has
its shortcomings. To classify them by composition, that is, by the kind
of tar acid used, is not satisfactory because of the vast number of types
made from mixed tar acids. For the purpose of this discussion it seems
best to classify the tar-acid resins by their general application into
six groups: for molding, for casting, for laminating, for surface coating
(paints, varnishes, and lacquers), for adhesives, and for miscellaneous
uses.
In 1937 approximately 66 percent of the United States production of
tar-acid resins was made from phenol; 18 percent from phenol-cresol
mixtures; 13 percent from cresol-cresylic acid mixtures; and 3 percent
from cresol-xylenol mixtures. Table 2 shows for recent years production
and sales of tar-acid resins by type of raw material. Pure phenol is used
for cast resins. Molding resins are usually made from pure phenol or from
tar-acid mixtures, chiefly phenol. Laminating and coating resins are
usually made from mixtures containing substantial amounts of the cresols
and xylenols (frequently spoken of by the trade as cresylic acid).
TABLE 2.—_Tar-acid resins: United States production and sales, by type of
raw material, 1933-37_
----+--------------------------------+---------------------------------
| Phenol | Tar-acid mixtures[1]
+----------+----------+----------+----------+----------------------
| | Sales | | Sales
Year|Production+----------+----------+Production+----------+-----------
|(net resin| Quantity | |(net resin| Quantity |
| content) |(net resin| Value | content) |(net resin| Value
| | content) | | | content) |
----+----------+----------+----------+----------+----------+-----------
| _1,000 | _1,000 | _1,000 | _1,000 | _1,000 | _1,000
| pounds_ | pounds_ | dollars_ | pounds_ | pounds_ | dollars_
| | | | | |
1933| 25,163 | 21,851 | 5,383 | 6,535 | 6,152 | 1,182
1934| 29,777 | 27,995 | 7,332 | 10,887 | 8,091 | 1,705
1935| 36,323 | 34,597 | 6,568 | 16,654 | 12,371 | 2,200
1936| 51,603 | 49,053 | 9,419 | 18,747 | 12,908 | 2,325
1937| 52,472 | 50,209 | 8,616 | 27,373 | 23,337 | 4,685
+----------+----------+----------+----------+----------+-----------
| Phenol-cresol | Cresol-cresylic | Cresol-xylenol
| mixtures | acid mixtures | mixtures
+----------+----------+----------+----------+----------+-----------
| | | | | |
|Production|Sales (net|Production|Sales (net|Production|Sales (net
|(net resin| resin |(net resin| resin |(net resin| resin
| content) | content) | content) | content) | content) | content)
+----------+----------+----------+----------+----------+-----------
| _1,000 | _1,000 | _1,000 | _1,000 | _1,000 | _1,000
| pounds_ | pounds_ | pounds_ | pounds_ | pounds_ | pounds_
1937| 14,046 | 13,238 | 10,702 | 8,467 | 2,625 | 1,632
----+----------+----------+----------+----------+----------+-----------
[1] Includes phenol-cresol mixtures, cresol-cresylic acid
mixtures, and cresol-xylenol mixtures. For 1937, where it is
possible, the totals of tar-acid mixtures are broken down into
these three groups.
Source: Dyes and Other Synthetic Organic Chemicals in the United
States, U. S. Tariff Commission.
Processes of resin manufacture.
The processes of and patents for the manufacture of tar-acid-formaldehyde
resins are numerous. No attempt is made here to describe in detail the
several processes of manufacture or the endless number of variations and
modifications. In general the processes in operation may be designated
(_a_) one stage wet, (_b_) two stage wet, and (_c_) dry.
The one-stage wet process consists in heating molecular proportions of
tar acid and formaldehyde (40-percent solution) in the presence of an
acid or alkaline catalyst. The formaldehyde is added all at once and the
reaction proceeds with the elimination of water. The difficulty with
this process is that of obtaining uniform batches because it cannot be
controlled exactly.
The two-stage process is probably the one most widely used today and
consists in introducing formaldehyde in two or more stages as the
reaction progresses. Much better process control and more uniform results
are so obtained. A soluble, fusible resin is formed from which the water
is easily removed. Fillers and pigments may be added during the latter
part of the operation.
The dry process is the least important and is used only where cast resins
are being made. Light-colored, transparent resins are obtained and the
operation is carried on to the final stage (C resin). In this process the
aldehyde used is solid paraformaldehyde or hexamethylenetetramine. These
materials are more costly than formaldehyde solution.
Proportions of raw materials used vary widely—Baekeland suggested 7
mols of formaldehyde and 6 mols of phenol (210 parts of 100-percent
formaldehyde to 564 parts of phenol), with a yield of resin equivalent
to 118 percent of the phenol. Larger proportions of formaldehyde are said
to increase the yield to as much as 140 percent of the phenol.
Catalysts used to aid in the condensation of the reacting bodies may be
acids or bases. Certain properties of the resins may be varied by the
kind and quantity of catalyst used. Large proportions of basic or acidic
catalysts may affect the filler or metal inserts. Basic catalysts used
include caustic soda, caustic potash, ammonia, carbonates, and alkali
sulphites. Acid catalysts are usually one of the mineral acids such as
hydrochloric acid or sulphuric acid.
While formaldehyde in the form of a 40-percent solution is the principal
aldehyde used with the tar acids, certain other aldehydes are used in
small amounts. Among these are acetaldehyde, butyraldehyde, benzaldehyde,
and others. Resins from furfural and phenol are discussed as “Furfural
Resins,” page 51.
Production in the United States.
The production of tar-acid resins in the United States has increased
markedly in the last 10 years. Table 3 shows the production and sales
of all coal-tar resins in 1927 and 1928 (when there was no further
break-down available but when this classification was made up chiefly of
tar-acid resins) and of tar-acid resins from 1929 to 1937. The figures
given are in net resin content and do not include fillers, modifiers, or
pigments. From 1929 to 1937 production increased from 26 million pounds
to 80 million pounds; sales from 25 million pounds valued at 9.9 million
dollars to 74 million pounds valued at 13.3 million dollars; the value
per pound dropped from 39 cents to 19 cents.
In 1937 the production of tar-acid resins for molding accounted for about
40 percent of the total; those for surface coatings, about 25 percent;
those for lamination, about 20 percent; and those for miscellaneous uses,
about 15 percent.
TABLE 3. _Tar-acid resins: United States production and sales 1927-37_
--------+-------------+----------------------------------------
| | Sales
| Production +------------+--------------+------------
Year | (net resin | Quantity | |
| content) | (net resin | Value | Unit value
| | content) | |
--------+-------------+------------+--------------+------------
| _Pounds_ | _Pounds_ | |
1927[1] | 13,452,230 | 13,084,313 | $6,094,656 | $0.47
1928[1] | 20,411,465 | 20,778,856 | 7,211,958 | .35
1929[2] | 26,235,792 | 25,129,701 | 9,869,274 | .39
1930[2] | 18,338,389 | 17,428,687 | 6,576,023 | .38
1931[2] | 22,647,000 | 21,496,000 | 6,646,000 | .31
1932[2] | 17,163,000 | 15,042,000 | 3,946,000 | .26
1933[2] | 31,697,780 | 28,002,799 | 6,564,670 | .23
1934[2] | 40,663,565 | 36,086,008 | 9,037,861 | .25
1935[2] | 52,731,728 | 46,733,378 | 8,730,438 | .19
1936[2] | 70,349,328 | 61,961,200 | 11,743,978 | .19
1937[2] | 79,844,825 | 73,545,880 | 13,300,870 | .19
--------+-------------+------------+--------------+----------
[1] All coal-tar resins.
[2] Resins from tar acids only.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Imports into the United States.
Imports of tar-acid resins into the United States are dutiable under
paragraph 28 at 7 cents per pound and 45 percent ad valorem based upon
American selling price. Discussion of this rate, other restrictions upon
imports in the earlier years, and of the rates upon articles made of
these resins will be found on pages 59 to 61.
Imports of tar-acid resins are not shown separately in official
statistics; the classification under which such imports are entered
includes all synthetic resins of coal-tar origin. Table 4 shows the
quantity and value of imports of all coal-tar resins since 1918, and
table 5 shows the principal sources of imports for certain years.
Invoice analyses of imports in the last 3 years show only very small
quantities of phenolic resins being imported. In 1934 there was an
importation of 950 pounds of Bakelite molding compound; in 1935 imports
of 100 pounds of molding compound and 22 pounds of aminophenol resin are
recorded, and in 1936 imports of Bakelite filament compound totaled 250
pounds and other resins 8,851 pounds.
Even if in the years up to 1933 all of the imports of resins of coal-tar
origin were tar-acid resins, imports of tar-acid resins have been
negligible when compared with production. The smallness of imports may
be accounted for by a combination of factors, (1) the prohibition of
imports of certain types, which conflicted with patent rights; (2) the
rate of duty upon imports; (3) the fact that the manufacture of tar-acid
resins developed more rapidly in the United States than in most foreign
countries; and (4) the allocation of markets through agreements between
affiliated producers in different countries. (See p. 58.)
TABLE 4.—_Synthetic resins of coal-tar origin: United States imports for
consumption, 1919-37_
--------+----------+----------+-----------+------------+---------------
| | | | Computed | Computed
Year | Quantity | Dutiable | Value per | ad valorem | specific
| | value | pound | rate | rate
--------+----------+----------+-----------+------------+---------------
| _Pounds_ | | | _Percent_ | _Per pound_
1919 | 1,114 | $2,860 | $2.57 | 32.0 | $0.82
1920 | 2,479 | 2,681 | 1.08 | 34.6 | .37
1921 | 1,420 | 2,366 | 1.67 | 33.0 | .55
1922 | 2,518 | 3,498 | 1.39 | 52.3 | .73
1923 | 3,183 | 10,512 | 3.30 | 62.1 | .20
1924 | 8,756 | 4,183 | .48 | 68.9 | .33
1925 | 1,537 | 889 | .58 | 57.1 | .33
1926 | 1,649 | 1,298 | .79 | 53.9 | .42
1927 | 11,359 | 4,266 | .38 | 63.6 | .24
1928 | 60,547 | 10,984 | .18 | 83.6 | .15
1929 | 67,529 | 17,503 | .26 | 72.0 | .19
1930 | 46,464 | 10,417 | .22 | 76.2 | .17
1931 | 6,074 | 6,180 | 1.02 | 51.9 | .53
1932 | 6,403 | 3,905 | .61 | 56.5 | .34
1933 | 3,776 | 2,508 | .66 | 55.5 | .37
1934 | 15,711 | 8,680 | .55 | 57.7 | .32
1935 | 18,015 | 6,075 | .34 | 65.8 | .22
1936 | 18,598 | 13,643 | .73 | 54.5 | .40
1937[1] | 18,977 | 14,278 | .75 | 54.3 | .41
--------+----------+----------+-----------+------------+---------------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 5.—_Synthetic resins of coal-tar origin: United States imports for
consumption, by principal sources, in specified years, 1929-37_
---------------+--------+-------+-------+-------+-------+-------+-------
Imported from— | 1929 | 1931 | 1933 | 1934 | 1935 | 1936 |1937[1]
+--------+-------+-------+-------+-------+-------+-------
| Quantity (pounds)
+-------+-------+-------+-------+-------+-------+-------
Germany | 50,770 | 3,166 | 2,724 | 9,801 | 2,220 |10,750 | 13,950
France | 20 | 2,331 | 740 | | 297 | 168 |
United Kingdom | 336 | | | 1,065 |13,242 | 1,979 | 2,215
Switzerland | 3,473 | 1,781 | 4,384 | 1,716 | | |
Canada | 1,372 | 135 | 1,266 | 594 | | |
All other | | | | | | |
countries | 16,403 | 577 | 312 | | 340 | 51 | 502
+--------+-------+-------+-------+-------+-------+-------
Total | 67,529 | 6,074 | 3,776 |15,711 |18,015 |18,598 | 18,977
+--------+-------+-------+-------+-------+-------+-------
| Value
+-------+-------+-------+-------+-------+-------+-------
Germany |$11,771 |$4,053 |$1,913 |$5,303 |$1,959 |$9,700 |$11,960
France | 21 | 1,760 | 465 | | 236 | 177 |
United Kingdom | 2,235 | | | 255 | 2,476 | 1,090 | 659
Switzerland | | | | 2,621 | 1,308 | 2,154 | 1,197
Canada | | | | 501 | 46 | 486 | 214
All other | | | | | | |
countries | 3,476 | 367 | 130 | | 50 | 36 | 248
+--------+-------+-------+-------+-------+-------+-------
Total | 17,503 | 6,180 | 2,508 | 8,680 | 6,075 |13,643 | 14,278
+--------+-------+-------+-------+---------------+-------
| Unit value
+--------+-------+-------+-------+-------+-------+-------
Germany | $0.23 | $1.28 | $0.70 | $0.54 | $0.88 | $0.90 | $0.86
France | 1.05 | .76 | .63 | | .79 | 1.05 |
United Kingdom | 6.65 | | | .24 | .19 | .55 | .30
Switzerland | | | | .75 | .73 | .49 | .70
Canada | | | | .37 | .34 | .38 | .36
All other | | | | | | |
countries | .21 | .64 | .42 | | .15 | .71 | .49
+--------+-------+-------+-------+-------+-------+-------
Average | .26 | 1.02 | .66 | .55 | .34 | .73 | .75
+--------+-------+-------+-------+-------+-------+-------
| Percent of total quantity
+--------+-------+-------+-------+-------+-------+-------
Germany | 75.2 | 52.1 | 72.1 | 62.4 | 12.3 | 57.8 | 73.5
France | .1 | 38.4 | 19.6 | | 1.6 | .9 |
United Kingdom | .5 | | | 6.8 | 73.5 | 10.6 | 11.7
Switzerland | | | | 22.1 | 9.9 | 23.6 | 9.1
Canada | | | | 8.7 | .8 | 6.8 | 3.1
All other | | | | | | |
countries | 24.2 | 9.5 | 8.3 | | 1.9 | .3 | 2.6
---------------+--------+-------+-------+-------+-------+-------+-------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Exports from the United States.
Appreciable quantities of phenolic resins are exported annually in the
form of molding compounds and as finished articles of wide variety.
Statistics of these exports are not compiled separately by the Department
of Commerce.
Exportation is limited by a number of factors, such as licensing
agreements, patents, allocation of markets, and high tariffs or embargoes
in certain countries. The largest domestic maker is affiliated with
producers in Great Britain, Germany, France, Italy, Canada, and Japan.
Other domestic firms have agreements as to patents and markets with
producers in England, Germany, and other countries.
TAR-ACID RESINS FOR MOLDING
The tar-acid resins were first developed for molding and they are still
used in large volume in this way. An article produced in large quantity
is more likely to be made of molded resin. The cost of the mold, which
may amount to several thousand dollars, then becomes very small per unit
produced. If the article is of such a shape that it would require a great
deal of labor to produce in metal or wood, it may be produced in quantity
much more cheaply from resin, since it will come from the mold almost in
finished form.
A few of the large molders find it economical to make their own
resins when they use one type in large volume or desire some special
modification. Most of the molders buy resins for molding in the form of
either powder or pre-formed pellets ready for use.
Molding powders and pellets.
Molding powder is made from B-stage resin (see p. 13), a filler, a
pigment, a lubricant, and a plasticizer. These materials are mixed and
put through rolls at a moderate heat and pressure. The resin softens
and amalgamates with the other materials. It hardens upon cooling and
is ground to powder. A pre-formed pellet may be made from the powder by
pressure; use in this form saves the time of the molder when filling the
mold, since he is not required to measure the powder.
The proper selection of the filler in a molding powder is important in
influencing the quality of the molded article. Fibrous fillers improve
the mechanical strength and shock resistance of the finished article.
Wood flour is the most widely used filler in tar-acid resins as well as
in other thermosetting resins. Pine, spruce, and fir are the principal
kinds used, and consideration must be given to the bulk, gum content,
color, and the size and shape of the wood particles. Color is the least
important since most of the tar-acid resins give brown or black moldings.
When the molding must withstand high temperatures, asbestos fiber is
used as a filler. In articles requiring high shock resistance, such as
golf club heads, a filler of paper pulp is used. Where high electrical
insulation and dielectric properties are required, ground mica is used
as the filler. Certain inorganic fillers such as powdered slate, gypsum,
barium sulphate, calcium sulphate, china clay, zinc oxide, and infusorial
earths, are sometimes used. Large proportions of these may be used where
hardness is more important than strength, as in phonograph records. Other
materials used include rubber, graphite, horn, bone, starch, pumice, and
cork.
Coloring matter used may be coal-tar dyes or pigments such as bone black,
carbon black, and iron oxides. Pigments are usually more satisfactory,
although dyes are sometimes preferred in articles for insulation.
A lubricant is added to the molding mixture to overcome the tendency to
stick in the mold. Metallic soaps, stearates, and stearic acid are those
most commonly used.
Sometimes a plasticizer is included, its function being to act as a
solvent for the resin, thus increasing the flow of the material in the
mold. The plasticizer should be one which will become infusible or at
least remain solid in the molded article.
[Illustration: PREFORM PRESS MAKING PELLETS FOR USE IN MOLDING.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
[Illustration: VACUUM CLEANER PARTS OF TAR-ACID RESIN ILLUSTRATING THE
INTRICATE MOLDED SHAPES POSSIBLE.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
[Illustration: RADIO CABINET AND TELEPHONE SET OF MOLDED TAR-ACID RESIN.
Source: Bakelite Corporation, 217 Park Avenue, New York, N. Y.]
A typical molding powder or pre-form pellet will contain by weight:
Resin 40 to 50 percent
Filler 35 to 50 percent
Plasticizer 5 percent
Lubricant 1 percent
Pigment 1 percent
The molding of tar-acid resins.
Ordinarily the molds used are made of hardened steel, highly polished.
They must stand working pressures of several thousand pounds per
square inch. The mold is placed in a hydraulic press, heated by steam,
electricity, or gas, and the molding material is placed in the mold. The
press is closed and heat and pressure are applied. The temperatures used
range between 250° F. and 365° F., and the pressures between 1,000 and
8,000 pounds per square inch. The molding time depends on the shape and
size of the article and on the composition of the molding material. As
little as one-half minute is required for small objects and as long as 10
minutes for large objects. Average molding time is about 3 minutes. The
article is removed from the mold, allowed to cool, and is then trimmed,
sanded, filed, or polished. Since the mold is highly polished, the
finishing operation is usually needed only to remove the flash. Inserts,
such as metal parts (binding posts, electrical contacts, etc.), or inlays
of polished metal in name plates, and signs, are often molded in; gear
shift knobs are molded over a hollow metal core; rubber inserts are used
in castors, electrical plugs, and similar objects.
The molding operation is an art, and has made remarkable progress in
recent years. Many articles molded of tar-acid resins are well-known to
the public. The automotive industry is the best customer, using such
molded parts as gear shift knobs, horn buttons, accelerator pedals,
light switches, ignition parts, and distributor heads. Other well-known
applications are builders’ hardware, electrical switch plates, switches
and fixtures, fountain pens, radio parts, telephone parts, handles for
stoves, vacuum cleaners, and other appliances, buttons, buckles, costume
jewelry, camera cases, radio cabinets, small containers, and hundreds of
others.
The importance of tar-acid resins in molded articles is shown by the fact
that more than 75 percent of all synthetic resin molded articles made in
1937 used this type of resin as a binder.
Production of tar-acid molding resins.
Domestic production of tar-acid molding powders and pellets was reported
to the Tariff Commission by 15 makers in 1937. Most of these firms have
specialized in resin development and manufacture. Among the well-known
brands are Bakelite, Durez, Durite, Resinox, Indur, and others (see p.
153 for list of trade names).
Statistics of production and sales of tar-acid resins used in molding
were collected separately for the first time in 1935. They show a net
resin output of about 21,000,000 pounds, with sales of 18,000,000 pounds
or about 40 percent of the total tar-acid resins. The average unit value
was 17 cents per pound. In 1937 the production of tar-acid resins for
molding exceeded 32,000,000 pounds, again about 40 percent of the total.
These statistics are based on net resin and do not include fillers,
modifiers, pigments, or inert material of any kind.
CAST PHENOLIC RESINS
Process of manufacture.
The production of cast phenolic resins requires pure materials, expensive
equipment, and extreme care in the control of the operation. A mixture
of phenol and formaldehyde and a catalyst (usually sodium or potassium
hydroxide) is charged into a nickel-lined reaction kettle and heated
until the water separates and is removed. The reaction is then allowed
to proceed to the desired point. Glycerin is added to aid in forming a
transparent product. All equipment, including pipe lines, valves, and
pumps, is nickel or nickel lined except that used for formaldehyde, which
is made of aluminum.
The resin is usually made in 1,000 pound batches, and the reaction cycle
ranges from 6 to 18 hours. It is colored with soluble coal-tar dyes and
cast into lead molds. These are placed in a heated room and allowed
to cure for 3 to 6 days. The resin is removed from the mold with air
hammers, and the lead molds are melted.
The appearance of the resin may be changed by varying its water content,
by the addition of dyes and fillers, and by the addition of other
substances to produce some desired effect, such as imitation ivory or
marble. The clarity of the resin depends upon its water content—the
greater the degree of dehydration the clearer the product. Range of
colors is complete, from crystal clear to the darker shades, with any
degree of transparency, translucency, or opaqueness.
Casting is in the form of sheets, rods, tubes, or special forms suitable
for the production of buckles, jewelry, and other small products. Molds
of complicated shape cannot be used, which means that most articles
if produced of cast resin must be produced from standard shapes by
subsequent working. Recently small radio cabinets have been cast.
Uses.
Cast phenolic resin can be machined in the same manner as hard wood. It
must be polished after machining, usually by tumbling with shoe pegs and
pumice or with muslin wheels. The smooth finish and low degree of heat
conduction give the material a pleasant feel, not cold to the touch as
is metal. The coloring is not superficial and therefore does not chip
or wear off. Electrical properties are excellent. A slow polymerization
continues for some time after fabrication, resulting in slight shrinkage.
Cast phenolic resins are marketed by the producers as rods, sheets,
cylinders, and special castings. Standard round rods range from ⅜ inch to
more than 5 inches in diameter. Special rods are available in such forms
as square, hexagon, octagon, and fluted. Standard sheets are in sizes
from 12 by 24 inches to 36 by 72 inches, and from ⅛ to 1 inch thick.
Stock cylinders are available in a wide range of inside and outside
diameters.
[Illustration: CAST PHENOLIC RESINS, STANDARD SHAPES AND SMALL ARTICLES
FABRICATED FROM THEM.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
Stock material is fabricated by a number of firms into an endless variety
of articles. Among these are toilet articles such as combs, backs for
brushes, cosmetic containers, and trinkets; fittings for automobiles,
electrical appliances, furniture, and display fixtures; jewelry, dress
ornaments, clock cases, handbag frames, vanity cases, smokers’ articles,
signs and advertising specialties, picture frames, handles for cutlery,
chessmen, pens, desk penholders, pencils, and many others. Probably the
largest consumption is in the making of buttons and buckles.
The cast phenolic resins are odorless, tasteless, nonflammable, resistant
to oils and greases, and practically nonbreakable.
Patents and licensing.
The basic patent covering the manufacture of cast phenolic resins is
United States Patent No. 1,854,600, issued April 19, 1932, to F. Poliak
and A. Ostersetzer, of Vienna, and assigned to Pollopas, Ltd., of London.
Many other patents have been granted on variations and modifications of
this one. The basic process is also patented in England, France, Germany,
and other countries.
United States and Canadian patent rights were purchased by the American
Catalin Corporation; German rights by the Interessen Gemeinschaft
Industrie A. G. (German I. G.); French rights by Kuhlmann Co., and
British rights by the Imperial Chemical Industries. These licensing
arrangements limited the licensee to sales in his own and, in some
instances, nearby countries.
The American Catalin Corporation has successfully defended the validity
of this patent and has licensed a number of domestic manufacturers to
produce cast phenolic resins on a royalty basis.
In 1937 there were seven domestic makers of cast phenolic resins located
in New Jersey, New York, Massachusetts, and Pennsylvania. These firms
produce and market resins under the following trade names: Catalin,
Prystal, Joanite, Fiberlon, Phenolin, and Marblette.
Production of cast phenolic resins.
Production was initiated about 1929 by the American Catalin Corporation.
The output increased substantially every year from that year through
1933. Statistics of production and sales are not publishable for
the years prior to 1934 because they would reveal the operations of
individual firms; they are given in table 6 for subsequent years.
TABLE 6.—_Cast phenolic resins: United States production and sales,
1934-37_
------+-------------+---------------------------------------
| | Sales
Year | Production +------------+-------------+------------
| | Quantity | Value | Unit value
------+-------------+------------+-------------+------------
| _Pounds_ | _Pounds_ | |
1934 | 4,968,445 | 4,793,658 | $2,099,035 | $0.44
1935 | 5,566,621 | 5,454,490 | 2,205,879 | .40
1936 | 6,111,632 | 6,013,855 | 2,476,619 | .41
1937 | 5,459,654 | 5,335,746 | 2,180,620 | .41
------+-------------+------------+-------------+------------
Source: Dyes and Other Synthetic Organic Chemicals in the
United States, U. S. Tariff Commission.
Imports and exports.
The licensing agreements, as outlined above, provide for the allocation
of markets for cast phenolic resins. Because of this arrangement there
are little or no imports and exports of this material.
TAR-ACID RESINS FOR LAMINATING
By laminating is meant the impregnation of sheets of paper, fiber, or
cloth with a solution of synthetic resin and the building up of these
layers into sheets of reinforced synthetic resin of various thicknesses.
When a tar-acid resin is used the paper or cloth is immersed in or coated
with a solution of the B-stage resin, dried, and layers of the material
are compressed and consolidated, under heat and pressure to form sheets,
rods, tubes, blocks, and other forms, in the infusible C-stage.
The coating of sheets of paper with solutions of natural resin and the
compacting of these sheets by heat and pressure is an old practice,
especially for electrical uses. Shellac and copal have been widely used
and yield a laminated board of good electrical and mechanical properties
when used at temperatures under 70° C. Above 70° C. the resin softens and
the desirable properties are lost. Since temperatures above 70° C. are
not uncommon in electrical equipment, the limitations of these natural
resins in this use can readily be seen. The use of tar-acid resins to
impregnate insulation material removes the temperature limitation and
otherwise improves the product; insulators so made are widely used in all
sorts of electrical and radio equipment.
Uses of tar-acid resin laminated products.
Laminated sheets of tar-acid resin are made with paper, canvas, duck,
linen, pulpboard, vulcanized fiber, plywood, and other materials. Paper
is the material generally used for electrical insulation, although cloth
is sometimes used when greater strength is needed. Canvas is used where
maximum strength is required, as in gears for automobiles and industrial
machinery. Impregnated linen is adapted to punched parts and small gears.
These laminated materials are uniformly dense, tough, resilient and light
in weight. They are nonabsorptive, have low thermal conductivity, and a
low coefficient of expansion. Their dielectric strength is excellent and
chemically they are inert to oils, brine, most acids, weak alkalies, and
many solvents. Structurally they are strong under tension, compression,
flexion, or impact; they are easy to machine and are sound absorbing.
Gears made of laminated canvas are widely used; they are silent and
outwear those made of metal. The development of such gears was brought
about by the demand for a positive drive without the clash and clatter
resulting from metal to metal contact. The laminated gear absorbs
vibrations, eliminates noise, and reduces wear. The laminated material is
one-seventh the weight of brass, one-sixth the weight of steel, one-fifth
the weight of cast iron and one-half the weight of aluminum. Laminated
gear blanks may be cut on automatic machines into helical, spur, bevel,
or worm gears.
Timing gears in automobiles are frequently of this type; they require no
adjustment and seldom need replacement during the life of the motor. The
light weight of the material reduces to a minimum flywheel effect on the
camshaft. Where lubrication is difficult a graphite impregnated blank may
be used.
Bearings made from laminated fabric are successfully used in heavy
rolling mills where they reduce replacement costs and decrease power
consumption. The laminated material possesses strength, smooth surface,
density, good load carrying capacity, high impact resistance, nonscoring
properties, and is practically frictionless. Power consumption is said to
be reduced as much as 40 to 60 percent of that of metal bearings and the
life of the laminated bearing has been as much as 10 times that of the
metal ones. It replaces Babbitt metal, brass, bronze, white metal, gun
metal, or lignum vitae in this application.
[Illustration: LAMINATING SHEET PRESS.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
[Illustration: GEARS MADE OF LAMINATED TAR-ACID RESIN.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
[Illustration: COCKTAIL LOUNGE USING TAR-ACID LAMINATED DECORATIVE
MATERIAL.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
In decorative uses, laminated materials have made remarkable progress
in recent years. In this application the material made from laminated
paper is veneered on wood or fiber board, and the surface is so durable
that refinishing is probably not necessary during the life of the
equipment. Table tops for public rooms such as restaurants, cafeterias,
and bars are widely used because of the beautiful designs obtainable and
because the material is not discolored by lighted cigarettes, alcohol
or other liquids, and does not chip or crack. Laminated sheets are used
for bathroom and kitchen walls, doors, window sills, store and theater
fronts, lobby walls in hotel and office buildings, and counter tops in
banks and post offices. The liner _Queen Mary_ is equipped with panels
of this material as is also the new Library of Congress Annex. Most of
the leading hotels have installed bar and cocktail lounges of laminated
materials because of the range of color and the ease with which novel
designs may be carried out.
Almost any solid color, design, or imitation of another material may be
given the laminated sheet simply by printing it upon the top sheet of
paper used in the impregnated assembly. Thus a beautiful piece of walnut
or mahogany may be photographed, inexpensively reproduced upon paper, and
the finished laminated sheet will closely imitate the polished wood. The
combination of beauty with long life should permit the widespread use of
this type of material in all sorts of building and equipment. It has been
suggested as a possibility in automobile body construction.
Other important uses are in trim and door strips for mechanical
refrigerators, in cafeteria trays, buckets and special containers, tires
for factory trucks, textile spools, miners’ safety helmets, gaskets,
valve discs and rings for pumps, pulleys, besides many others.
Production of tar-acid resins for laminating.
Statistics of production and sales of synthetic resins for laminating
were not separately compiled prior to 1935. Since that year the resins
made from cresylic acid have been used to the greatest extent in
laminating, followed by those made from phenol. Tar-acid resins reported
as “used in paints, varnishes, and lacquers” may include appreciable
quantities of resin varnishes used for laminating. The total production
and sale in 1937 of tar-acid resins used in laminating, therefore, would
be the sum of the 20 percent of the total (see table 3) reported for
laminating plus some part of the 25 percent reported for surface coatings.
Domestic producers of tar-acid resins for laminating are located
in Delaware, New Jersey, New York, Illinois, Massachusetts, and
Pennsylvania. The makers of the laminated materials are located in
Delaware, New Jersey, New York, Ohio, Illinois, Pennsylvania, Indiana,
and Connecticut. Their products are marketed under a number of trade
names, including Micarta, Dilecto, Celoron, Formica, Textolite,
Phenolite, Insurok, Spauldite, Synthane and Phenol Fibre.
Imports into the United States.
There has been practically no importation of synthetic resins for
laminating. Imports of laminated products (rods, tubes, blocks, strips,
blanks, or other forms) of which synthetic resin is the chief binding
agent totaled only 215 pounds, valued at $612 in 1931 (principally from
the United Kingdom); 13 pounds, valued at $71 in 1932; none in 1933 and
1934; 609 pounds, valued at $579 in 1935 from Canada, Germany, and the
Netherlands; and 3,260 pounds, valued at $9,468 in 1936 from Austria,
Germany, and the United Kingdom.
Exports from the United States.
Exports of phenolic or other synthetic resins for laminating and of
laminated articles are not separately recorded in official statistics. It
is known that appreciable quantities of laminated articles are exported
to Canada, England, and other countries.
TAR-ACID RESINS FOR SURFACE COATINGS
Synthetic resins are widely used for surface coatings, chiefly because
of the ease with which new types can be produced to meet special
requirements and because of their uniformity. Tar-acid resin coatings may
be varied in composition and properties to meet a particular purpose.
Possible variations depend on the type or mixture of tar acid used
(phenol, cresols, xylenols, tertiary amyl phenol, tertiary butyl phenol,
phenyl phenol), whether the condensation takes place in the presence of
an acid or an alkali, and on the proportion of formaldehyde used. The
resin so formed may be modified with natural resins, synthetic resins
of the alkyd type, fatty acids, or other materials. The almost endless
opportunities for different types can, therefore, readily be appreciated.
Types of resin used and the resultant coatings.
The tar-acid resins used in varnishes and other surface coatings are
usually oil-soluble types. They may be divided into three general
classes: (1) Phenol-formaldehyde condensation products rendered
oil-soluble by chemical combination or physical dispersion in other
materials, such as rosin and copal; (2) condensation products made
from tar acids other than simple phenol, which are themselves soluble
in drying oils and thinners; and (3) products from the condensation
of the substituted phenols and formaldehyde. These three classes of
oil-soluble tar-acid resins differ widely in their chemical and physical
properties and in their functions. The first group are usually called
modified phenolic resins, the second group are referred to as unmodified
or 100-percent soluble, and the third group are known as substituted
phenolic resins.
The unmodified resins are extensively used in long-oil tung varnishes,
to which they impart greater drying speed, durability, and resistance
to alkalis and gases. The modified types impart the same properties to
tung oil varnishes but to a lesser extent. In addition the modified
types possess considerable hardness so that greater gloss and fullness
are obtained. Modifiers are either drying oils or natural resins; tung
oil is the most widely used oil and rosin the principal natural resin.
Substituted phenols such as para tertiary amyl phenol and para tertiary
butyl phenol may be used in place of simple phenol; while these are
relatively high priced components, the resins made therefrom have
increased in recent years to an appreciable volume because of their
improved properties.
Other synthetic resins, such as those of the alkyd, petroleum, urea,
and vinyl types, are sometimes incorporated with the phenolics in the
same surface coating to obtain some desired property. The addition of a
plasticizer, such as tricresyl phosphate or dibutyl phthalate, improves
the flexibility of the film.
Spirit varnishes, in which the synthetic resin is dissolved in a solvent,
are also available. In this type the soluble fusible resin (form A) is
dissolved in an organic solvent such as acetone or the various alcohols,
and conversion of the resin to the insoluble, infusible state (form C) is
effected by baking the film.
Coatings made from tar-acid resins are widely used in so-called 4-hour
enamels and varnishes, for both interior and exterior application.
They are also used in the manufacture of linoleum, artificial leather,
adhesives, and printing inks. When incorporated with nitrocellulose
or cellulose acetate lacquers they improve the adhesion, luster, and
resistance to alkalies.
Production in the United States.
In 1937 the output of tar-acid resins for surface coatings exceeded 20
million pounds (net resin). Those from phenol and the substituted phenols
accounted for a very large part of the total. They were followed by
resins from cresylic acids and the xylenols in that order.
In 1937 there were about 20 domestic makers of this type of synthetic
resin, with factories located in California, Connecticut, Illinois,
Indiana, New Jersey, New York, Massachusetts, Michigan, Missouri, Ohio,
Pennsylvania, and Rhode Island.
Imports into and exports from the United States.
Imports of oil-soluble phenolic resins have been negligible. This is due,
in part, to licenses and agreements between certain domestic and foreign
makers, to the remarkable advancement and pioneering work done in this
country, to the holding of many basic patents by Americans, and to the
relatively high duty on imports.
Exports of these products, usually in the form of enamels, varnishes, and
lacquers, have been appreciable and are probably increasing each year.
Official statistics are not reported separately.
TAR-ACID RESINS IN ADHESIVES
A comparatively new use for tar-acid resins is in the manufacture of
wood adhesives. Ordinary vegetable and animal glues have long been used,
although their deficiencies in certain characteristics are well known.
These include (a) their inability to produce uniform products, (b) the
tendency of most alkaline glues to stain wood, (c) the bad effects
of moisture on them, and of bacteria and fungi in the case of animal
glues. The tar-acid resins have none of these objectionable qualities.
Being chemically inert they are free from attack by fungi and bacteria.
Moisture does not affect them, and they do not stain wood.
Three types of resins are used as wood adhesives, principally in bonding
plywoods and veneers: (1) Hot press liquid, (2) cold press liquid, and
(3) resin film. Furniture, radio cabinets, games, and building products
constructed from plywoods bonded with resins can be shipped to tropical
countries, the bond not being affected by extreme climatic conditions.
These resin adhesives are more expensive than the usual animal and
vegetable glues, a factor which has limited their application. Their
advantages may, however, open up to resin bonded plywoods uses in which
the more ordinary types are not satisfactory.
TAR-ACID RESINS FOR OTHER USES
The application of tar-acid resins in casting, molding, laminating,
surface coatings, and adhesives has been described. There are many other
uses, but most of them approach the types of application dealt with.
Impregnation of all sorts of materials with tar-acid resins is an
increasing use; such applications are in fabrics for aircraft, crease
resistant textiles, wood, asbestos, concrete, and electrical coils. Wood
with resin forced into the fiber under pressure is used for furniture,
flooring, heads for golf clubs, and handles for utensils. Resin is used
as a binder in the manufacture of brake linings for automobiles, as well
as in the manufacture of abrasive and grinding wheels.
An interesting application is in the construction of corrosion-resistant
chemical plant equipment. In 1922 the German firm of Saureschutz
Gesellschaft was incorporated to fabricate equipment composed of a
special acid-resisting type of phenolic resin and asbestos. Sometime
later its manufacture was started in the United States. All sorts of
industrial plant equipment is now available, including cylindrical and
rectangular tanks up to 9 feet in diameter and 12 feet high, piping for
corrosive liquids and gases, valves, pumps, fans and ventilators, filter
press plates and frames, buckets, dippers, etc.
Another new use is for making matrices in which to mold rubber printing
plates. Such plates are used at present chiefly in printing cotton and
paper bags but extensive experimentation promises to broaden their use.
The matrix is made of fiber board of very open structure impregnated with
tar-acid resin in the process of manufacture.
4. ALKYD RESINS
Description and uses.
The alkyd resins, used principally in paints, varnishes, and lacquers,
are a group of condensation products synthesized by reacting polyhydric
alcohols, such as glycerin and the glycols, with dibasic organic acids,
such as phthalic, maleic, succinic, and sebacic. The condensation product
is almost always modified to give properties to the resin desirable or
essential to the specific application contemplated. The modifying agent
may be a drying, semidrying, or nondrying oil; the fatty acid of an oil;
a natural resin, such as rosin; a synthetic resin of the tar-acid group
or of the urea-formaldehyde type; or other substance. Up to the present
time unmodified alkyd resins have not been commercially important.
A wide variety of types is obtained by the use of different materials
and different modifiers. The variations begin with the dibasic acid
used, and with the polyhydric alcohol used. The modifications possible
are practically endless, and almost any fixed oil or the corresponding
fatty acid, and most of the natural or synthetic resins may be used. The
importance of the modifier is shown by the proportion used in most alkyd
resins. On the average, approximately 50 percent of the total weight of
the drying and semidrying alkyd resin products is modifier, 30 percent
dibasic acid, and 20 percent polyhydric alcohol. The proportions will, of
course, vary with individual types. Certain types on the market contain
only 25 percent modifier while others have as much as 75 percent.
In a new industry such as this, rapid changes in types and applications
must be expected. Extensive research is being carried on by various
groups. The raw material makers are seeking cheaper products or those
with special properties; the resin makers are investigating an endless
number of modifications, and the makers of surface coatings are testing
most of the new types offered.
Development and patents.
Probably the earliest record of research leading to the development of
the alkyds was that of van Bemmelen, who reported in a German technical
journal in 1856 the sirupy products obtained by heating together succinic
acid and glycerin or citric acid and glycerin. The first investigation
of the phthalic anhydride-glycerin resins was recorded in 1901.[3]
Watson Smith, while engaged in research on phthalein dyes, obtained a
transparent, highly refractive resinlike substance when glycerin and
phthalic anhydride were heated together. Smith recommended the product as
a cement for ceramic wares.
During the period 1910-16 the research laboratories of the General
Electric Co., engaged in research on a synthetic resin from glycerin
and phthalic anhydride. As a result of these studies numerous patents
were granted for this type of resin to which the trade name Glyptal
was applied. Intensive research was carried on by several firms, many
variations were developed, and literally hundreds of patents were granted.
The paint and varnish industry has been undergoing radical readjustment.
Methods and natural products, which for decades or centuries had changed
very little, are giving way to synthetic creations of our laboratories.
The first important departure from the traditional practices was the
development of nitrocellulose lacquers. The commercial application of
the alkyd resins followed, and their use is increasing rapidly. Because
this development is still comparatively young, the large number of
modifications offered has confused the coating manufacturer. It is
probable that many of the synthetic products now being marketed have no
special technical or economic justification and that they will in time
lose out in competition with better products known at present, or still
to be developed.
United States Patent No. 1,893,873, dated January 10, 1933, granted to R.
H. Kienle and assigned to the General Electric Co., was considered one of
the basic patents in this field. Early in 1936 it was declared invalid
in a suit claiming infringement brought against the Paramet Chemical Co.
of Brooklyn, N. Y. The decision in this case seems to have opened the
glycerin-phthalic anhydride resins to a large number of manufacturers.
Among the principal brands of alkyd resins now on the domestic market are
Beckosol, Dulux, Esterol, Glyptal, Rezyl, and Teglac. Each of these trade
names identifies a series of products.
Classification of alkyd resins.
A number of classifications of the alkyd resins are possible and
practical. Since by far the most important applications are in
surface coatings, and their use in molding compositions is relatively
unimportant, it seems advisable at this time to emphasize the
more important use. For the purpose of this survey the following
classification is used:
(1) Drying alkyd resins.
(a) Unmodified.
(b) Modified with natural materials.
(c) Modified with other synthetic resins.
(d) Modified with other synthetic resins and oil extended.
(2) Semidrying alkyd resins.
(3) Nondrying alkyd resins.
(4) Miscellaneous modified alkyd resins.
(5) Alkyd resins in water dispersion.
(6) Alkyd resins in molding compositions.
At least 75 percent of the alkyd resin finishes used at present are of
the drying type and about 15 percent of the nondrying type.
_Unmodified drying alkyd resins._—This class of alkyd resins consists of
a series of compounds made from polyhydric alcohols, polybasic acids, and
fatty acids in chemical combination. The alcohol is usually glycerin, and
the polybasic acid largely phthalic anhydride or acid, although others,
such as maleic anhydride (acid) are increasing rapidly in importance. The
fatty acid or oil used may be linseed, tung, perilla, hempseed, soybean,
sunflower, safflower, or other drying oil. It is believed that tung oil
and perilla oil are the most important at this time.
Unmodified drying alkyd resins are characterized by excellent durability
but limited resistance to water in air-dried finishes. Both in air-dried
and in baked finishes they are outstanding as to flexibility, quick
drying, long luster life, and permanent adhesion. Their principal uses
are in finishes for interior walls and woodwork, automobiles, coatings on
steel such as for refrigerators, railway equipment, bridges, advertising
signs, and lithographed containers. In these applications the products
of this type compete with nitrocellulose lacquers and the older types
of varnishes and paints. While the initial cost is higher, greater
durability is obtained together with faster drying, flexibility, and
hardness.
Probably the largest field for surface coatings is outdoor wood finishes.
Several attempts have been made to adapt pure alkyd finishes to this
use but with limited success because the hard and non-porous finish
does not permit the escape of moisture contained in the wood and the
pressure developed from vaporization of the moisture by the sun’s rays
tends to lift the coating from the wood surface. Recently it has been
found practicable to incorporate from 15 to 20 percent alkyd resins in
conventional types of outdoor paints for wood. Here the use of alkyds has
contributed greater durability and retention of fresh appearance over a
longer period. Paints of this type are now on the retail market.
_Drying alkyd resins modified with natural materials._—This type of
alkyd resin is modified principally with natural resins, such as rosin,
damar, mastic, shellac, or copal. The use of these natural resins imparts
hardness to the resin but shortens its durability. They make the product
less expensive, permit easier incorporation of the drying oil, and in
some instances increase the water resistance.
Their principal application is to modify nitrocellulose lacquers and
lacquer sealers, in order to impart gloss, hardness, and easy sanding. It
has been said that the commercial production of drying alkyds modified
with natural resins was as important a development in the surface coating
industry as the discovery of the alkyds themselves.
_Drying alkyd resins modified with other synthetic resins._—Drying alkyd
resins may be modified with tar-acid formaldehyde resins, tar-acid
furfural resins, urea-formaldehyde resins, petroleum resins, and the
coumarone and indene resins.
Modification with tar-acid resins gives a quicker setting, harder drying
finish with a higher gloss. Alkyd resins so modified are adapted to both
air-drying and baked undercoats and finishes; they have good durability
and adhesion and good resistance to grease, oils, alcohol and abrasion.
For some uses the tar-acid resin modification gives better qualities
than either component possesses alone, but in light colored finishes it
has a tendency to cause the finish to yellow. Coatings made of drying
alkyd resins modified with tar acid resins are widely used on automobile
chassis, fenders, and bodies, machinery coatings, steel fixtures and
toys; they are especially suitable for primers, undercoats, and finishes
on metal.
Modification with urea resins produces baked-finish coatings. As much as
40 percent of the urea resin is incorporated. It makes possible coatings
with a full range of permanent colors and improves their hardness and
mar-proofness, whereas without the ureas the combination of color range
with hardness had been difficult to obtain. The urea resin modified
alkyds find use on metal surfaces of articles which must stand rough
handling, such as toys, furniture, and motors.
Modification with petroleum resins produces air-dried finishes. For
industrial use on metal they give coatings with better adhesion,
dispersion of pigments, and resistance to acids, alkalies, and moisture
at a lower cost than is obtained by ester gum or tar-acid resin
modification. The petroleum resin modification minimizes skinning and
improves the luster and the flow.
_Drying alkyd resins modified with other synthetic resins and oil
extended._—Excellent water resistance and versatility are the
characteristics of finishes made of alkyd resins modified with other
synthetic resins (usually tar-acid) and oil extended. The incorporation
of drying oils gives a low cost finish with better compatibility and
brushing and with the combined properties of a quick-setting varnish
and an alkyd resin. Although not so durable or quick setting as the
unmodified finishes, they have better water resistance. These finishes
may be brushed or sprayed, air-dried or baked. They have wide industrial
and architectural uses.
_Semidrying alkyd resins._—Cottonseed oil is the principal modifier in
semidrying alkyd resins. Alkyd resins of this type are used in finishes
requiring maximum gloss and color retention. When baked on metal at
high temperatures they show no tendency to wrinkle. They are used as
reinforcing agents to increase flexibility and durability, and to
plasticize other finishes.
_Nondrying alkyd resins._—The nondrying or nonoxidizing alkyd resins
are those containing a nondrying oil, such as castor oil or coconut
oil, or the fatty acid of a nondrying oil, such as stearic, palmitic,
or oleic acid. Nondrying oils make the resin less sensitive to heat
hardening and impart greater flexibility. These resins are used
principally as plasticizers in nitrocellulose lacquers. In this use they
have the advantage of better retention of plasticizing efficiency than
other plasticizers, many of which are lost by evaporation, migration,
absorption, or oxidation. These modified nitrocellulose lacquers, either
clear or pigmented, are used for coating wood, composition board, cloth,
paper, rubber, leather, and similar surfaces.
_Miscellaneous modified alkyd resins._—This group includes alkyd resins
modified with materials other than those already discussed. To date
(1938) there has been little, if any, commercial production of such
resins. There are many modifiers which have been suggested and which
might be used but for the fact that they are too expensive. Among these
are butyl alcohol and benzoic acid.
_Alkyd resins in water dispersion._—Emulsions of alkyd resins in water
are now available for use in clear and pigmented coatings. These are sold
in the form of paste containing 40 to 50 percent solids and are diluted
with water at the time of application. They are especially suitable for
coating porous surfaces, such as brick, concrete, plaster, stucco, and
masonry of all kinds. They are applied by brushing or spraying and they
combine the ease of application of water paints with the durability,
washability, and hardness of oil paints. They dry quickly, and the dried
film cannot again be dissolved or suspended in water; the coating can
therefore be washed or, after several weeks, scrubbed with cleansers.
Compared with oil paints, they give better coverage, are easier to apply,
and cost appreciably less. Compared with other types of water paints,
such as kalsomine, they give a glossier coating of greater durability and
superior appearance; they seal porous surfaces better; their covering
capacity is greater; and their applied cost is slightly less per square
yard of surface.
Coatings of this type may be applied directly over fresh plaster without
a sizing coat, since they allow the curing of the plaster to continue.
The usual paint pigments may be incorporated.
A special use of the water dispersed alkyds is on asphalt or tar since
they are nonbleeding in the solvents of these materials. This quality
permits their use for traffic and zone markers on streets.
_Alkyd resins in molding compositions and other uses._—The alkyd resins
are much less important as binders in molded articles than in coatings
and finishes. Conversion of the resin to the insoluble infusible form is
extremely slow, requiring days as compared with minutes for the tar-acid
and urea resins.
The alkyds are used as binders for flake, powder, and split mica to
produce insulation material of high electrical strength. Other uses are
in the production of linoleums; gaskets; brake linings; laminated fabric,
paper, and cardboard sheets; printing inks; and coated paper, textiles,
and leathers.
Pigments and solvents in alkyd finishes.
Since the alkyd resins are largely used in surface coatings and finishes
and since this application in this field is producing great changes in
the industry, it is appropriate to consider the effect of their use on
other materials.
The average alkyd resin consists of 50 percent glycerol phthalate
modified with 50 percent oil, fatty acid, natural resin, or synthetic
resin. The alkyd and modifier are dissolved in a solvent, usually a
coal-tar light oil such as toluol, or xylol, or a petroleum solvent, and
pigmented with titanium dioxide or other pigment. Highly basic pigments
such as zinc oxide, carbonate white lead, whiting and aluminum hydrate
(all important pigments in the conventional types of finishes) are not
used in alkyd finishes.
Production in the United States.
Prior to 1929, the domestic production of resins from phthalic anhydride
was confined largely to one maker. The quantities produced were
relatively small. In 1929 there were three producers, the volume of whose
production exceeded one million pounds for the first time. Beginning with
1933 the Tariff Commission collected and compiled production and sales
statistics for these resins. They are shown in table 7.
TABLE 7.—_Alkyd resins from phthalic and maleic anhydride: United States
production and sales, 1933-37_
--------+-----------+------------+------------------------------------
| | | Sales
Year | Number of | Production +------------+-----------+-----------
| makers | | | |
| | | Quantity | Value | Unit value
--------+-----------+------------+------------+-----------+-----------
| | _Pounds_ | _Pounds_ | |
1933 | 6| 9,930,705| 3,654,854 | $673,890 | $0.18
1934 | 10| 15,219,247 | 7,084,602 | 1,022,436 | .14
1935 | 15| 34,312,713 | 15,836,942 | 3,482,078 | .22
1936[1] | 31| 46,952,452 | 24,252,535 | 5,312,121 | .22
1937[1] | 39| 61,254,019 | 34,738,295 | 6,864,194 | .20
--------+-----------+------------+------------+-----------+-----------
[1] Includes resins from maleic anhydride.
Source: Dyes and Other Synthetic Organic Chemicals in the United
States, U. S. Tariff Commission.
In 1933 there were 6 makers of resins from phthalic anhydride, in 1935
there were 15, and in 1937 there were 35. The 1937 output of alkyd resins
from phthalic anhydride was 58,450,032 pounds net resin, with sales
of 32,583,307 pounds valued at $6,446,011. Producing plants are well
scattered through northern and eastern United States. In 1936 fewer than
one-third of the makers accounted for about 90 percent of the output.
The domestic production of resins from maleic anhydride was reported for
the first time in 1933. The output in that year consisted of experimental
quantities produced by two firms. A small increase in production occurred
in 1934 when another maker began operation. In 1936 there were eight
producers and the output was many times that of 1934. In 1937 there were
12 makers of these resins with an output of 2,803,987 pounds and sales of
2,154,988 pounds, valued at $418,183. It is the opinion of some persons
in the industry that in volume of production and sales the resins from
maleic anhydride will in the near future approach that obtained from
phthalic anhydride.
Imports into and exports from the United States.
No imports of alkyd resins have been recorded in official statistics.
Exports of alkyd resin coatings and finishes are not separately shown,
but data collected from the several producers show that appreciable
quantities were exported in recent years, principally to Central and
South American countries.
5. UREA RESINS
One of the most important series of thermosetting resins is the group
made by condensing urea and formaldehyde. As early as 1897 it was
discovered that an amorphous condensation product was obtained from the
reaction of urea and formaldehyde. The clear glass-like mass obtained led
to considerable research work toward the development of a substitute for
glass. It was found, however, that the resin obtained absorbed moisture,
resulting in a dimming of its luster, and that on standing for a time,
the condensation continued producing cracks, fissures, and disfigurements
in the molded article. In 1926 a successful commercial product was
developed in England by the use of thiourea. Cost of production, however,
was high. The addition of thiourea gave the product greater strength
and water resistance than that obtained with urea alone but retarded
the rate of cure. Also the sulphur present attacked steel molds, which
necessitated the use of expensive chromium plated or stainless steel
molds.
About 1929 the first successful straight urea product was perfected in
the United States. It was found that a filler, such as highly refined
alpha cellulose, minimized the stresses. The filler (as much as 30 to 40
percent is usually incorporated), destroys the transparency but permits
the manufacture of translucent articles in a wide range of color. Many of
the colors possible with the urea resins, particularly the light shades,
cannot at present be obtained in molded tar-acid resins.
An interesting fact concerning these resins is that they are produced
indirectly from four gases: Ammonia, carbon dioxide, hydrogen, and carbon
monoxide. Ammonia and carbon dioxide react to form urea, and hydrogen and
carbon monoxide yield methyl alcohol which is converted to formaldehyde.
Description and uses.
The urea resins are outstanding largely because of their brilliancy and
depth of color, properties not readily obtained in other thermosetting
resins. Being odorless and tasteless and completely resistant to oils
and greases, they are adapted to use in the manufacture of cosmetic
containers. Concentrated acids and alkalies attack the resin. The
electrical properties of the urea resins compare favorably with those of
the tar-acid resins. They have a lower power factor at high-frequencies
than the tar-acid resins, and are replacing, to some extent, established
materials in heavy duty electrical equipment where “tracking” causes
trouble. Molded articles made from urea resins are resilient but not
unbreakable.
[Illustration: THERMOSTAT CASE OF MOLDED UREA RESIN.
Source: Plaskon Company, Inc., 2112 Sylvan Avenue, Toledo, Ohio.]
[Illustration: SCALES CASE OF MOLDED UREA RESIN.
Source: Plaskon Company, Inc., 2112 Sylvan Avenue, Toledo, Ohio.]
The important uses of the urea resins are dictated by their pleasing
color and appearance. In 1935 the largest outlets were in buttons and
buckles, in bottle closures, and in such premium items as biscuit cutters
and cereal bowls distributed by a large food manufacturer. Tableware,
bathroom fixtures, all sorts of containers and closures, housings for
radios, clocks, scales, and other machines for retail stores, and
light-colored wall plates and switches, knobs, handles, and trim on dash
panels of automobiles, and handles and trimming on gas and electric
ranges were among the widespread applications of the urea resins. In
1938 probably the fastest growing outlet for urea resins is in lighting
equipment. Use in packaging, in closures, and in housings, is also
increasing. Tableware, the principal outlet for a number of years, is
declining markedly.
A comparatively new use is in shades and reflectors, replacing opal
glass. The unpigmented resin is highly translucent and gives high
light transmission and an exceptional degree of light diffusion. These
properties, together with low unit manufacturing costs, reduced shipping
costs, and resistance to breakage make the urea resins an ideal material
for all sorts of shades and reflectors for direct and indirect lighting
fixtures. Many of the shades used in railway cars are of this material.
The resin is available in degrees of denseness and opacity to give
particular ratios of reflection and transmission. Reflectors as large as
28 inches in diameter are on the market.
Although molded articles are the large outlets for the urea resins, other
applications are of increasing importance. Sirups used to impregnate
paper and cloth are used in laminating and the resulting materials have
unusual decorative possibilities. The surface is hard and durable and the
wide range of colors possible permits very attractive applications. The
urea resins are used both as the principal binding material for laminated
sheets or on the surface laminae of sheets where tar-acid resins are used
as the chief binder. The latter practice permits a wide color range in
decorative materials without loss of strength or other characteristics
of the tar-acid resins. In 1937 there were seven makers, and their
production of urea resins for laminating accounted for slightly less than
10 percent of the total of all urea resins.
Another application of urea resins which has grown rapidly in the past 2
years is in combination with alkyd resins in surface coatings. In 1937
there were three makers, and their output of urea resins for coatings
amounted to more than 10 percent of the total production of urea. Until
recently the use of urea resins in paints and varnishes was discouraged
by their insolubility in organic solvents and their instability. On the
other hand, their lack of color, their high transparency, their hardness,
and their freedom from after-yellowing were desirable characteristics.
The development of methods for preparing condensates, which overcome the
undesirable properties, has made available resins for this use. They
are marketed as water-white viscous solutions in a mixture of organic
solvents and are intended for use in baking finishes. They cannot be
used alone because the cured resin is extremely hard and brittle and
lacks adhesion. When combined with more elastic film-forming materials
such as drying or nondrying oil alkyd resins, they produce coatings that
are mar-proof, resistant to alcohol, grease, oil, and fruit acids, and
available in a full range of colors. Applications are in metal furniture
finishes, toys, refrigerators, can, and drum coatings.
The value of urea resins as adhesives has been known for many years and
one of the first patents issued for such use was United States Patent
No. 1,355,834 granted in 1920. Commercial development and application,
however, did not take place until the last 2 years. Several brands of
urea adhesives are now on the market. These meet the need for a hot-press
adhesive which is applied in liquid form, cures rapidly at moderate
temperatures, and is economical. For greater economy, the urea adhesive
may be mixed with various proportions of flour (up to 50 percent) without
affecting its water resistance. Diluted thus it comes within the cost
range of animal and vegetable glues and is more durable. At present, it
sells for 18 to 20 cents per pound; mixing it with 50 percent flour gives
an adhesive for plywood, costing about 10 cents per pound. In 1937 three
producers made urea resins for this use.
Other uses are in the treatment of textiles to obtain crease-proof
properties and in the impregnation of wood. United States Patent No.
1,951,994 issued on March 20, 1934, reports the preparation of artificial
silk from urea resins.
Production in the United States.
Commercial production of urea resins in the United States was reported
for the first time in 1929. Early in that year the American Cyanamid Co.
concluded an arrangement with the British Cyanides Co. of England for
the American rights to manufacture and sell in the United States a resin
made from urea, thiourea, and formaldehyde and marketed as Beetle molding
powder. A manufacturing unit was built at Bound Brook, N. J., and in 1930
the output was substantial.
In 1931 another producer, the Toledo Synthetic Products Co., began
manufacture of urea resins. Several years prior to that time the Toledo
Scale Co. started a search for a material light in weight to replace the
heavy porcelain-on-steel used in cases for scales. The search led to the
urea resins and to commercial production by their subsidiary. In 1935 the
Toledo Synthetic Products Company reached an agreement with the Imperial
Chemical Industries of England for the interchange of technical and
commercial information and of free patent licenses on urea molding and
laminating resins. The name of the domestic firm was later changed to the
Plaskon Co.
In 1932 the Unyte Corporation started commercial production of urea
resins at Grasselli, N. J. This firm was affiliated with the American
I. G. Corporation. Late in 1936 the Plaskon Co. took over the Unyte
Corporation.
The output of urea resins increased markedly in 1936 and 1937. Statistics
for those years cannot be published without disclosing operations of
individual firms. It may be stated, however, that the increase in both
years over the previous year was considerably greater than for any
earlier period. Most of the production was used in molded articles
although appreciable quantities were consumed in laminated articles, in
surface coatings, in the impregnation of fabric, and in adhesives.
There were 10 domestic makers of these resins in 1937.
Domestic production and sales of urea resins are shown in table 8.
TABLE 8.—_Urea resins: United States production and sales, 1933-37_
--------+------------+------------------------------------
| | Sales
Year | Production +-----------+------------+-----------
| | Quantity | Value | Unit value
--------+------------+-----------+------------+-----------
| _Pounds_ | _Pounds_ | |
1933 | 3,234,356 | 2,977,791 | $1,422,671 | $0.48
1934 | 3,470,916 | 3,115,608 | 1,290,802 | .41
1935 | 4,202,536 | 4,005,083 | 1,828,565 | .46
1936-37 | ([1]) | ([1]) | ([1]) |
[1] Not publishable; figures would reveal operations of
individual firms.
Source: Dyes and Other Synthetic Organic Chemicals in the United
States, U. S. Tariff Commission.
United States imports and exports.
Resins obtained from urea and thiourea, if imported, would probably be
classified under paragraph 11 of the Tariff Act of 1930. The present rate
of duty under this classification is 4 cents per pound and 30 percent ad
valorem.
There has been no importation of these resins. This is due principally
to the international licensing arrangements which usually include the
allocation of markets.
Exports are not shown separately in official statistics.
6. ACRYLATE RESINS
A new development of widespread importance in the synthetic resin
industry is the commercial production of the polymers of certain
derivatives of acrylic acid. The commercial exploitation of the acrylates
is another example of the belated realization of the value of substances
known for many years. Acrylic acid has been known for about a hundred
years, and the polymer of methyl acrylate was first described in 1880. It
was not until 1927, however, that a suitable method for their commercial
production was developed. The study of the many derivatives of acrylic
and methacrylic acids leads to the conclusion that those of greatest
practical application in the resin field are the lower esters, such as
methyl and ethyl, polymerized separately or together.
Colorless transparency, stability against aging, thermoplasticity, and
chemical resistance to many reagents are the general characteristics
of the acrylate resins. In consistency they range from soft, sticky,
semiliquids to hard, tough, thermoplastic solids. Since these widely
varying properties are obtained by control of manufacturing conditions,
rather than by the use of plasticizers, the resins retain their initial
properties indefinitely. Aging and weathering have no effect as they
are stable under exposure to heat, light, and oxidizing agents. The
methacrylates are harder and tougher but less elastic than the acrylates.
Properties and uses.
The acrylate resins are marketed in a number of forms, such as solutions
in organic solvents, dispersions in water, solid cast sheets, rods and
tubes, and molding powders. All of these are distinguishable from many
other resins by their colorless transparency, adhesive qualities,
great elasticity, and chemical resistance. The brilliant water-white
color makes it possible to secure masses having a high degree of light
transmission and great optical clarity.
The earliest commercial use of the acrylate resins was in laminated
safety glass marketed as Plexigum in the United States and as Luglas and
Sigla in Europe. The extensibility and elasticity of the resin film gives
the laminated glass a flexible or yielding type of break when subjected
to a hard impact. Having excellent adhesion to glass there is no need of
an auxiliary cement to bond the resin to the glass, nor is it necessary
to seal the edges since the resin has good resistance to moisture. The
acrylate resin used for this purpose is in the form of a viscous solution
in an organic solvent. A film is applied to each sheet of glass, the
solvent removed by drying, and the sheets are pressed together.
The harder acrylic resins are used in the form of solid thermoplastics.
Methyl methacrylate is of special interest. As the monomer is a mobile
liquid it can be cast-polymerized to a solid of any desired shape in
predesigned molds or produced in finely divided form for use as molding
powder. The cast resin is marketed in this country as Crystalite,
Plexiglas and Lucite, and in England as Diakon.
The solid acrylate resins are clearer than cast phenolic resins, not as
brittle as the polystyrene resins, and not as tough as cellulose acetate
or nitrocellulose plastics. Their transparency and resistance to aging
and weather permit their use in applications not previously considered
for synthetic resins. Sheets of this resin may be formed or molded
into many useful shapes. The aircraft industry has found them suitable
for windshields and cockpit enclosures to effect streamlining and thus
greatly reduce wind resistance.
Methyl methacrylate is probably the nearest approach to organic glass
thus far developed. Its optical properties make it suitable for spectacle
lenses, camera lenses, magnifying glasses, and protective goggles.
Spectacle lenses are now being made to prescription by molding. It is
estimated that 900 molds will supply the requirements of about 98 percent
of the prescriptions. The excellent light transmitting quality of methyl
methacrylate permits its use in edge lighting, advertising displays, and
instrument dials. It is also used in inspection windows in various types
of machinery where curved sections are necessary and where glass might be
broken.
A synthetic resin combining the properties mentioned, together with high
tensile and impact strength, good dielectric properties, ultraviolet
transmission, and resistance to water, oil, acids, and alkalies is an
important contribution. The acrylates may be colored or have fillers
added to give any desired translucency or opaqueness. They can be sawed,
cut, blanked, turned, drilled, ground, polished, and sanded much the same
as are nitrocellulose plastics.
[Illustration: AIRPLANE COCKPIT ENCLOSURES OF CAST ACRYLATE RESIN.
Source: Rohm & Haas Company, 222 W. Washington Square, Philadelphia, Pa.]
[Illustration: SPECTACLE LENSES MOLDED TO OPTICAL PRESCRIPTION FROM
ACRYLATE RESIN.
Source: Rohm & Haas Company, 222 W. Washington Square, Philadelphia, Pa.]
A new and interesting application of the acrylate resins is as molded
reflectors in a system of indirect highway lighting. The reflectors are
pressed from colorless, transparent methyl methacrylate resin and are
1⅝ inches in diameter. They are assembled in a pressed metal housing to
form a double facing marker which is snap-locked to the top of an angle
iron post. The posts are so located that the reflectors are accurately
aligned 3 feet above the pavement edge. An installation has been made
on U. S. Highway No. 16 between Detroit and Lansing, Mich., at a cost
of about $340 per mile. The motorist provides his own light from his
headlights which strikes the reflectors and is returned as a narrow beam
of brilliant illumination. The chief of the United States Bureau of
Public Roads states that this is a definite contribution to the safety
and utility of the highways at night. The reflector is a group of tiny
cube corners, over 300 in each disk. Each cube corner is a complete
retrodirective optical system; a light ray entering the front surface
is reflected from surface to surface of the cube and after the third
reflection is directed back toward the headlight regardless of the
entrance angle. If the cubes are made with a high degree of dimensional
accuracy, the reflected light has a high candlepower, strong enough to be
seen for a mile.
Other uses for these resins are in sound recording records, dentures,
telephone and radio transmitter diaphragms, novelties, and lighting
fixtures.
The monomer (unpolymerized methyl methacrylate) may be used to impregnate
wood, cloth, wallboard, cork, paper, electrical coils, tile, or stone,
and then polymerized to form the resin. Paper and cloth so treated have
many uses, such as in the electrical and food-packaging industries.
Laminated sheets find wide possibilities for use in the aircraft field,
and for lamp shades. Wood may be impregnated with as much as 60 percent
of the monomer. Solutions of these resins in organic solvents, such as
ethylene dichloride, ethyl acetate, and toluol, are used in surface
coatings, undercoats on difficult adhesion jobs, to impregnate paper and
textiles, and in insulation. These coating solutions are marketed in the
United States under the trade name Acryloids and in Europe under the
trade names, Borron, Plexigum, and Acronol. They may be brushed, sprayed,
dipped, and baked. Baking is recommended to give a higher gloss, better
adhesion, and a harder film. The dried film has an elasticity of 1,000
percent at ordinary room temperature and the light transmission of clear
films is intermediate between ordinary window glass and quartz.
Acrysol is an adhesive consisting of a dispersion of the resin in water
and is recommended for use where adhesion is difficult, as on rubber or
rubberized surfaces.
Production in the United States.
Commercial production of acrylate resins in the United States was started
in 1931 by Rohm and Haas, Philadelphia, Pa., under United States Patents
Nos. 1,388,016 of August 16, 1921, and 1,829,208 of October 27, 1931.
Commercial production of methyl methacrylate resins was started in 1937
by E. I. du Pont de Nemours & Co. This development is under United States
Patent No. 1,980,483, issued in 1934. The liquid monomer is produced at
Belle, W. Va., and shipped to Arlington, N. J., where it is polymerized
by heat to the solid resin.
The output of acrylate resins was hardly more than experimental in 1935
but increased somewhat in 1936 and very appreciably in 1937. Although
statistics of production are not publishable, it can be stated that
in 1937 the output approached that of other synthetic resins made in
commercial quantities. The properties of these resins indicate very
large commercial production in the near future. Prices of the several
types are still high as compared with other resins but should eventually
be somewhat lower than those of cellulose acetate and nitrocellulose
plastics and slightly higher than those of cast phenolic resins.
Imports into and exports from the United States.
There have been no recorded imports of acrylate resins. The two domestic
producers have agreements, licenses, or affiliations with the principal
foreign makers of these products, one in England and one in Germany. Such
arrangements would account for the absence of imports, except for sample
or experimental lots, and might also limit export markets.
7. COUMARONE AND INDENE RESINS
Coumarone and indene are present in appreciable quantities in certain
coal-tar fractions, especially in the solvent naphtha fractions
distilling between 160° and 190° C. No attempt is made to isolate
them from the solvent naphtha. Such a procedure would be difficult
and expensive and, since polymerization readily takes place in dilute
solutions, it is more economical to use fractions of solvent naphtha rich
in these substances. The resins obtained are mixtures of polymerized
coumarone and polymerized indene.
The solvent naphtha must be refined by fractional distillation and
the polymerization very carefully controlled. The polymerizing agent
is usually sulphuric acid although metallic salts, such as aluminum
chloride, are sometimes used. The yield and color of the resin are
affected by temperature and amount of acid used. Light colored resins
are the most desirable. After polymerization the acid or metallic salt
is removed, the product washed and neutralized and finally distilled.
Several byproducts, such as naphtha, paracoumarone soap, and high boiling
oils, are also obtained.
Description and uses.
Coumarone and indene resins are produced and marketed in the United
States under the trade names Cumar and Neville. A number of grades are
available, including the following:
Designation: _Melting point_
Rubber grade, soft 50°- 65° C.
Medium soft 65°- 85° C.
Rubber grade, hard 85°-100° C.
Medium hard 100°-135° C.
Varnish grade 135°-160° C.
In addition to these, certain types are produced for special purposes.
The coumarone and indene resins are used to a large extent in varnishes
for metal and wood. In this application they may be used to replace
all or part of the higher priced natural resins and, to some extent,
ester gum. Their application is somewhat limited by their rather
short durability and elasticity. They are neutral, nonoxidizing and
nonsaponifiable and impart to varnishes greater inertness and adhesion,
fair dielectric strength, and shorter drying time than many of the
natural resins. They cannot be used in nitrocellulose lacquer since they
are not compatible with that plastic.
Another important use of these resins is as an ingredient in mastic
floor tile, in the production of which a thermoplastic binder is
used. Originally, asphalt was used, but demand for light colored tile
necessitated some other binder, the requirements for which were met by
the coumarone and indene resins.
The next largest application of these resins is in rubber compounding,
their effect being to soften the rubber during milling and to facilitate
its handling on rolls. They do not affect the aging qualities of rubber
and are used as a softener for reclaimed as well as for new rubber.
Coumarone and indene resins are used, to some extent, in linoleum, for
impregnating roofing felt, in electrical and friction tapes, paper
and cloth sizing, printing inks, brake linings, adhesives, artificial
leather, oil cloth, and shoe polishes. As a substitute for chicle as
much as 10 percent may be incorporated in the chewing gum mixture.
Their application in molded articles is very limited because of their
brittleness and low tensile strength.
Production in the United States.
There are three domestic makers of these resins. Statistics of production
and sales cannot be published without disclosing the operations of
individual companies. The output, however, has increased appreciably
in recent years and this type of synthetic resin is now among the most
important produced.
Imports into and exports from the United States.
There have been no recorded imports of coumarone and indene resins in
recent years. This is understandable because the duty alone would usually
be more than the domestic price.[4]
Official export statistics do not separately record these resins,
although quantities are exported to nearby countries, including Canada.
8. PETROLEUM RESINS
Considerable research work has been done on the synthesis of resins from
petroleum. It has long been known that cracked petroleum distillates,
when stored for a time, have a tendency to form gums. This tendency is
so pronounced that inhibitors are added to arrest such formation. These
gums are of little value as resins, but it is possible to obtain good
varnish resins by oxidation or controlled polymerization of certain
distillates of petroleum cracking. By carefully controlling operations,
resins of varied properties are obtained and several of them have become
commercially important. The unsaturated compounds, largely olefins
and diolefins, present in highly cracked petroleum distillates can be
polymerized, with certain catalysts. The resin produced depends upon the
types of unsaturated hydrocarbons present and upon the conditions of
polymerization.
Properties and uses.
Several types of petroleum resins are on the market, one made from the
“polymer slop” obtained in the high temperature, vapor-phase cracking
operation, and the other prepared primarily for the production of resin.
The former is marketed under the trade name Petropol and the latter as
Santoresin.
The “Petropol” resins are marketed in two grades, No. 1158 and No. 2138.
The specifications for these are as follows:
-----------------+--------------------------+-------------------------
| Petropol No. 1158 liquid | Petropol No. 2138 liquid
-----------------+--------------------------+-------------------------
Gravity | 15.5-18.5 | 10-11 A. P. I.
Flash | 175° F. minimum. | 230° F. minimum.
Fire | 215° F. minimum. | 280° F. minimum.
Viscosity | 200-225 at 212° F. | 225-300 at 210° F.
Pour | 0° F. maximum. | 45° F. approximate.
Iodine No. | 195 minimum. | 200 minimum.
Molecular weight | 300 approximate. | 425 approximate.
Percent solids | 60-65. | 80-85.
-----------------+--------------------------+-------------------------
Miscible in all proportions with petroleum solvents.
Petropol No. 1158 is used by core oil makers to replace such vegetable
oils as linseed, tung, and perilla. It is used also as a binder and
waterproofing agent on rock wool insulation, replacing rosin and mineral
oil. For spraying coal to minimize dusting, it has the advantage over
calcium chloride of increasing the B. t. u. content of the fuel.
Petropol No. 2138 is a surface coating material which dries by
polymerization. A low cost paint is obtained by combining a pigment and
a plasticizer with the resin. Such paint dries in about one-fourth the
time of linseed oil paints, adheres better to metal, and has greater
resistance to water, acids, and alkalies. In varnishes and enamels it
replaces 12 to 15 percent of tar-acid resin, minimizes skinning, and
gives a higher luster and better flow. Another use of this Petropol is as
a binder in brake linings, replacing certain tar-acid resins.
These two Petropol resins are among the lowest priced synthetics, selling
at present (1938), in tank carlots, for 2 to 5 cents per pound.
The Santoresins are clear, hard, neutral products, melting at 100° C.
They are soluble in drying oils, accelerate the gelatination of tung
oil, are nonreactive with pigments, do not yellow on outdoor exposure,
and are resistant to alkalies, acids, alcohol, and water. Applications
are in protective coatings for wood, metal, paper, leather, cement,
plaster, and other materials, in printing inks, plastic tile, linoleum,
and fiber packages. Being odorless and tasteless they may be used to line
food containers. Their high resiliency and purity recommend their use
as a base for chewing gum. Other uses are as an agent for wetting and
dispersing pigments in rubber and in surface coatings, to replace ester
gum or modified tar-acid resins.
At present the Santoresins are offered at 15 cents per pound in lots of
20,000 pounds or more. Their approximate specifications are:
Appearance A clear hard resin.
Melting point 110° to 120° C. A. S. T. M. (Ring & Ball).
Acid value 0 to 1.
Iodine value 125 to 135.
Specific gravity (at 20° C.) 1.02 or 8.5 lbs. per gallon.
Color (50 percent solution
by weight in toluol) 13 to 15 Gardner Holt standard.
Odor slight when cold, sweet and aromatic when melted. Soluble in
aromatic hydrocarbons, petroleum thinners, turpentine, and varnish oils.
Insoluble in alcohols, esters, ketones, and not completely compatible
with nitrocellulose.
Production.
In the United States two makers of petroleum resins are producing in
commercial quantities and several others are carrying on extensive
research. Production was small in 1935, but increased in 1936 and in
1937. The development and expansion of these resins over the past 2 years
indicate that they will become important.
Imports into and exports from the United States.
There has been no importation of petroleum resins into the United States.
Exports have been confined to samples and experimental quantities.
9. POLYSTYRENE RESINS
The polystyrene resins are thermoplastic products discovered about
100 years ago and are therefore the oldest synthetic resins known.
Their practical application has been greatly retarded by the lack
of inexpensive raw materials of high purity and by the difficulties
experienced in their manufacture.
Ethylene, from petroleum or natural gas, is combined with benzene, from
byproduct coke-oven operations, to form ethyl benzene, which is cracked
to vinyl benzene or styrene. This monomer is polymerized by heat at
100°-150° C. The resin may be extremely tough or very brittle, depending
on the conditions of polymerization. Products having different properties
are obtained by (_a_) low temperature polymerization, (_b_) high
temperature polymerization, and (_c_) catalytic polymerization.
The low-temperature polymers, sometimes designated as alpha-metastyrol,
are produced by polymerizations of vinyl benzene at temperatures under
175° C. A transparent resin, colorless to light yellow, is produced which
is remarkably tough, has excellent tensile strength, unusually good
dielectric properties, and is resistant to most chemicals.
Polymerization at high temperatures (above 175° C.) yields a brittle
resin designated as beta-metastyrol. This type is transparent but usually
dark in color, has low tensile strength and shock resistance.
When vinyl benzene is polymerized in the presence of catalysts, the
resulting resin is similar to resins obtained at high temperatures,
except that it is lighter in color. It is sometimes designated as
gamma-metastyrol. Oxidizing agents are usually the catalysts. Clear,
colorless, vitreous resins are obtained by excluding air during
polymerization.
Properties and uses.
Polystyrene resin is a clear, colorless, highly thermoplastic molding
material with high insulating property, moisture resistance, inertness,
dimensional stability, and impact strength. It can be molded directly
by heat and pressure, and the molded articles are remarkably resistant
to discoloration by light. Polystyrene has a dielectric constant of
2.6, a power factor of 0.02 percent, and is equivalent to fused quartz
as an electrical insulator of low dielectric loss. Films of 0.002 inch
thickness have a dielectric strength of more than 2,000 volts per mil
thickness, which is better than that of any other available synthetic
resin and even better than that of shellac. The tensile strength of
the resin is 5,500 to 7,000 pounds per square inch, and its impact
resistance remains unchanged at temperatures as low as minus 70° C. It
transmits all wave lengths of light down to 3,000 Angstrom units.
Polystyrene is adapted to large scale production of transparent,
translucent, and opaque moldings in a wide variety of colors. It is
easily molded by injection processes, softening at about 150° F. and is
molded at 300° to 375° F., under 3,000 to 30,000 pounds pressure per
square inch. As much as 40 percent filler may be used without seriously
affecting the tensile strength, although the filler does affect the
dielectric properties. Since the resin is thermoplastic there is no waste
in the molding operation; scrap material may be reground and used again.
The unusual properties of these polystyrene resins should give them
widespread applications when the cost is low enough to make them
competitive with other materials. Potentially large volume outlets are
in radio frequency insulation; in dentures because of the strength, low
specific gravity, ease of coloring, and absence of odor and taste of the
material; in electrical parts for submarine and aircraft storage battery
cases and separators; and for the manufacture of glass eyes.
Other possible applications of polystyrene resins are in metal lacquers
and in light colored enamels. Their toughness and light color, together
with their solubility in cheap solvents, suggest their use for these
purposes. Such lacquers are said to be quick-drying, resistant to water,
and moderately so to acids and alkalies.
Production in the United States.
For a number of years, the Naugatuck Chemical Division of the United
States Rubber Co. produced small quantities of polystyrene resins, which
were marketed under the trade name Victron when for general purposes and
under the trade name Marvelyn when for use in dentures. Little progress
was made because of high costs and failure to produce a water-white
product. The sales price was between $1.50 and $2 per pound. Early
in 1937 the Naugatuck Chemical Division transferred its patents on
polystyrene resins to the Carbide and Carbon Chemicals Corporation.
The Dow Chemical Co., Midland, Mich., late in 1937 announced commercial
production of clear, colorless polystyrene in several forms. Styron
is the trade name for the resin from this source. In January 1938,
the Bakelite Corporation announced Bakelite Polystyrene. The plants
manufacturing polystyrene have a capacity in excess of 2,000,000 pounds a
year, and the resin is currently offered at 72 cents per pound.
At least one other domestic firm is doing research on the polystyrenes
and expects to produce commercially in the near future.
Imports into and exports from the United States.
At least two commercial types of polystyrene resins are produced abroad.
Both are made in Germany and marketed under the trade names Resoglas
and Trolitul. Resoglas is a water-white, transparent thermoplastic
resin softening at about 150° C. Its water absorption is low, it is
nonoxidizing, and does not discolor on weathering and baking. Appreciable
quantities are produced in Germany and the sales price there was reported
to have been 40 cents per pound during 1936.
[Illustration: MOLDED POLYSTYRENE RESINS.
Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.]
Small quantities of Resoglas and Trolitul have been imported from Germany
in recent years. Table 9 shows the quantities imported in recent years.
TABLE 9.—_Resoglas and Trolitul: United States imports for consumption,
1933-37_
--------+-----------------------------+---------------------------
| Resoglas (polystyrol) | Trolitul
Year +----------+-------+----------+--------+-------+----------
| Quantity | Value |Unit value|Quantity| Value |Unit value
--------+----------+-------+----------+--------+-------+----------
| _Pounds_ | | |_Pounds_| |
1933 | 771 | ([1]) | | 672 | ([1]) |
1934 | 991 | ([1]) | | 200 | ([1]) |
1935 | 110 | $97 | $0.88 | 4,608 |$3,782 | $0.82
1936 | 2,220 | 1,901 | .86 | 4,671 | 3,641 | .78
1937[2] | None | None | | 6,788 | 4,077 | .60
--------+----------+-------+----------+--------+-------+----------
[1] Not available.
[2] Preliminary.
Source: Analyses of invoices of paragraph 28, act of 1930—U. S.
Tariff Commission.
With the more advanced development of polystyrol resins in Germany prior
to 1938, evidenced by larger commercial production, by wider application,
by the marketing of a water-white product at a considerably lower price,
it might be expected that imports into the United States would have been
in considerably larger amount than shown in table 9. That they were small
was probably due to the high rate of duty which made them expensive
as compared with other synthetic resins in the United States and thus
limited their market to uses in which the others were less satisfactory.
Resoglas was reported to have been selling for 40 cents per pound in
Germany. The imported resin is assessed for duty under the provisions of
paragraph 28 of the Tariff Act of 1930 at 45 percent ad valorem based
on American selling price (as a competitive product) and 7 cents per
pound. The American selling price of the resin made in the United States
until late in 1937, as determined by the Bureau of Customs, Treasury
Department, was $1.85 per pound. The duty was therefore 90 cents per
pound. Imports of Trolitul were valued at 75 cents per pound, giving a
cost of $1.75 per pound laid down, duty paid, in domestic markets. With
the present American selling price of 72 cents per pound, the duty would
be approximately 36 cents per pound.
10. VINYL RESINS
Vinyl acetate, vinyl chloride, and to a lesser extent vinyl
chloroacetate, are the raw materials (monomers) for the several vinyl
resins commercially produced in the United States, Canada, and Germany.
These are all esters of the hypothetical vinyl alcohol and are made by
the action of acetic and hydrochloric acids on acetylene.
The spontaneous polymerization of vinyl derivatives has been known for
many years, although its significance and industrial application have
been realized only recently. Vinyl acetate, probably the most important
of the vinyl esters, was discovered in 1912 and first made in Canada in
1917.
Vinyl resins may be classified into (_a_) polyvinyl acetate, (_b_)
copolymers of vinyl acetate and vinyl chloride, (_c_) polyvinyl chloride,
and (_d_) polyvinyl chloroacetate.
Description and uses.
_Polyvinyl acetate resins._—The several commercial types of vinyl acetate
resins are marketed under the trade names Vinyloid A, Alvar, Gelva,
Formvar, and Mowilith. The first of these is a product of Carbide and
Carbon Chemicals Co., New York, the next three are products of Shawinigan
Chemicals Limited, Shawinigan Falls, Canada, and the last is made by
the Interessen Gemeinschaft Industrie A. G., Germany. Vinyloid A and
Gelva represent the simplest series of vinyl acetate resins and are
made by polymerizing the monomer. The softening point and viscosity of
the polyvinyl acetate resins increase with higher polymerization. Such
resins are colorless, tasteless, odorless, thermoplastic products. They
are soluble in coal-tar solvents and are compatible with certain alkyd
resins, tar-acid resins, and natural resins. Films of polyvinyl acetate
resin are not discolored by exposure, and after irradiation they become
opaque to ultraviolet light, are hard and tough, and have good adherence
and endurance. Their dielectric strength is good and they do not show a
carbon track after the passage of an electric arc. Various grades having
softening points from 80° to 200° C. are available.
Polyvinyl acetate resins are used in making transparent papers,
paper to metal laminations, glassine papers for food packaging, as a
substitute for chicle in chewing gum, and as a component of paints,
varnishes, and lacquers. They have the desirable properties of
compatibility, durability, resistance to abrasion, and rust inhibition
in the surface-coating use. Having the same refractive index as pyrex
glass, they leave no line of demarcation when used as a cement for that
material. They have been used to stiffen toe-caps in shoes and articles
made from paper pulp suspensions. Gelvas are not molded as such because
of their tendency to cold flow. They are used, however, as a binder for
ground mineral fillers in advertising signs and for wood flour in molded
artificial wood carvings. In nitrocellulose lacquers they improve the
adhesion, luster, and toughness.
Alvars are made by replacing part or all of the acetate groups in
Gelva with acetaldehyde. Their viscosity varies with the degree of
polymerization and their properties vary according to the extent of
replacement of the acetate groups. The Alvar types do not cold flow
when molded, are tougher, harder, and have better adhesion but are less
resistant to weathering than the Gelva types. Other properties are about
the same as those of the Gelvas. Alvars having 70 to 80 percent acetate
group replacement are used chiefly in spirit type varnishes, lacquers,
and enamels that must stand exposure to weather. Another Alvar type
is used in injection and press molding. The high binding power of the
resin permits the use of large percentages of filler without loss of
desirable properties. Such moldings may be machined and polished, and
take inserts, such as the wood core in shoe heels. Flexible phonograph
and transcription records made from the Alvars have gained wide approval.
An 85 percent (acetate replacement) type has better impact strength and
is used in toilet articles. Sheets, rods, and tubes of this resin may be
machined in much the same way as nitrocellulose plastic and used where
noninflammability is an asset.
Formvars are made by replacing part or all of the acetate groups in Gelva
with formaldehyde. These resins are colorless, odorless, tasteless, and
thermoplastic. They have higher softening points and greater tensile and
impact strength than the Alvars. They are resistant to alcohols, coal-tar
solvents, fats, oils, or water. Moisture transmission rate through a film
of this resin is about one-tenth that through regenerated cellulose and
one-fourth that through cellulose acetate.
The grades of the Formvars available are designated by the extent of
replacement of the acetate group. The 75-percent replacement type has
excellent mechanical strength and flexibility and is unaffected by
sunlight. Formvars of 95 percent acetate displacement have a tensile
strength as high as 10,000 pounds per square inch and offer possibilities
in the manufacture of artificial silk and photographic film.
The vinyl resins have made possible a new type of safety glass superior
to any heretofore marketed. By condensing butylaldehyde with vinyl
acetate, a polymer is obtained which is used as the inner layer between
two sheets of glass. Heat and pressure secure complete adhesion and yield
a sheet with greater resistance to breakage at low temperatures than the
types now in general use.
Although safety glass was invented in 1905, and many substitutes for the
original nitrocellulose inner layer have been proposed, only two reached
commercial importance before the development of the vinyl resins. These
are cellulose acetate and the acrylate resins. Safety glass used in
automobile windshields up to about 1930 discolored after a year or two
of service. This discoloration was due to the action of the actinic rays
of the sun on the nitrocellulose layer. Since 1930 this difficulty has
been largely overcome by using an actinic ray filter glass (a special
glass with a high iron content) in front of the nitrocellulose sheet, or
by using cellulose acetate, which is not discolored to the same extent
by light, as a substitute for nitrocellulose. Both cellulose nitrate
and cellulose acetate, however, have a tendency to lose toughness and
strength at low temperatures, to absorb moisture, and to separate from
the glass around the edge unless sealed, and to lose their plasticizer
and shrink.
Although a vast improvement over ordinary plate glass, laminated glass
made with cellulose nitrate or acetate has the serious defect of being
brittle at low temperatures, such as prevail in the winters of northern
States. It is easily shattered at zero Fahrenheit, while at 60° F.
and above it is quite strong. This shortcoming led to the development
of the vinyl resin sheet for safety glass with a remarkable degree of
toughness. At normal temperatures it has rubberlike toughness which,
although decreased at low temperatures, is not punctured by the impact
of a half-pound steel ball falling from a 30-foot height at minus 10°
F., whereas nitrocellulose or acetate laminated glass withstands the
impact of a fall from not greater than one-tenth this height. A further
advantage of the vinyl sheet is that it is water resistant, making the
sealing of the edges of the glass unnecessary and thus reducing costs.
Exposure to ultraviolet light in Florida sunlight for more than 2 years
did not discolor it.
The many desirable properties of the vinyl resins, as outlined above,
indicate their widespread use in laminated safety glass when it is
available in sufficient quantities. It is estimated that our annual
output of safety glass interlayer sheets exceeds 17,000,000 pounds, of
which 25 to 30 percent are for windshields, and 70 to 75 percent for side
and back windows of automobiles.
At least one of the series of Mowiliths made in Germany is polymerized
vinyl acetate. It is recommended as an ingredient of water-white
lacquers. It is compatible with nitrocellulose and is extremely durable
and not disintegrated or discolored on exposure to weather.
_Copolymers of vinyl acetate and vinyl chloride._—The simultaneous
polymerization of mixtures of vinyl acetate and vinyl chloride yields
resins with the desirable properties of the two reactants. The extent
of plasticity is largely controlled by varying the ratio of the vinyl
derivatives. Resins high in vinyl chloride content are better suited to
molding, and those high in vinyl acetate are better lacquer ingredients.
These resins are marketed as Vinylites by the Carbide and Carbon
Chemicals Co., New York. They are thermoplastic, odorless, tasteless, and
practically nonflammable. Their outstanding properties are resistance
to water, soap, acids, alkalies, and alcohol, and their strength and
good dielectric properties. Their stability to light is improved by
the addition of ultraviolet absorbing compounds and their stability to
heat by the addition of lead oleate, calcium stearate, or other bases.
Water absorption and compatibility with other resins is increased as the
chloride content increases.
The principal types of copolymers are:
Vinylite VYN, high molecular weight. This resin is used in dentures
where good fatigue resistance, impact strength, and tensile strength are
required. It contains 85 to 88 percent vinyl chloride.
Vinylite VYN, medium molecular weight. This resin is used in general
molding and extending applications including sheets, rods, and tubes. Its
vinyl chloride content averages 85 to 88 percent.
Vinylite VYN, low molecular weight. This resin is used in moldings,
coated paper, lacquers, floor tile, phonograph records, and felt
impregnation. It contains 85 to 88 percent vinyl chloride.
Vinylite VYC. This resin of low molecular weight is compatible with
nitrocellulose and is used in lacquers and finishes for industrial
applications. Lacquers from the Vinylites are called Vinyloids.
The Vinylites for molding are thermoplastic and shrink very little,
making them applicable to large moldings. They may be used in extension
processes such as tooth-brush preforms, pipe lining, and wall trim.
Fillers and pigments may be added, although pigments containing iron and
zinc have harmful effects on the stability of the resin. The fillers
used are wood flour, mica, talc, and alpha cellulose. Fillers reduce the
mechanical strength of the resin and lessen its resistance to water.
Plasticizers, such as dibutyl phthalate or tricresyl phosphate, give a
softer, more flexible resin. Resins from the copolymers resemble the
cellulose derivatives in their molding characteristics, mechanical
strength, and appearance.
In lacquers the Vinylites offer high resistance to water, oils, and
chemicals. The drying of such lacquers is by evaporation rather than
by oxidation. They are suitable for lining food containers, coating
concrete, coating paper for bottle cap liners, and as a stiffener for
box toes of shoes. Their most successful application at present is as an
inside coating for beer cans. Floor tile containing these resins mixed
with slate flour or other filler has good possibilities.
_Polyvinyl chloride resins._—Vinyl chloride may be polymerized to give
nonflammable resins of varying solubilities. The completely polymerized
resin is practically insoluble at ordinary temperatures and is used as a
rubber substitute. It is marketed as Koroseal by B. F. Goodrich Rubber
Co., Akron, O. Compared with natural rubber, it has greater resistance to
acids, alkalies, oils, and alcohol, more flexing life, better resistance
to sunlight, water, and oxidation. Solutions of this resin marketed as
Korolac are used in special types of varnishes.
_Polyvinyl chloroacetate resins._—These resins known as Mowiliths are
made in Germany. Application is largely for surface coating. Practically
no information on this type is available.
_Divinyl acetylene and synthetic rubber._—Two products closely related
to those described above but probably not synthetic resins as defined
for this discussion are divinyl acetylene, a synthetic drying oil, and
Neoprene, a synthetic rubber.
Acetylene, when passed into a solution of copper chloride and ammonium
chloride, combines with itself. When two molecules of acetylene react
monovinyl acetylene is formed, and when three molecules of acetylene
react divinyl acetylene is formed. Monovinyl acetylene reacts with
hydrochloric acid to give chloroprene, which is polymerized to synthetic
rubber or Neoprene.
Divinyl acetylene is a colorless liquid which darkens on exposure to
light and which has an onionlike odor. When polymerized liquids are
formed, then as the reaction progresses viscous products and finally
insoluble, infusible, inert resins. By arresting the reaction before the
gel point is reached, an amber colored heavy liquid, soluble in aromatic
hydrocarbons, is obtained. Since divinyl acetylene will continue to
polymerize at ordinary temperatures, this property is taken advantage of
in using it as a basis for paints, under the name “synthetic drying oil.”
Clear, amber films are obtained from solutions of this oil in solvent
naphtha. Divinyl acetylene is quick drying, is many times more impervious
to moisture than linseed oil, and is thermosetting. It is not attacked
by solvents but is attacked by strong oxidizing agents, and the gelled
material may ignite spontaneously.
Although not classified as a resin, synthetic rubber is discussed here
because of its close chemical relationship to the vinyl resins. It is
made commercially by E. I. du Pont de Nemours & Co., Wilmington, Del.,
and is marketed as Neoprene. It is sold as a plastic polymer which is
vulcanized and processed much the same as natural rubber except that
sulphur is not essential to vulcanization. Synthetic rubber is higher in
price than natural rubber, but it has certain properties which make it
suitable for service conditions where natural rubber is unsatisfactory.
Among these properties are its resistance to gasoline, oils, and greases,
and to elevated temperatures. It does not check or crack on exposure to
sunlight, nor does it oxidize as rapidly as natural rubber. Its principal
applications are in special gaskets, printing rolls, jackets for high
tension cable, linings for gasoline or oil hose lines, balloon fabrics,
diaphragms for regulators, and packing for compressors. Its existence
acts as a limit to the increase in the price of natural rubber and
assures a supply in emergencies.
Production in the United States.
Some of the products described are commercially produced in the United
States; others in Canada or in Germany. Those made in the United States
are usually not made by more than one firm, so that statistics of
production and sales are not publishable. The vinyl acetate resins have
been produced principally in Canada; the copolymers of vinyl chloride and
vinyl acetate are domestic products. In 1935 the United States output of
all vinyl resins exceeded 1,000,000 pounds, a figure that was increased
in 1936 and 1937.
The Canadian output of Gelva and Alvar has reached commercial quantities;
that of Formvar is still confined to experimental plant lots.
The acceptance of vinyl resin sheets for safety glass will greatly
increase the output in 1938. The basic patent, known as the
Morrison-Blaike patent, United States No. 2,036,092 issued on March 31,
1936, is owned by Shawinigan Chemicals, Ltd., Montreal, Canada, who have
licensed several domestic producers. The monomer (vinyl acetate) is now
produced at Niagara Falls, N. Y., by the Niacet Chemicals Corp., which
is jointly owned by this Canadian firm, Carbide and Carbon Chemicals
Corporation, and E. I. du Pont de Nemours & Co. It is also produced by
du Pont at Belle, W. Va. It is shipped, in tank cars, to polymerization
and sheet-forming plants at Indian Orchard, Mass., Arlington, N. J., and
Charleston, W. Va. The Indian Orchard plant, known as the Shawinigan
Resin Products Co., and jointly owned by the Canadian firm and the
Fiberloid Corporation, is now in operation. The plant of the du Pont
Company at Arlington, N. J., began production in May 1938, and that
of Carbide and Carbon Chemicals Corp, at Charleston, W. Va., is in
production. These plants have a combined annual capacity of about 10
million pounds of vinyl resin sheets. According to present plans this
new safety glass will be available for 1939 model automobiles. The resin
sheet to be used is 0.0015 inch thick as compared with the 0.0025 inch
thickness of the present cellulose acetate and nitrocellulose sheet.
Several trade names have been adopted for the vinyl resin sheets, among
which are Vinylite X, and Butvar. The licenses granted to domestic makers
under the Morrison-Blaike patent also permit them to make vinyl acetate
resins for purposes other than safety-glass sheets. Considerable progress
has been made in adapting these resins to injection molding operations
for the production of tooth-brush handles, combs, closures, and other
parts.
Imports into the United States.
The official statistics of imports of vinyl resins prior to 1936 are not
satisfactory for purposes of comparison. Imports could be entered under
either paragraph 2 or paragraph 11 and could be included either with the
statistics of imports of vinyl acetate (see table 91, page 141) or be
thrown into a general group of non-coal-tar synthetic gums and resins, n.
s. p. f., which in addition to vinyl resins would include the acrylates
and ureas. Table 10 gives imports of synthetic resins under paragraph 11
of the Tariff Act of 1930.
TABLE 10.—_Synthetic resins classified under paragraph 11:[1] United
States imports for consumption 1931-37_
--------+----------+-------+-----------
Year | Quantity | Value | Unit value
--------+----------+-------+-----------
| _Pounds_ | |
1931 | 453 | $173 | $0.38
1932 | 454 | 29 | .06
1933 | 1,120 | 496 | .44
1934 | 4,084 | 1,576 | .39
1935 | 3,105 | 1,804 | .58
1936 | 146 | 65 | .45
1937[2] | 1,963 | 439 | .22
--------+----------+-------+-----------
[1] Statistical classification 838.914, synthetic gums and
resins, n. s. p. f. (not coal tar) 1931-35; 838.939 same, other
than those in chief value of vinyl acetate, 1936 and 1937.
[2] Preliminary.
Source: Compiled by the U. S. Tariff Commission from official
statistics of the U. S. Department of Commerce.
A better idea of the imports of vinyl resins prior to 1936 is obtained
by an invoice analysis of imports through the Port of New York under
paragraphs 2 and 11. Table 11 shows imports of vinyl acetate resins based
on such an analysis for 1934 and 1935 and on official statistics for the
years 1936 and 1937.
Similarly table 12 shows imports of Mowilith resins based upon import
analysis for the period 1932-1935, and upon official statistics for 1936
and 1937.
TABLE 11.—_Vinyl acetate resins: United States imports for consumption,
1934-37_
----------+----------+--------+-----------
Year | Quantity | Value | Unit value
----------+----------+--------+-----------
| _Pounds_ | |
----------+----------+--------+-----------
1934[1] | 42,000 | |
1935[1] | 240,000 | |
1936[2] | 600,808 |$144,782| $0.24
1937[2][3]| 652,730 | 201,213| .31
----------+----------+--------+-----------
[1] Invoice analysis of imports entered through the New York
customs district.
[2] Statistical classification 817.58 (par. 2), vinyl acetate,
polymerized, and synthetic resins made in chief value from vinyl
acetate, n. s. p. f. (excluding imports from Germany) and 838.938
(par. 11), synthetic resins made in chief value from vinyl
acetate, n. e. s.
[3] Preliminary.
Source: Compiled by the U. S. Tariff Commission from official
statistics of the U. S. Department of Commerce.
TABLE 12.—_Mowilith resins: United States imports for consumption,
1932-37_
----------+----------+--------+-----------
Year | Quantity | Value | Unit value
----------+----------+--------+-----------
| _Pounds_ | |
----------+----------+--------+-----------
1932[1] | 555 | $229 | $0.41
1933[1] | 741 | 247 | .33
1934[1] | 2,950 | 1,668 | .57
1935[1] | 3,372 | 3,175 | .94
1936[2] | 7,056 | 2,410 | .34
1937[2][3]| 220 | 308 | 1.40
----------+----------+--------+-----------
[1] Analysis of invoices of imports entered through the New York
customs district.
[2] Imports from Germany under statistical classification 817.58
(par. 2), vinyl acetate, polymerized, and synthetic resins made
in chief value of vinyl acetate.
[3] Preliminary.
Source: Compiled by the U. S. Tariff Commission from official
statistics of the U. S. Department of Commerce.
Prior to January 1, 1936, the rate of duty on imports of vinyl resins
was 6 cents per pound and 30 percent ad valorem under paragraph 2, and
4 cents per pound and 30 percent ad valorem under paragraph 11 of the
Tariff Act of 1930. Under the terms of the trade agreement with Canada,
the duty under both paragraphs was reduced to 3 cents per pound and 15
percent ad valorem. This rate was generalized to the other countries from
which we have received imports, with the exception of Germany.
Exports from the United States.
Exports of vinyl resins are not separately shown in official statistics.
11. OTHER SYNTHETIC RESINS
The synthetic resins already discussed are those in substantial
commercial production but, by no means, the only ones known or produced.
Several thousand new ones have been reported and the search continues
in laboratories throughout the world. A successful new product must be
one made from inexpensive raw materials or must possess some property or
advantage that will permit its sale at a price level above that of other
resins.
No attempt is here made to list the host of less important resins.
Certain ones of unusual interest or possessing unique properties are
described below. These include resins obtained from adipic acid, aniline,
citric acid, diphenyl, furfural, lignin, sugar, and sulphonamide.
Adipic acid resins.
The resins from adipic acid are classed as alkyd resins. Those obtained
by the condensation of adipic acid and glycerin are soft and rubbery and
are used to some extent in surface coatings and in photographic films.
In these the resin is formed in three stages as in other alkyd types: A
soluble liquid, a viscous rubbery product, and a form insoluble in the
usual solvents.
Commercial domestic production of these resins was reported for the first
time in 1935 and the output has increased each year since then.
Aniline resins.
Resins obtained by condensing aniline and formaldehyde have been
developed in recent years. Much of the research on this type of resin
was done in Switzerland by the Ciba Co., which holds a number of patents
on it. The Swiss product, called Cibanite, has excellent electrical and
mechanical properties. At least one domestic manufacturer is licensed
under the Swiss-owned patents.
Citric acid resins.
Considerable interest has recently been manifest in synthetic resins
derived from citric acid. The sharp decline in the price of citric acid,
as a result of large scale synthesis from sugar has placed it within the
realm of possibility as a raw material for synthetic resins.
The citric acid resins, classed as alkyd resins, are obtained by
condensing citric acid and glycerin. Commercial production is said to
have started in Europe, but there is no known domestic production as yet.
Diphenyl resins.
A series of products known as Aroclors and made by chlorinating diphenyl
are available in commercial quantities.
Diphenyl was commercially produced for the first time by Swann Research,
Inc., at Anniston, Ala., about 1928. The demand for it as a heat-transfer
medium resulted in large scale output. Later it was found that certain of
the chlorinated compounds of diphenyl possess valuable resin properties.
The Aroclors range from a clear mobile oily liquid to an amber colored
transparent solid. They are thermoplastic, do not polymerize or oxidize,
and are therefore nondrying. They may be dissolved in varnish oils, such
as tung oil and linseed oil, to give varnishes which are resistant to
alkali and water. The diphenyl resins are good adhesives on metal and
glass and give strong joints between such surfaces. They have a high
dielectric constant, resistivity, and a low power factor. Their chief use
is in wire insulation.
The domestic production of chlorinated diphenyls is, at present, solely
by the Monsanto Chemical Company, St. Louis, Mo.
Furfural resins.
Large scale commercial production of furfural, an aldehyde obtained from
oat hulls and other farm waste, has made it available for synthetic resin
manufacture.
Tar-acid furfural resins possess certain outstanding properties, such
as great dimensional accuracy, great reaction speed to the infusible
solid stage, and unusual strength and toughness. They are available in
dark shades only. Printing plates as large as those of metropolitan
daily papers are molded from them as are radio tube bases, all sorts
of electrical parts, and machined parts requiring great dimensional
accuracy. Other uses are in abrasive wheels, varnishes, and adhesives.
Probably the largest domestic maker of furfural resins is the Durite
Plastics Division of Stokes and Smith Company, Philadelphia, Pa.
Resins from sugar.
Many attempts have been made to utilize sugar as a raw material for
synthetic resins. United States Patent No. 1,949,831, dated March 6,
1934, claims a process for the manufacture of molding compounds by
condensing saccharide with aldehydes and urea. Pure sucrose yields a
clear, colorless, nonresilient resin, while molasses and cane sugar
give dark-colored resins. The trade name Sakaloid is used to designate
certain of these resins; there is, however, no known domestic production.
Sucrolite is the trade name of a brand of resins from sugar produced in
Europe.
Sulphonamide resins.
The sulphonamide resins were developed from para toluenesulphonamide, a
byproduct obtained in the manufacture of saccharin (synthetic sweetening
agent).
Para toluenesulphonamide, condensed with formaldehyde or other aldehyde,
forms a viscous mass which, on heating, is converted to a hard
colorless resin. Such resins are compatible with cellulose acetate or
nitrocellulose in lacquers, the combination yielding clear, colorless
lacquers of good gloss and adhesion. Other possible uses are as an
adhesive in safety glass, in certain molding compositions, in insulating
materials, and to deluster artificial silk.
Domestic production of sulphonamide resin is entirely by the Monsanto
Chemical Co., St. Louis, Mo. It is marketed under the trade name
Santolite.
12. ORGANIZATION OF THE SYNTHETIC RESIN INDUSTRY
The discussion of the various synthetic resins on pages 11 to 52 carries
in each case, under the heading of production, a notation of the number
of companies producing that particular resin; and the discussion on pages
86 to 141 of important raw materials for these resins describes briefly
the conditions under which these materials are produced. We shall now
consider the interrelationships between industries producing the several
resins, and the relation of the resin industries to their raw materials
and to some of the important resin-consuming industries.
No description of the organization of a rapidly expanding industry can be
expected to remain accurate for long. But regardless of future changes
that may be expected, the general pattern seems definite enough to
make possible a few broad generalizations. At present the producers of
synthetic resins may be classified in two groups: those making alkyd and
tar-acid resins, and those making all other synthetic resins.
The alkyd resins and the tar-acid resins are produced in large volume,
and for these resins the patent situation is such that there is nothing
to exclude new producers. The result has been that new firms have entered
the field and there has been a marked tendency for concerns using these
resins on a large scale to produce them. This general situation may be
expected to continue as long as the volume of consumption of these resins
is rising. But when consumption levels off, it would not be surprising if
increased competition for new business resulted in consolidations of some
of the producing units.
Each of the other synthetic resins is produced by a small number of
firms and this may be expected to continue as long as the production of
a particular resin is small, or basic patents dominate the situation.
When and if the situation in these respects changes for some of the other
resins, they will probably develop the same tendencies as now exist in
the production of the tar-acid and alkyd resins.
Horizontal relationships between resin producers.
Horizontal relationships between companies are those between different
units in the same industry (say two tar-acid resin producers), or in
different industries each operating at the same stage of industrial
production (say a tar-acid resin producer and a producer of urea
resin). As a rule, extensive horizontal relationships are not common
in relatively young industries, and this is true of the production
of synthetic resins. In general, it has not been necessary to absorb
competitors to achieve a greater volume of sales, and efforts have been
directed to exploiting the possibilities of expansion in a growing
market. This necessitated solving technical problems concerning
improvement of the product and its production on an ever larger scale;
legal problems regarding patents (protection of those owned, and the
policy to be adopted toward unadjudicated patents owned by others); and
the marketing problem of convincing prospective customers of the worth
of a new product. These and other problems incidental to successful
competitive production and sale of a given type of synthetic resin have
been sufficient to restrain the desire to produce more than one type.
The patent situation of most synthetic resins is extremely complicated.
In the case of tar-acid molding resins the basic Baekeland patents have
expired, but for other synthetic resins either the basic patent is
still in force, or it is difficult to say which is the basic patent,
because of lack of adjudication by the courts. In all cases dozens of
supplementary patents are in force and sometimes hundreds. As a result
the patent situation, though one of the bars against entering into a new
field, frequently forces some relationship between producing units in
the same synthetic resin field. Cast phenolic resins afford an example
of patent-licensing of several corporations by another with the payment
of royalties as compensation. In a number of other branches of the resin
industry, such as the laminated tar-acid resins and the alkyd resins, the
mutual desire of producers to avoid litigation has apparently resulted in
“gentlemen’s agreements” not to sue.
Vertical relationships of resin producers.
A vertical relationship is one between producers operating at different
stages of industrial production, such as a firm producing resin and a
firm producing a resin raw material or between the former and a firm that
is a resin consumer. The incentive for a consuming industry operating on
a large scale to make its own resins is naturally greater than for one
using only small quantities. Therefore we may expect to find instances
where a process consuming the resin in quantity and resin manufacture are
both performed by the same company provided other conditions (such as the
patent situation and knowledge of the art of manufacture) are favorable.
_Tar-acid resins for molding._—The present practice of molding resins
is favorable to large-scale production. The shaping of the mold is
expensive, involving skilled labor upon hardened steel; but once the mold
is made it may be used to produce tens or hundreds of thousands of units.
Subsequent labor upon the molded product is usually limited to the simple
task of smoothing the line where the flash is broken off, since the
product comes from the mold in the color and with the surface and shape
desired.
The usual arrangement at the present time is to have a battery of
presses, grouped around central units which supply hydraulic pressure
and steam for heat. A measured amount of molding powder or a pellet
of compressed molding powder is applied to each cavity by the press
operator, who controls by hand the time of application of heat and
pressure and removes the article from the press. The cycle is a matter of
minutes, and since each cycle produces a finished article if the molding
is large, or a number of them if it is small, daily production per worker
is high. The estimated average costs of the different elements in the
process have been apportioned as follows: the cost of raw material is
about one-third the cost of the finished product; and the combined cost
of the mold allocated per unit, the labor cost per unit, and overhead
the remaining two thirds.[5] On small runs labor cost and particularly
allocated mold cost would be much higher, so that molding is usually
uneconomic where only small quantities of the finished product are
desired.
In 1937 there were eight molders that produced their own tar-acid resins
in whole or in part. One of these molders was the third largest producer
of such resins. In the same year six producers of tar-acid resins for
molding, including the first, second, fourth, and fifth largest, confined
their activities to resin making. One producer of raw materials for
tar-acid resins also made the resin on a moderate scale.
This picture of interstage relationship as it existed in 1937 may be
somewhat modified by new developments in molding presses. There are
now available self-contained presses which are not dependent upon
other units for their supplies of heat and pressure and which are
either semiautomatic or automatic. The semiautomatic press requires an
operator for charging the cavity and removing the molded product, but
once adjusted automatically applies the heat and pressure and controls
the time of the pressing cycle. The automatic press, adapted as yet
only to the simpler moldings, requires no attention whatever. These
presses are more expensive, but may be set up anywhere and require less
skilled labor. There is the possibility that they may be installed by
some industrial users of molded articles, and thus take some business
from the custom molder. If this occurs, such molders will presumably buy
their resin from companies that are primarily resin makers, since their
requirements of the material would not ordinarily be large enough to
justify making their own.
_Tar-acid resins for laminating._—The manufacture of laminated resin
products is most economic when done on a large scale, in which case the
impregnation of the paper or fabric becomes a continuous process, the
material feeding from a roll through resin sirup and then through drying
towers, where time and heat may be controlled. The impregnated material
contains resin in the B-stage. The material is then cut up and the sheets
piled together (the number depending on the thickness desired) and sent
to huge presses which, with heat and pressure, compact and unite the
layers and convert the resin to the C-stage. If it is desired to produce
decorative panels with a smooth surface, the top sheet used is one
colored or printed with a design (perhaps a photographic reproduction
of the surface of a cabinet wood) and placed between polished
chromium-plated metal sheets before going to the press. Rods and coil
forms as well as flat sheets are commonly made from laminated material.
Any of these forms may undergo subsequent fabrication; rods and coil
forms cut to required length, thin sheets stamped to shape, gear blanks
cut to final form on automatic gear machines, and decorative panels sawed
to shape.
Many laminators purchase all their resin requirements, but a number of
them make part or all of the tar-acid resin they use. In 1937 there
were seven laminators who made tar-acid resins (including the second,
third, and fourth largest producers of such resins) and four producers
of tar-acid resins for this use (including the largest) which did no
laminating.
_Cast phenolic resins._—The firms producing cast phenolic resins market
them in sheets, rods, and tubes. The castings are made in molds of lead
or glass, and the range of possible shapes is limited. The consumers of
these products fabricate them into finished form by cutting, turning,
and polishing, much as they might fabricate wood or soft metal. Since
considerable labor is required per unit, fabrication is not particularly
adapted to large-scale production. In 1937 there were nine producers of
cast phenolic resins. One of the smaller producers was also a fabricator
of cast resins, and another a producer of raw materials used in making
the resin.
_Tar-acid resins for coatings._—The use of tar-acid resins in surface
coatings has been overshadowed by the more rapid development of alkyd
resins. Nevertheless the volume of tar-acid resins used as raw materials
by varnish and lacquer manufacturers is growing rapidly. They are used in
marine varnishes unmodified by other synthetic resins, but to a greater
extent in combination with other plastics, especially the alkyds and
nitrocellulose. The coating industry includes many units producing on
a large as well as a greater number producing on a smaller scale. In
general, they are not producing their own tar-acid resins. In 1937 there
were 11 producers of tar acid resins for coatings (including the three
largest) who confined their activities to resin production. In addition
there were eight manufacturers of varnishes and lacquers and one producer
of resin raw materials, who also produced tar-acid resins for use in
coatings.
_Tar-acid resins for miscellaneous uses._—The chief uses for tar-acid
resins other than for molding, casting, laminating, and in coatings are
as a bonding material, and as an adhesive. These resins form a valuable
bonding agent for asbestos in brake linings and chemical tanks, for
abrasives and for ground cork in special uses. As an adhesive they are
used in making moisture-resistant plywood.
In 1937 there were five producers of tar-acid resins for miscellaneous
uses, including the largest, who confined their activities to the making
of resins and two, including the second largest, who also made products
in which these resins were consumed.
_Alkyd resins made from phthalic anhydride._—The rapid increase in
the production of alkyd resins for use in coatings is one of the most
remarkable in the whole resin industry. They go into varnishes, lacquers,
and enamels for spraying, brushing, and dipping. The coatings may be
air-dried, with a wide range of drying time, or dried by oven baking. The
volume of alkyd resins used by the coating industry has grown so large
that a number of coating firms have gone into the production of alkyds
and now make part or all of their own requirements. In 1937 there were
24 paint, varnish, and lacquer firms producing alkyd resins. Included in
this number were the first and second largest producers of such resins.
Eleven producers of these resins, including the third and fourth largest,
made alkyd resins for sale only. Each of these groups included one firm
which also made phthalic anhydride.
_Alkyd resins made from maleic anhydride._—In 1937 there were seven
producers of alkyd resins from maleic anhydride who produced for sale
only. This group included the two largest producers and also one firm
which produced maleic anhydride. In addition there were five paint,
varnish, and lacquer firms producing part or all of their needs of
resins of this type. The general conditions under which these resins are
consumed are the same as for alkyd resins made from phthalic anhydride.
_Urea resins for molding._—The conditions under which urea resins are
molded are not greatly different from those already discussed for
tar-acid resins. The molding cycle is somewhat longer and, because of
the light colors used, special precautions must be taken to prevent
discoloration of the molded product by dirt or flecks of molding powder
from other operations, carried through the air or upon the person of the
laborer. In 1937 there were four producers of urea resins for molding.
Three of them, including the two largest, produced for sale only; the
other consumed his own production.
_Urea resins for other uses._—Until recently urea resins were thought
of exclusively for molding, but they are now being used for laminating,
for surface coatings, and also as an adhesive. Ordinarily the ureas are
used only in impregnating the outside laminae of a laminated sheet where
they are valuable for the light colors they make possible. The volume of
urea resins used in surface coatings is small compared with the alkyd or
tar-acid resins used for this purpose, but is increasing. The use of urea
resins in adhesives is still new but promises to become important.
In 1937 there were four producers of the ureas for uses other than
molding, who produced for sale only; and two producers who consumed their
own product.
_Coumarone and indene resins._—Coumarone and indene resins are produced
in connection with the production of solvent naphtha. There were three
producers in 1937, all of whom sold their product. These resins go into
varnishes, where they replace natural resins or ester gum.
_Other resins._—In 1937 there were four producers of vinyl resins in
the United States, and two of these also produced their raw materials.
The vinyl resins were used chiefly in surface coatings, molding, and
in safety glass. The polystyrene resins, used chiefly for molding and
laminating, were offered by two producers for the first time in 1937.
Two other producers offered acrylate resins, which are cast, molded, or
used in surface coatings. In the same year petroleum resins were sold in
good volume, their only producer obtaining them as a byproduct of the oil
industry.
Relationship of the resin industry to other industries.
The term “synthetic resin industry” is a very broad one, referring
in reality to a group of industries producing the varied synthetic
resins—much as the term “steel industry” includes the manufacture of pig
iron, structural steel, tin plate, and wire. But it is interesting to
examine briefly the connection of the synthetic resin industry with some
of the other large industrial groupings.
_Relationship to the chemical industry._—Since the processes involved
in the production of the synthetic resins are essentially of a chemical
nature, the whole industry might be legitimately classed as a branch
of the chemical industry. Historically, the synthetic resin industry
in the United States developed outside of the chemical industry as
it was constituted at the time, but with the passage of years and
the development of a greater variety of resins the connections have
multiplied. Chemical companies supply some of the important raw materials
for synthetic resins; their skilled experts possess the technical
training to develop new resin processes; their research programs from
time to time lead to the discovery of valuable facts regarding resin;
and they possess, or can, more easily than a new company, obtain the
capital necessary to exploit a process.
At present the interest of the large chemical corporations in synthetic
resins ranges from active participation to apparent indifference; but
the growing number of corporations thought of as chemical which are
now engaged in experimental production would seem to indicate that in
time they will be increasingly important in the production of synthetic
resins. Some of the larger chemical companies that are important
producers of synthetic resins in 1938 are:
American Cyanamid Co Urea resins.
Carbide & Carbon Chemicals Corporation Vinyl resins.
Dow Chemical Co Polystyrene resins.
E. I. du Pont de Nemours & Co Alkyd, acrylate, vinyl resins.
Monsanto Chemical Co Petroleum resins.
_Relationship to the surface coating industry._—The use of tar-acid,
alkyd, urea, and vinyl resins as raw material for the surface coating
industry has already been mentioned, and also the fact that the coating
industry is manufacturing a substantial part of its consumption of alkyd
resins.
At present the synthetic resins go chiefly into varnishes, lacquers, and
enamels for inside use and into finishes for outside use on metal. Now
that coatings incorporating synthetic resins are successfully adapted to
outside finishes on wood, the incentive for the production of resins by
the coating industry will presumably increase because of the large volume
of house paints sold.
_Relationship to the electric industry._—The electric industry offered
one of the first large markets for synthetic resin products. Molded and
laminated parts for appliances and fixtures gave good insulation at
ordinary voltages, and frequently allowed a simplification of the design.
This development, coming at a time of rapid expansion in the manufacture
of electric equipment, was a distinct benefit to both the electrical and
synthetic resin industries. The larger electrical manufacturing firms
soon began to do their own molding and laminating and became important
as custom molders. Later the General Electric Co. and the Westinghouse
Electric & Manufacturing Co. manufactured their own tar-acid resins.
Another important outlet for synthetic resins appeared with the
development of the radio industry. Radio now offers a market for
special synthetic resins possessing high dielectric constants at radio
frequencies, and much larger volumes of tar-acid and urea resins are used
in molding the smaller cabinets. As a rule the radio industry purchases
its resin products already molded to order.
_The relationship to the auto industry._—The automobile manufacturing
industry and makers of automobile parts together furnish a substantial
market for synthetic resins. In general, the automobile manufacturers
purchase parts made of resin, already fabricated; parts makers usually
purchase the resins they require. The Ford Motor Co. makes tar-acid
resins for its own use. Working parts, such as timer heads and horn
buttons, are usually of molding tar acid resin; the timing gear usually
of laminated tar-acid resin. For decorative parts, such as dash
instrument knobs and radiator ornaments, urea and cast phenolic resins
have been used. Most of these parts are small, but altogether they
have taken a substantial volume of synthetic resin. Safety glass for
automobile windshields is now being made from vinyl resin.
The future possibilities are difficult to appraise. The automobile
industry is constantly experimenting with new materials and methods, and
its policy of bringing out models annually makes possible rapid adoption
of new developments. Molded window frames have been tried, and such a
use, or use for the complete instrument panel, would obviously consume
synthetic resins in much larger volume. Even whole motor car bodies of
laminated resin have been suggested.
13. THE UNITED STATES TARIFF AND INTERNATIONAL TRADE IN SYNTHETIC RESINS
Synthetic resins enter into the foreign trade of the United States only
to a small extent. This becomes apparent if a comparison is made between
the United States production of these resins and our imports and exports
of them. Table 13 gives the imports and production of synthetic resins in
the United States for 1934 through 1937. Exports are so small that they
are not separately reported.
TABLE 13.—_Synthetic resins: United States production and imports,
1934-37_
[Pounds]
-------------------+------------+------------+-------------+------------
| 1934 | 1935 | 1936 | 1937
-------------------+------------+------------+-------------+------------
Production in the | | | |
United States[1] | 56,059,489 | 95,133,384 | 132,912,821 | 162,104,713
Imports into the | | | |
United States | [2] 19,795 | [2] 21,120 | [3] 626,608 | [3] 673,880
-------------------+------------+------------+-------------+------------
[1] Does not include coumarone and indene resins, sulfonamide
resins.
[2] Does not include imports of vinyl acetate resins which were
not shown separately until 1936.
[3] Includes vinyl acetate resins and all other types imported.
The small size of the international trade in synthetic resins is also
emphasized if we compare the imports of all synthetic resins with the
imports or exports of some of the important raw materials used in their
manufacture. Table 14 makes such a comparison.
TABLE 14.—_Comparison of international trade of the United States in
synthetic resins and in certain raw materials for resins, 1934-37_
[1,000 pounds]
-----------------------------+--------+--------+--------+--------
Imports into or exports from | | | |
the United States | 1934 | 1935 | 1936 | 1937[1]
-----------------------------+--------+--------+--------+--------
Imports: | | | |
Resins | 20 | 21 | 627 | 674
Crude cresylic acid[2] | 7,332 | 7,010 | 13,794 | 16,745
Crude naphthalene | 47,995 | 48,455 | 39,806 | 52,664
Crude glycerin | 15,081 | 8,220 | 11,149 | 13,441
Refined glycerin | 2,214 | 69 | 3,447 | 7,535
Exports: | | | |
Phenol | 329 | 323 | 149 | ([3])
Formaldehyde | 2,597 | 2,598 | 1,844 | 2,865
-----------------------------+--------+--------+--------+--------
[1] Preliminary.
[2] Conversion factor 8.7 pounds per gallon.
[3] Not available.
There are three factors that together largely account for the small size
of our foreign trade in synthetic resins. As a result of the comparative
youth of the resin industry, the complicated patent situation, and the
substantial tariff rates upon imports of resins into the United States,
domestic producers have experienced little competition from abroad. The
first two of these forces plus the tariff barriers of other countries
have caused them to pay little attention to export markets. But it
should be observed that both of the first two forces will become less
important with the passage of time. When home markets have been more
fully exploited, problems of production have become less pressing, and
most of the basic patents on resins have expired, international trade in
synthetic resins may be expected to increase from its present low levels.
If this occurs, the United States, with its large scale production for
the home market and with its generally favorable position with regard to
the raw materials and the technical skills necessary, is more likely to
become a net exporter than a net importer of synthetic resins.
Rapid expansion of business in home markets.
Being young industries and having potentially large home markets awaiting
development, the synthetic resin industries in the United States
naturally began by concentrating first on their numerous production
problems to meet a rapidly expanding domestic demand, improving their
products and devising useful applications.
The tar-acid-formaldehyde resins for molding were the first to develop.
The industry producing them may be said to have started around 1910,
but did not become important until after the World War, when the drop
in price of phenol made the resins available at lower prices. The alkyd
resins and the urea-formaldehyde resins in the United States began to be
important in 1929 and 1930, respectively. The others may be said to be
still in their earliest stages of development as industries, however much
research work may have been done as to their properties and production.
The effect of patents on international trade.
A second factor involved in limiting international trade in resins is
that relating to patents. The basic patents on tar-acid resins have
expired; but while they were in force, they prevented imports into the
United States. In the United States a valid patent can be enforced at
law not only against domestic products which infringe but also against
imports. In addition to court action, the provisions of our tariff law
prohibiting unfair competition in the import trade were invoked to
prevent entry of synthetic phenolic (tar-acid) resin, form C, but when
the basic patent for this material expired, the exclusion order no longer
applied to single color material, except in the matter of certain marking
requirements.[6]
The patent situation may militate against exports as well as imports.
Where a company owns foreign patents it may set up a company to exploit
them abroad, or it may license their use by others. Again, mutual
interest may dictate an exchange (by cross-licensing) of certain patents.
International licensing of patents is usually accompanied by divisions
of international markets through formal or informal understanding. Such
agreements may outlive the life of the patents, especially if bolstered
with financial connections. But unless the original producers continue
to dominate their respective markets, any agreements between them are
likely to diminish in importance, because after the patents expire new
competitors would have a free hand in foreign as well as domestic markets.
The original United States producer of tar-acid resins set up or
licensed companies to manufacture in a number of foreign countries. The
urea-formaldehyde process was developed in Europe and the first American
producer was a licensee of a British corporation. Similar arrangements
exist with regard to most of the other resins.
The United States tariff on resins and resin products.
_Synthetic resins._—Imports of tar-acid, alkyd, coumarone and indene,
styrol, adipic, and aniline resins are dutiable under the provisions of
paragraph 28 of the Tariff Act of 1930, which reads in part: “synthetic
phenolic resin and all resinlike products prepared from phenol, cresol,
phthalic anhydride, coumarone, indene, or from any other article or
material provided for in paragraph 27 [coal-tar intermediates] or
[paragraph] 1651 [coal-tar crudes], all these products whether in a
solid, semisolid, or liquid condition; ... 45 per centum ad valorem
[based on American selling price[7] or United States value[8]] and 7
cents per pound.” Where these resins are produced in the United States,
imports are “competitive” and the dutiable value is based upon American
selling price. If the American selling price is higher than the foreign
value, the effect of this method of valuation is to increase the duty
to which imports are subject. The duty of 45 per cent ad valorem and 7
cents per pound was equivalent to 54 per cent ad valorem on the American
selling price of the small imports of coal-tar resins in 1937. If it
could calculated upon foreign value it would be much higher.
Synthetic resins of non-coal-tar origin, except vinyl resins, are
dutiable under paragraph 11, which reads “synthetic gums and resins not
specially provided for, 4 cents per pound and 30 per centum ad valorem”
on foreign value. This rate was the equivalent of 48 per cent ad valorem
upon the small amount of imports in 1937. The most important resins
included are the urea and acrylate resins.
Between 1930 and 1936 there was some doubt whether vinyl resins were
dutiable under paragraph 11 at the rate quoted or under paragraph 2
which provided for “vinyl alcohol ... homologues and polymers of all the
foregoing; ethers, esters, salts and nitrogenous compounds of any of
the foregoing, whether polymerized or unpolymerized, ... not specially
provided for, 6 cents per pound and 30 per centum ad valorem” on foreign
value. But the Canadian trade agreement, effective January 1, 1936,
reduced the rate on vinyl resins under either paragraph 2 or paragraph 11
to 3 cents per pound and 15 percent ad valorem.[9] The reduced rate was
equivalent to 25 percent ad valorem upon the imports in 1937.
Under these rates, imports of synthetic resins, other than vinyl resins,
have been insignificant.[10] After the reduction of duty, imports of
vinyl resins in 1936 amounted to approximately 600,000 pounds, valued at
$145,000 and in 1937 to 650,000 pounds, valued at $200,000. (See table
11.)
_Articles made of synthetic resins._—Laminated products of which
synthetic resin is the chief binding agent and manufactures of such
products are dutiable under paragraph 1539 (b) at the following rates:
15 cents per pound and 25 percent on laminated sheets or plates[11];
50 cents per pound and 40 percent on laminated rods, tubes, blocks,
strips, blanks, or other forms; and 50 cents per pound and 40 percent on
manufactures of such laminated products. Paragraph 1539 (b) also provides
a duty of 50 cents per pound and 40 percent on manufactures of any other
product of which any synthetic resin is the chief binding agent. These
are, for the most part, molded synthetic resin articles. Paragraph 1539
(b) does not cover articles made entirely of synthetic resin (cast
synthetic resin articles). Such articles unless specifically provided for
in the law are dutiable under paragraph 1558 as manufactured articles,
not specially provided for, at 20 percent ad valorem.
A great many articles, which are made in whole or in part of synthetic
resin, are not dutiable under either paragraph 1539 (b) or paragraph
1558. These are articles which are specifically mentioned in other
paragraphs and subject to the duties provided therein. Table 15 lists a
number of them.
TABLE 15.—_Tariff classification and rates of duty in Tariff Act of 1930
on certain articles made of synthetic resin_
------------------------------+-----------+------------------------
Article | Tariff | Rate of duty
| paragraph |
------------------------------+-----------+------------------------
Beads | 1503 | 75 percent ad valorem.
Buttons | 1510 | 45 percent ad valorem.
Dice, dominoes, chessmen, and | |
poker chips | 1512 | 50 percent ad valorem.
Phonograph records | 1542 | 30 percent ad valorem.
Cigar and cigarette holders | 1552 | 5 cents each plus 60
| | percent ad valorem.
Ash trays, humidors, etc. | 1552 | 60 percent ad valorem.
Umbrella handles | 1554 | 75 percent ad valorem.
------------------------------+-----------+------------------------
In general, the available statistics of imports do not segregate imports
of the specified articles made of synthetic resin from those of the same
articles made of other materials; and the same situation is true of
imports of unspecified articles wholly of synthetic resin which enter
under paragraph 1558. Imports of manufactured articles, n. s. p. f. in
which synthetic resin is the chief binding agent under paragraph 1539
have been small. Figures for recent years are given in table 16.
TABLE 16.—_Manufactured articles n. s. p. f. in which synthetic resin is
the chief binding agent: United States imports for consumption, 1931-37_
----------------------------+--------+--------+--------+--------
Type | 1931 | 1932 | 1933 | 1934
----------------------------+--------+--------+--------+--------
_Quantity (pounds)_ | | | |
Laminated products: | | | |
Sheets and plates | | 10 | | 13
Rods, tubes, blocks, etc. | 215 | 13 | |
Manufactures, n. e. s. | 203 | 453 | 787 | 783
Nonlaminated | 17,623 | 8,511 | 5,352 | 5,729
+--------+--------+--------+--------
Total | 18,041 | 8,987 | 6,139 | 6,525
| | | |
_Value (dollars)_ | | | |
Laminated products: | | | |
Sheets and plates | | 9 | | 16
Rods, tubes, blocks, etc. | 612 | 71 | |
Manufactures, n. e. s. | 1,001 | 883 | 2,133 | 2,299
Nonlaminated products | 31,992 | 10,113 | 7,914 | 10,673
+--------+--------+--------+--------
Total | 33,605 | 11,076 | 10,047 | 12,988
----------------------------+--------+--------+--------+--------
----------------------------+--------+--------+----------
Type | 1935 | 1936 | 1937[1]
----------------------------+--------+--------+----------
_Quantity (pounds)_ | | |
Laminated products: | | |
Sheets and plates | | |
Rods, tubes, blocks, etc. | 609 | 514 | 668
Manufactures, n. e. s. | 1,703 | 3,260 | 10,397
Nonlaminated | 8,423 | 8,069 | 8,759
----------------------------+--------+--------+----------
Total | 10,735 | 11,843 | 19,824
| | |
_Value (dollars)_ | | |
Laminated products: | | |
Sheets and plates | | |
Rods, tubes, blocks, etc. | 579 | 1,329 | 1,920
Manufactures, n. e. s. | 3,778 | 9,468 | 39,232
Nonlaminated products | 11,064 | 10,846 | 18,001
----------------------------+--------+--------+----------
Total | 15,421 | 21,643 | 59,153
----------------------------+--------+--------+----------
[1] Preliminary.
Source: Compiled from Department of Commerce statistics.
14. SYNTHETIC RESIN PRICES, PROPERTIES, AND USES
Synthetic resins as substitutes.
Any new material will in the course of time be applied to the uses
for which it has special advantages, displacing older materials which
formerly served those purposes. The resulting product may sometimes be
used in the same manner as before, or the properties of the substitute
material may widen the usefulness of the finished product, or even make
possible a product almost wholly new.
Before the development of molded synthetic resins, electrical plugs and
sockets were usually made of porcelain or molded of marble dust and
shellac. In this use substitution has been almost complete. Wall plates
for electric switches and outlets were usually of brass. Today molded
tar-acid or molded urea resins are substituted in part. In neither of
these examples has the substituted material any important effect upon the
use of the product.
An example of a substitute material widening the usefulness of the
product is afforded by a new computing scale, where a molded urea resin
casing (substituted for metal in the older model) has aided in decreasing
the weight and has improved the appearance. Another example is the use
of laminated synthetic resin coil forms in radio frequency transformers
which, because of their better electrical properties at high frequencies,
have aided in the design of more compact units.
Examples of synthetic resins making possible a wholly new product are
more difficult to find, but the following will serve as illustrations:
Cast acrylate sheets to form curved cockpit enclosures for airplanes;
molded acrylate buttons for reflecting road markers; and new special
coatings, which make possible the use of metal cans for preserving foods
and beverages hitherto impossible to can without loss of flavor.
Motives for substitution.
One of the most important reasons why a manufacturer may decide to
substitute a synthetic resin for another material is the resulting
economy in the sense of economy in total costs. As a rule, the synthetic
resin will be more expensive pound for pound than the material for which
it is substituted; but frequently the manufacturing cost is enough lower
to more than make good the difference in material cost, because the resin
part will come from the mold almost in finished form, whereas the part
made of wood or metal will require considerable fabrication. In some
cases there may be a saving in marketing costs. For example, the shades
for large office fixture lights are now made of synthetic resin as well
as of opal glass. The resin shades are less expensive to ship because
they are lighter and require less expensive packing.
Another incentive toward substitution is to give novelty, and hence sales
appeal, to an old product. In many cases the use of synthetic resins fits
in with the present tendency to redesign an old-style product so that it
will be more compact, have more pleasing lines, and more color.
Still another incentive toward substitution is to give the product
greater usefulness, or lower costs in use. The great expansion in the
use of synthetic resins in surface coatings has come about because, with
these materials, coatings can be developed to fit special purposes, and
dry rapidly, which means an important saving to those who use them.
Materials displaced by synthetic resins.
The wide range of uses to which synthetic resins are now applied implies
that the materials displaced are numerous. For example, cast or wrought
iron or steel is displaced in timing gears and in many small machine
parts, such as cradle-type telephones; nonferrous metals in small machine
parts and novelties, such as inexpensive bracelets; glass in lamp shades
and in cosmetic containers; natural resins in lacquers; plastics, such
as cellulose acetate in safety glass or cellulose nitrate in colored
lacquers; other adhesives in bonding plywood; and cork or metal in bottle
closures.
In general, the quantity of material displaced is a very small part of
that material’s total market. Frequently, however, industries producing
the finished product have had to make substantial changes in their
equipment in order to use synthetic resins. This has been true in the
button industry, in the bottle closure industry, in the varnish and
lacquer industry, and in the various electrical supply industries; and
readjustment is now proceeding in the fancy container industry and in the
safety glass industry.
Competition between synthetic resins.
Any particular synthetic resin must compete for its market with other
synthetic resins, as well as with other materials. The basis of choice
or substitution will be the same as that which has already been briefly
discussed in connection with the displacement of other materials by
resins. As between a number of resins with properties fitting them for a
particular use, the total costs of using each will be compared and the
choice will go to the least expensive; but where a resin has special
advantages in a particular use it may win out over a less expensive
resin.
It should be emphasized that this battle of materials for markets
is a never-ending one. The fact that a specific synthetic resin has
achieved a certain position is no guarantee that it may not lose it
wholly or in part to some newer resin or other material. Thus cast
phenolic resin was for a time the only resin available in light colors
but urea resins became available in pastel shades and more recently
water-clear polystyrene and acrylate resins have come on the market.
Until recently tar-acid resins were without competition in laminating,
but urea resins now are used to some extent for the surface laminae and
the tar-acid resins now face a potential threat in a new product offered
to laminators. If the use of this cellulose sheet, which looks much like
blotting paper and which has lignin incorporated in it to act as a binder
in the press, should materially decrease the cost of laminated sheets, it
will mean serious new competition for the tar-acid laminating resins.
The general effect of the increase in number of types of synthetic resin
has been to modify the market outlook of the producers of each type. They
are now more inclined to view the market as being limited by the price
at which they can supply their product and by the physical properties of
each resin rather than attempt to exploit it as a universal resin for all
purposes.
Resins classified by cost.
At present the resins produced in largest volume are the alkyd resins for
use in surface coatings; the tar-acid resins for molding, laminating, and
surface coatings; the urea resins, chiefly for moldings; and the cast
phenolic resins. Roughly, the price per pound of pure resin material[12]
for these various resins may be compared as follows:
_Average sales price
of net resin, 1937
(per pound)_
Type of resin:
Cast phenolic $0.41
Tar-acid:
For molding .18
For laminating .13
For coatings .17
Alkyd .20
Urea .45
Because the cost of the filler is less per pound than the cost of the
resin, the cost of the tar-acid and urea molding powders will be less
than the figures given for the pure resin. On the other hand, wholesale
prices paid by consumers will include transportation and distribution
costs not included in the figures of manufacturers’ sales.
Vinyl resins, acrylate resins, and polystyrene resins are at present
produced in much smaller volume than those just listed. If and when the
volume of production is increased the price may be decreased. In 1937,
the price per pound of pure resin[12] was as follows:
_Average sales price
of net resin, 1937
(per pound)_
Type of resin:
Vinyl $0.69
Acrylate 1.66
Early in 1938, acrylate resins were being offered for sale at 85 cents
per pound for molding powder and $1.25 per pound for the cast material;
polystyrene resins at 72 cents per pound.
Petroleum resins, in 1937, sold for an average of 2 cents per pound net
resin content.[12] This low price puts them beyond competition of the
other synthetic resins in the uses in laminating and coating to which
they are adapted.
The physical properties of a resin and its uses.
A more expensive resin will be used in preference to a cheaper one, only
if the higher cost is more than offset by some physical property, such as
color, which makes it more desirable in a particular use. The most common
molding resin at present is the tar-acid type, but it is available only
in the darker colors and therefore has been at a disadvantage, where a
light color is desired, in competition with cellulose nitrate (celluloid)
and cellulose acetate plastics or with urea and cast phenolic resins. In
recent years the production of cellulose acetate molding compounds and
of urea resins has increased rapidly, largely under this stimulus. The
desire for color also promises well for the future of the acrylate and
polystyrene resins which are produced in water-clear grades or colored
with dyes or pigments.
TABLE 17.—_Synthetic resins and other plastics: Properties that affect
appearance_
-----------------------+---------+-------------+-----------+-------------
Type |Machining| Clarity | Color |Burning rate
|qualities| possibilities
-----------------------+---------+-------------+-----------+-------------
Synthetic resins: | | | |
| | | |
Tar-acid—Formaldehyde:| | | |
| | | |
Molded, wood flour | Fair to | Opaque | Limited | Very low
filler. | good | | |
| | | |
Molded, mineral | do | do | do | Nil
filler. | | | |
| | | |
Molded, fabric | do | do | do |Approximately
filler. | | | | nil
| | | |
Laminated, paper | Fair to | do | do | Very low
base. |excellent| | |
| | | |
Laminated, fabric | do | do | do | do
base. | | | |
| | | |
Laminated, asbestos | do | do | do |Approximately
cloth base. | | | | nil
| | | |
Cast |Excellent|Transparent, | Unlimited | Very low
| |translucent, | |
| | opaque | |
| | | |
Tar-acid—Furfural: | | | |
| | | |
Wood flour filler. | Fair to | Opaque | Limited | do
| good | | |
| | | |
Mineral filler. | do | do | do | Nil
| | | |
Fabric filler. | do | do | do | do
| | | |
Urea—Formaldehyde. | Fair |Translucent, | Unlimited | Very low
| | opaque | pastel |
| | | shades |
| | | |
Vinyl, unfilled. | Good |Transparent, | Unlimited | Nil
| |translucent, | pastels |
| | opaque | to black |
| | | |
Vinyl, filled. |Excellent| do | do |Approximately
|(organic | | | nil
| filler) | | |
| | | |
Acrylate |Very good|Transparent | Unlimited | Slow
| |(95% light | |
| |transmission)| |
| | | |
Polystyrene | Poor to |Transparent, | do | do
| good | opaque | |
| | | |
Other plastics: | | | |
| | | |
Shellac compound. | do | Opaque | Limited, | High (wood
| | | pastels | filler)
| | | excluded |
| | | |
Cold molded: | | | |
| | | |
Nonrefractory. | Poor | do |Dark colors| Nil
| | | only |
| | | |
Refractory. | do | do | Gray | do
| | | |
Rubber compounds: | | | |
| | | |
Chlorinated rubber. | |Translucent, | Unlimited | do
| | opaque | |
| | | |
Modified isomerized | Good |Transparent | do | Slow
rubber. | | | |
| | | |
Hard rubber. | Fair | Opaque | Limited | Medium
| | | |
Casein | Good |Translucent, | Unlimited | Very low
| | opaque | |
| | | |
Cellulose compounds: | | | |
| | | |
Ethyl cellulose | do |Transparent, | do | Slow
| |translucent, | |
| | opaque | |
| | | |
Cellulose acetate | do | do | do | do
sheet | | | |
| | | |
Cellulose acetate | do | do | do | do
molding | | | |
| | | |
Cellulose nitrate | do | do | do | Very high
-----------------------+---------+-------------+-----------+-------------
-----------------------+---------------+--------------+-----------
Type | Effect of age | Effect of |Refractive
| | sunlight |index No[1]
-----------------------+---------------+--------------+-----------
Synthetic resins: | | |
| | |
Tar-acid—Formaldehyde:| | |
| | |
Molded, wood flour | None | Light shades |
filler. | | discolor |
| | |
Molded, mineral | do | do |
filler. | | |
| | |
Molded, fabric | do | do |
filler. | | |
| | |
Laminated, paper | Improves | Lowers |
base. | mechanical | surface |
| and | resistance |
| electrical | |
| properties | |
| | |
Laminated, fabric | do | do |
base. | | |
| | |
Laminated, asbestos | do | |
cloth base. | | |
| | |
Cast | Hardens | Colors | 1.5-1.7
| slightly | may fade |
| | |
Tar-acid—Furfural: | | |
| | |
Wood flour filler. | do |Light shades |
| | discolor |
| | |
Mineral filler. | do | do |
| | |
Fabric filler. | do | do |
| | |
Urea—Formaldehyde. | do | None | 1.54-1.6
| | |
Vinyl, unfilled. | Strength | Darkens | 1.53
| unaffected | |
| | |
Vinyl, filled. | None | Discolors |
| | |
Acrylate | do | None | 1.49
| | |
Polystyrene | do | Yellows | 1.67
| | |
Other plastics: | | |
| | |
Shellac compound. | | None |
| | |
Cold molded: | | |
| | |
Nonrefractory. | | |
| | |
Refractory. | | |
| | |
Rubber compounds: | | |
| | |
Chlorinated rubber. | Slight | Darkens | 1.56
| embrittlement | |
| | |
Modified isomerized | None | Slight |
rubber. | | surface |
| | crazing |
| | |
Hard rubber. | do | Discolors |
| | surface, |
| | resistivity |
| | decrease |
| | |
Casein | Hardens | Colors |
| slightly | may fade |
| | |
Cellulose compounds: | | |
| | |
Ethyl cellulose | Slight | Slight | 1.47
| | |
Cellulose acetate | do | do | 1.49-1.50
sheet | | |
| | |
Cellulose acetate | do | do | 1.47-1.50
molding | | |
| | |
Cellulose nitrate | Slight |Discolors and | 1.50
| hardening | becomes |
| | brittle |
-----------------------+---------------+--------------+-----------
[1] Specified refractive degree.
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedures and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, no. 2, opp. p. 120. October
1937.
TABLE 18.—_Synthetic resins and other plastics: Molding properties_
------------------------------+--------------+-------------+-------------
| General | Compression | Compression
Type. | molding | molding | molding
| qualities | temperature | pressure
------------------------------+--------------+-------------+-------------
| | _°F._ |_Pounds per
| | | square inch_
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler | Excellent | 280-360 | 1,600-4,500
Molded, mineral filler | Excellent | 270-350 | 1,600-6,000
| to fair | |
Molded, fabric filler | Good to fair | 270-330 | 3,000-8,000
Laminated, paper base | | 250-365 | 1,000-3,000
Laminated, fabric base | | 250-365 | 1,000-3,000
Laminated, asbestos cloth | | 250-325 | 1,000-3,000
base | | |
Cast | | |
Tar-acid—Furfural: | | |
Wood flour filler | Excellent | 330-400 | 1,000-3,000
Mineral filler | do | 330-360 | 1,000-3,000
Fabric filler | Good to fair | 300-360 | 1,000-3,000
Urea—Formaldehyde (alpha | Excellent | 290-325 | 1,500-6,000
cellulose filler) | | |
Vinyl, unfilled | Good | 240-275 | 1,500-2,000
Vinyl, filled | Excellent | 250-300 | 2,000-2,500
Acrylate | do | 285-315 | 1,500-5,000
Polystyrene | Good | 280-325 | 300-2,000
Other plastics: | | |
Shellac compound | do | 240 | 1,000-1,200
Cold molded: | | |
Nonrefractory | Fair | |4,000-12,000
Refractory | do | |4,000-12,000
Rubber compounds: | | |
Chlorinated rubber | do | 200-225 | 2,000-5,000
Modified isomerized rubber| Good | 260-300 | 1,200-4,000
Hard rubber | Fair | 285-350 | 1,200-1,800
Casein | Poor | 200-225 | 2,000-2,500
Cellulose compounds: | | |
Ethyl cellulose | Excellent | 212-300 | 1,000-5,000
Cellulose acetate sheet | do | 210-320 | 500-5,000
Cellulose acetate molding | do | 250-350 | 500-5,000
Cellulose nitrate | Good | 185-250 | 2,000-5,000
------------------------------+--------------+-------------+-------------
------------------------------+-------------+--------------+-------------
| Injection | Injection | Compression
Type. | molding | molding | ratio
| temperature | pressure |
------------------------------+-------------+--------------+-------------
| _°F._ | _Pounds per |
| | square inch_|
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | _|
Molded, wood flour filler | 275-375 | 2,000-10,000 | 2.5-3.0
Molded, mineral filler | 275-350 | 2,000-15,000 | 2.2-7.1
Molded, fabric filler | | | 2.5-11.0
Laminated, paper base | | | 1.5-3.0
Laminated, fabric base | | | 1.5-3.0
Laminated, asbestos cloth | | |
base | | |
Cast | | |
Tar-acid—Furfural: | | |
Wood flour filler | 250-290 | 300-5,000 | 2.5-3.0
Mineral filler | 250-290 | 300-5,000 | 2.5-6.0
Fabric filler | 250-290 | 300-50,000 | 4.0-15.0
Urea—Formaldehyde (alpha | | | 3.0
cellulose filler) | | |
Vinyl, unfilled | | | 2.0
Vinyl, filled | | | 1.5-3.5
Acrylate | 325-475 | 3,000-30,000 | 2.0
Polystyrene | 300-375 | 3,000-30,000 | 2.5
Other plastics: | | |
Shellac compound | | |
Cold molded: | | |
Nonrefractory | | | 2.5
Refractory | | | 3.5
Rubber compounds: | | |
Chlorinated rubber | | | 2.0-3.0
Modified isomerized rubber| | | 3.0
Hard rubber | 180-220 | 2,000-5,000 | 4.0-6.0
Casein | | |
Cellulose compounds: | | |
Ethyl cellulose | | | 2.2-2.9
Cellulose acetate sheet | | |
Cellulose acetate molding | 300-440 | 3,000-30,000 | 2.0-2.8
Cellulose nitrate | | |
------------------------------+-------------+--------------+-------------
------------------------------+-------------------+-----------
| Mold | Effect
Type. | shrinkage | on metal
| | inserts
------------------------------+-------------------+-----------
| _Inches per inch_ |
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler | 0.006-0.010 | Inert.
Molded, mineral filler | .002- .006 | Do.
| |
Molded, fabric filler | .003- .007 | Do.
Laminated, paper base | | Do.
Laminated, fabric base | | Do.
Laminated, asbestos cloth | | Do.
base | |
Cast | | Do.
Tar-acid—Furfural: | |
Wood flour filler | .005- .009 | Do.
Mineral filler | .002- .006 | Do.
Fabric filler | .0025-.006 | Do.
Urea—Formaldehyde (alpha | .007- .011 | Do.
cellulose filler) | |
Vinyl, unfilled | .001 | Not used.
Vinyl, filled | .000 | Inert.
Acrylate | .002- .003 |
Polystyrene | .002-.0025 |
Other plastics: | |
Shellac compound | .002 | Do.
Cold molded: | |
Nonrefractory | .000- .022 | Do.
Refractory | .000 | Do.
Rubber compounds: | |
Chlorinated rubber | |
Modified isomerized rubber| .000 | Do.
Hard rubber | |
Casein | |
Cellulose compounds: | |
Ethyl cellulose | .0003-.0007 | Do.
Cellulose acetate sheet | ([1]) | Do.
Cellulose acetate molding | ([1]) | Do.
Cellulose nitrate | |
------------------------------+-------------------+-----------
[1] Positive and injection 0.002-0.003; semipositive 0.005-0.007;
flash 0.008-0.009.
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedures and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October
1937.
Table 17 lists the properties which affect appearance and gives in
addition to the color range, the clarity, material, the burning rate,
the effect of age and sunlight, the refractive index, and the machining
quality of each synthetic resin.
Table 18 lists molding properties of synthetic resins. Of special
interest are the possibilities of using a resin in injection molding. The
thermoplastic resins and plastics (see softening point in table 20) are
generally preferred to the thermosetting materials for injection molding
because they permit the reuse of material otherwise wasted.
Table 19 lists the strength properties of the synthetic resins; table 20
the heat properties; table 21 the electrical properties; and table 22 the
resistance to acids, alkalies, and solvents. All of these qualities are
important in some uses and each quality may be paramount in a few. Each
material has its limitations and its special advantages and the consuming
industry must choose the one best suited to its purposes. The tie-up
between specific properties and particular uses is exemplified by vinyl
resins, which because of their great elasticity at low temperatures, are
used in safety glass, and by the polystyrene resins, which because of
their electrical properties at high frequencies, are used in laminated
electrical parts. As production of the various resins increases new uses
will probably be found for most of them.
TABLE 19.—_Synthetic resins and other plastics: Strength properties_
-------------------------------+--------------+------------+-------------
Type | Tensile | Elongation | Modulus of
| strength | | elasticity
-------------------------------+--------------+------------+-------------
|_Pounds per | _Percent_ |_Pounds per
| square inch_ | | square inch_
Synthetic resins: | | | _× 10³_
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler | 6,000-11,000 | | 10-15
Molded, mineral filler | 5,000-10,000 | | 10-45
Molded, fabric filler | 6,500- 8,000 | | 7-12
Laminated, paper base | 6,000-13,000 | | 5-20
Laminated, fabric base | 8,000-12,000 | | 5-15
Laminated, asbestos cloth | 9,000 | |
base | | |
Cast | 5,000-12,000 | | 5-15
Tar-acid—Furfural: | | |
Wood flour filler | 5,000-12,000 | | 10-25
Mineral filler | 4,000-12,000 | | 10-45
Fabric filler | 5,000-10,000 | | 7-12
Urea—Formaldehyde | 8,000-13,000 | | 16
Vinyl, unfilled | 8,000-10,000 | | 3.5-4.1
Vinyl, filled | 6,000-12,000 | | 3.5-8.5
Acrylate | 7,000- 9,000 | 1.0 | 6
Polystyrene | 5,500- 7,500 | 1.0 | 4.6-5.1
Other plastics: | | |
Shellac compound | 900- 2,000 | |
Cold molded | | |
Nonrefractory | | |
Refractory | | |
Rubber compounds: | | |
Chlorinated rubber | | |
Modified isomerized rubber | 4,300 | 0.013 | 4.7
Hard rubber | 4,000-10,000 | 8-15 | 5.3
Casein | 7,600 | | 5.1-5.7
Cellulose compounds: | | |
Ethyl cellulose | 2,000- 7,000 | | 2.8
Cellulose acetate sheet | 6,000-11,000 | 20-55 | 1-3
Cellulose acetate molding | 3,500-10,000 | 10-48 | 2-4
Cellulose nitrate | 5,000-10,000 | 10-40 | 2-4
-------------------------------+--------------+------------+-------------
-------------------------------+---------------+---------------
Type | Compressive | Flexural
| strength | strength
-------------------------------+---------------+---------------
| _Pounds per | _Pounds per
| square inch_ | square inch_
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler | 16,000-36,000 | 8,000-15,000
Molded, mineral filler | 18,000-36,000 | 8,000-20,000
Molded, fabric filler | 20,000-32,000 | 10,000-13,000
Laminated, paper base | 20,060-40,000 | 13,000-20,000
Laminated, fabric base | 20,000-44,000 | 13,000-20,000
Laminated, asbestos cloth | 18,000-40,000 | 17,000
base | |
Cast | 15,000-30,000 |
Tar-acid—Furfural: | |
Wood flour filler | 28,000-36,000 | 10,000-16,000
Mineral filler | 24,000-36,000 | 8,000-14,000
Fabric filler | 26,000-30,000 | 10,000-16,000
Urea—Formaldehyde | 24,000-35,000 | 13,000-15,000
Vinyl, unfilled | | 10,000-13,000
Vinyl, filled | |
Acrylate | 8,000 | 15,000-17,000
Polystyrene | 13,000-13,500 | 6,500- 8,000
Other plastics: | |
Shellac compound | |
Cold molded | 6,000-15,000 | 5,300- 7,500
Nonrefractory |} 16,000 | 6,000
Refractory |} |
Rubber compounds: | |
Chlorinated rubber | |
Modified isomerized rubber | 8,500-11,000 | 7,000- 9,000
Hard rubber | 8,000-12,000 |
Casein | |
Cellulose compounds: | |
Ethyl cellulose | |
Cellulose acetate sheet | 4,000-16,000 |
Cellulose acetate molding | 11,000-16,000 | 5,200- 8,800
Cellulose nitrate | |
-------------------------------+---------------+---------------
-------------------------------+----------------------------+------------
Type | Impact strength[1] | Hardness[2]
| (foot pounds) |
-------------------------------+----------------------------+------------
| |
| |_Brinell No_
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler | 0.10-0.28; I, N | 30-45
Molded, mineral filler | 0.11-0.36; I, N |
Molded, fabric filler | 0.4-2.4; I, N |
Laminated, paper base | 0.4-1.2; I, N | 24-40
Laminated, fabric base | 0.8-5.2; I, N | 30-45
Laminated, asbestos cloth | |
base | |
Cast | 0.1-1.5; I, N | 30-45
Tar-acid—Furfural: | |
Wood flour filler | 0.08-0.52; C, N | [3]35-40
Mineral filler | 0.08-0.48; C, N | [3]44-46
Fabric filler | 1.6-3.1; C, N | [3]30-35
Urea—Formaldehyde | 0.7-1.5; C, U | [4]48-54
Vinyl, unfilled | 0.3-0.6; I, N | 15-25
Vinyl, filled | 0.1-0.7; I, N | 15-25
Acrylate | 0.25-0.5; C, N | [4]18-20
Polystyrene | 0.16-0.25; I, N | 20-30
Other plastics: | |
Shellac compound | |
Cold molded | 0.4; C |
Nonrefractory | 0.4; C |
Refractory | |
Rubber compounds: | |
Chlorinated rubber | 3.0+; C, U |
Modified isomerized rubber | 2.6-6.2; I, N | [5]85-90
Hard rubber | 0.5; I | 31
Casein | 1.0; I | 23
Cellulose compounds: | |
Ethyl cellulose | 1-4; I, N (per in. sq.) |
Cellulose acetate sheet | 2-7; C, N (per in. sq.) | [6]6-11
Cellulose acetate molding | 3-12; C, N (per in. sq.) | [6]6-7.5
Cellulose nitrate | 3-12; C, N (per in. sq.) | [6]8-11
-------------------------------+----------------------------+------------
[1] ASTM D256-34T. C = Charpy; I = izod; N = notched; U =
unnotched.
[2] 2.5 mm ball; 25 kg. load unless otherwise noted.
[3] 50 kg. load.
[4] 10 mm. ball; 500 kg. load.
[5] Shore.
[6] 10 kg. load.
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedures and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, No. 2, opp. p. 120; October
1937.
TABLE 20.—_Synthetic resins and other plastics: Heat properties_
-----------------------------------+--------------------+---------------
| Thermal | Specific
| conductivity | heat
+--------------------+---------------
Type | 10⁻⁴ calories |
| per second per |
| square centimeter | Calories per
| per 1°C. | °C. per gram
| per centimeter |
-----------------------------------+--------------------+---------------
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler | 4-12.2 | 0.35-0.36
Molded, mineral filler | 8-20 | 0.25-0.35
Molded, fabric filler | 3-5 | 0.30-0.35
Laminated, paper base | 5-8 | 0.3 -0.4
Laminated, fabric base | 5-8 | 0.3 -0.4
Laminated, asbestos cloth base | |
Cast | 3-5 | 0.3- 0.4
Tar-acid—Furfural: | |
Wood flour filler | 3.5-5 | 0.3- 0.4
Mineral filler | 10-20 | 0.3- 0.4
Fabric filler | 5-8 | 0.3- 0.4
Urea—Formaldehyde | 7.13 |
Vinyl, unfilled | 4 | 0.244
Vinyl, filled | Varies | Varies
Acrylate | 4.3-6.8 | 0.45
Styrol | 1.9 | 0.324
Other plastics: | |
Shellac compound | |
Cold molded: | |
Nonrefractory | |
Refractory | |
Rubber compounds: | |
Chlorinated rubber | |
Modified isomerized rubber | 2.6-2.9 |
Hard rubber | 3.2 | 0.33
Casein | |
Cellulose compounds: | |
Ethyl cellulose | |
Cellulose acetate sheet | 5.4-8.7 | 0.3- 0.4
Cellulose acetate molding | 5.4-8.7 | 0.3- 0.45
Cellulose nitrate | 3.1-5.1 | 0.34-0.38
-----------------------------------+--------------------+---------------
-----------------------------------+-------------------+----------------
| Thermal | Resistance to
| expansion |continuous heat
+-------------------+----------------
Type | |
| |
| 10⁻⁶ per °C. | °F.
| |
| |
-----------------------------------+-------------------+----------------
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler | 3.7-7.5 | 350
Molded, mineral filler | 2.5-4 | 450
Molded, fabric filler | 2-6 | 250-350
Laminated, paper base | 2 | 212-300
Laminated, fabric base | 3 | 212-350
Laminated, asbestos cloth base | 2 | 400-500
Cast | 2.8 | 160
Tar-acid—Furfural: | |
Wood flour filler | 3 | 280-400
Mineral filler | 2 | 350-500
Fabric filler | 4.5 | 280-350
Urea—Formaldehyde | 1.5 | 160
Vinyl, unfilled | 6.9 |
Vinyl, filled | Varies |
Acrylate | 8.5 |
Styrol | 10.2 |
Other plastics: | |
Shellac compound | | 150-190
Cold molded: | |
Nonrefractory | | 500
Refractory | | 1,300
Rubber compounds: | |
Chlorinated rubber | |
Modified isomerized rubber | 7-8 |
Hard rubber | 8.0 |
Casein | 8 |
Cellulose compounds: | |
Ethyl cellulose | |
Cellulose acetate sheet | 14-16 | 140-180
Cellulose acetate molding | 14-16 | 140-180
Cellulose nitrate | 12-16 | ca. 140
-----------------------------------+-------------------+----------------
-----------------------------------+-----------+------------+-----------
| Softening | Distortion |
| point | under heat |
+-----------+------------+
Type | | |
| | | Tendency
| °F. | °F. | to cold
| | | flow
| | |
-----------------------------------+-----------+------------+-----------
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler | None | 240-285 | None.
Molded, mineral filler | do. | | Do.
Molded, fabric filler | do. | | Do.
Laminated, paper base | do. | 320 | Do.
Laminated, fabric base | do. | | Do.
Laminated, asbestos cloth base | do. | | Do.
Cast | | |
Tar-acid—Furfural: | | |
Wood flour filler | Chars 450 | 268-288 | Do.
Mineral filler | Chars 550 | 277-297 | Do.
Fabric filler | Chars 400 | | Do.
Urea—Formaldehyde | None | 260 | Do.
Vinyl, unfilled | 130-160 | 140-150 | Slight.
Vinyl, filled | 130-160 | 140-158 | Do.
Acrylate | 170-235 | 158 | Do.
Styrol | 110-200 | 185 | Do.
Other plastics: | | |
Shellac compound | 150 | | Do.
Cold molded: | | |
Nonrefractory | | |
Refractory | | |
Rubber compounds: | | |
Chlorinated rubber | 175-230 | 140 | Do.
Modified isomerized rubber | 165-220 | 167-221 | Do.
Hard rubber | 150-190 | | Do.
Casein | | 200 |
Cellulose compounds: | | |
Ethyl cellulose | | 210-266 |
Cellulose acetate sheet | 140-230 | 122-212 | Do.
Cellulose acetate molding | 145-260 | 122-212 | Do.
Cellulose nitrate | 160-195 | |
-----------------------------------+-----------+------------+-----------
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedures and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October 1937.
TABLE 21.—_Synthetic resins and other plastics: Electrical properties_
----------------------------------+-------------------+----------------
|Volume resistivity | Breakdown
| (50 percent | voltage, 60
Type |relative humidity) | cycles (volts
| (ohm = cms) | per mil
| |(instantaneous))
----------------------------------+-------------------+----------------
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler |10¹⁰-10¹² |300-500
Molded, mineral filler |10⁹-10¹¹ |250-400
Molded, fabric filler |10⁹-10¹¹ |300-450
Laminated, paper base |10¹⁰-10¹³ |400-1,300
Laminated, fabric base |10¹⁰-10¹² |150-600
Laminated, asbestos cloth base| |90
Cast |10⁹-10¹⁴ |300-450
Tar-acid—Furfural: | |
Wood flour filler |10¹⁰-10¹² |400-600
Mineral filler |10⁹-10¹¹ |200-500
Fabric filler |0.4 × 10¹¹ |200-500
Urea—Formaldehyde |(2-2.8) × 10¹³ |650-720
Vinyl, unfilled |10¹⁴ |400-500
Vinyl, filled |10¹¹ |350-400
Acrylate |10¹⁵ |480
Polystyrene |10¹⁷-10¹⁸ |500-700
Other plastics: | |
Shellac compound | |100-400
Cold molded: | |
Nonrefractory |1.3 × 10¹² |85
Refractory | |
Rubber compounds: | |
Chlorinated rubber | |2,300
Modified isomerized rubber |(5-7) × 10¹⁶ |
Hard rubber |10¹²-10¹⁵ |250-900
Casein | |400-700
Cellulose compounds: | |
Ethyl cellulose | |1,500
Cellulose acetate sheet |(5-30) × 10¹² |800-2,500
Cellulose acetate molding |(4.2-6.2) × 10¹² |800-850
Cellulose nitrate |(2-30) × 10¹⁰ |600-1,200
----------------------------------+-------------------+----------------
----------------------------------+-------------------------------
| Dielectric constant
+---------+----------+----------
Type | | |
|60 cycles|10³ cycles|10⁶ cycles
| | |
----------------------------------+---------+----------+----------
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler |5-12 |4-8 |4.5-8
Molded, mineral filler |5-20 |4.5-20 |4.5-20
Molded, fabric filler |5-10 |4.5-6 |4.5-6
Laminated, paper base | | |4-6
Laminated, fabric base | | |4.5-7
Laminated, asbestos cloth base| | |
Cast |5-10 | |5-7
Tar-acid—Furfural: | | |
Wood flour filler | |4-8 |6-7.5
Mineral filler | |4.5-20 |5-18
Fabric filler | |4.5-6 |5-7.5
Urea—Formaldehyde |6.6 | |6
Vinyl, unfilled | | |4
Vinyl, filled | |4.7 |4
Acrylate |4-6 | |2.8
Polystyrene |2.6 |2.65 |2.7
Other plastics: | | |
Shellac compound | | |
Cold molded: | | |
Nonrefractory |15 | |6
Refractory | | |
Rubber compounds: | | |
Chlorinated rubber |ca. 3 | |
Modified isomerized rubber |2.7 |2.68 |
Hard rubber |2.8 | |3
Casein | | |6.15-6.8
Cellulose compounds: | | |
Ethyl cellulose | |3.72 |
Cellulose acetate sheet |5.1-7.5 | |4.2-5.3
Cellulose acetate molding |5.8-6.0 | |4.4-4.6
Cellulose nitrate |6.7-7.3 | |6.15
----------------------------------+---------+----------+----------
----------------------------------+----------------------------------
| Power factor
+-----------+----------+-----------
Type | | |
| 60 cycles |10³ cycles|10⁶ cycles
| | |
----------------------------------+-----------+----------+-----------
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler |0.04-0.30 |0.04-0.15 |0.035-0.1
Molded, mineral filler |0.10-0.30 |0.10-0.15 |0.005-0.1
Molded, fabric filler |0.08-0.30 |0.08-0.20 |0.04-0.1
Laminated, paper base | | |0.02-0.05
Laminated, fabric base | | |0.02-0.08
Laminated, asbestos cloth base| | |
Cast |0.025-0.20 |0.005-0.08|0.01-0.045
Tar-acid—Furfural: | | |
Wood flour filler | |0.04-0.15 |0.035-0.1
Mineral filler | |0.1-0.15 |0.04-0.1
Fabric filler | |0.08-0.20 |0.035-0.1
Urea—Formaldehyde |0.034 | |0.01-0.03
Vinyl, unfilled | |0.0143 |0.0175
Vinyl, filled | |0.02-0.15 |0.02-0.065
Acrylate |0.06-0.08 | |0.02
Polystyrene |0.0003 |0.0001 |0.0001
Other plastics: | | |
Shellac compound | | |
Cold molded: | | |
Nonrefractory |0.20 | |0.07
Refractory | | |
Rubber compounds: | | |
Chlorinated rubber |0.003 | |
Modified isomerized rubber |0.006 | |0.0016
Hard rubber | | |0.003-0.008
Casein | | |0.052
Cellulose compounds: | | |
Ethyl cellulose | |0.011 |
Cellulose acetate sheet |0.025-0.07 | |0.038-0.091
Cellulose acetate molding |0.042-0.058| |0.038-0.042
Cellulose nitrate |0.062-0.144| |0.074-0.097
----------------------------------+-----------+----------+-----------
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedures and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October 1937.
TABLE 22.—_Synthetic resins and other plastics: Specific gravity,
specific volume, and resistance to other substances_
------------------------------+---------+--------------+-----------
| | |Water
Type |Specific | Specific |absorption,
| gravity | volume |immersion
| | |24 hours[1]
------------------------------+---------+--------------+-----------
Synthetic resins: | |_Cubic inches |
Tar-acid—Formaldehyde: | | per pound_ |
Molded, wood flour filler |1.34-1.52| 20.7-18.2 |0.2-0.6
Molded, mineral filler |1.70-2.09| 16.4-13.3 |0.01-0.3
Molded, fabric filler |1.37-1.40| 20.2-19.8 |1.0-1.3
Laminated, paper base |1.34-1.55| 20.7-17.8 |0.5-9.0
Laminated, fabric base |1.34-1.55| 20.7-17.8 |0.5-9.0
Laminated, asbestos cloth |1.6-1.65 | 17.3-16.8 |0.5
base | | |
Cast |1.27-1.32| 21.8-20.0 |0.01-0.5
Tar-acid—Furfural: | | |
Wood flour filler |1.3-1.4 | 21.3-19.8 |0.2-0.6
Mineral filler |1.6-2.0 | 17.3-13.9 |0.01-0.15
Fabric filler |1.3-1.4 | 21.3-19.8 |0.8-1.4
Urea—Formaldehyde |1.48-1.50| 18.7-16.5 |1-2
Vinyl, unfilled |1.34-1.36| 20.7-20.4 |0.05-0.15
Vinyl, filled |1.35-2.5 | 20.5-11.1 |0.2-4.0
Acrylate |1.18 | 23.3 |0.3
Polystyrene |1.05-1.07| 26.3-25.8 |0
Other plastics: | | |
Shellac compound |1.1-2.7 | 25.2-10.3 |
Cold molded: | | |
Nonrefractory |1.98-2.0 | 14.0-13.9 |1.5
Refractory |2.2 | 12.6 |0.5-15
Rubber compounds: | | |
Chlorinated rubber |1.5 | 18.5 |0.1-0.3
Modified isomerized rubber|1.06 | 26.1 |0.02
Hard rubber |1.12-1.8 | 24.7-15.4 |0.02
Casein |1.35 | 20.5 |3-7
Cellulose compounds: | | |
Ethyl cellulose |1.14 | 24.3 |[6]1.25
Cellulose acetate sheet |1.27-1.37| 21.8-20.2 |1.5-3.0
Cellulose acetate molding |1.27-1.63| 21.8-17.0 |1.4-2.8
Cellulose nitrate |1.35-1.60| 20.5-17.3 |1.0-3.0
------------------------------+---------+--------------+-----------
------------------------------+---------------+------------------
| |
Type |Effect of weak | Effect of strong
| acids | acids
| |
------------------------------+---------------+------------------
Synthetic resins: | |
Tar-acid—Formaldehyde: | |
Molded, wood flour filler |None to slight.|Varies[2]
Molded, mineral filler | do | do[2]
Molded, fabric filler | do | do[2]
Laminated, paper base | do | do[2]
Laminated, fabric base | do | do[2]
Laminated, asbestos cloth | do | do[2]
base | |
Cast | do |
Tar-acid—Furfural: | |
Wood flour filler | do | do[2]
Mineral filler | do | do[2]
Fabric filler | do | do[2]
Urea—Formaldehyde | do |Decomposed or
| |surface attacked
Vinyl, unfilled |Resistant |Resistant
Vinyl, filled |Dependent on |Dependent on
| filler. |filler.
Acrylate |None |Oxidizing acids
| |attack surface.
Polystyrene | do |None
Other plastics: | |
Shellac compound |Deteriorates |Deteriorates
Cold molded: | |
Nonrefractory |Slight |Decomposes
Refractory |Decomposes | do
Rubber compounds: | |
Chlorinated rubber |Resistant |Resistant
Modified isomerized rubber| do | do
Hard rubber | do |Attacked by
| |oxidizing acids
Casein | do |Decomposes
Cellulose compounds: | |
Ethyl cellulose |Slight |Decomposes
Cellulose acetate sheet | do | do
Cellulose acetate molding | do | do
Cellulose nitrate | do | do
------------------------------+---------------+------------------
------------------------------+------------+------------+---------------
| | |
Type | Effect of | Effect of | Effect of
| weak | strong | organic
| alkalies | alkalies | solvents
------------------------------+------------+------------+---------------
Synthetic resins: | | |
Tar-acid—Formaldehyde: | | |
Molded, wood flour filler | Slight to |Decomposes |None.[3]
| marked | |
Molded, mineral filler | do | do | do[3]
Molded, fabric filler | do | do | do[3]
Laminated, paper base | do | do | do[3]
Laminated, fabric base | do | do | do[3]
Laminated, asbestos cloth | do | do | do[3]
base | | |
Cast | do | do | do
Tar-acid—Furfural: | | |
Wood flour filler | do | do | do
Mineral filler | do | do | do
Fabric filler | do | do | do
Urea—Formaldehyde | do | do | do
| | |
Vinyl, unfilled |Resistant |Resistant |([4]).
Vinyl, filled |Dependent on|Dependent on|([4]).
| filler. | filler. |
Acrylate |None |Slight |([5]).
| | |
Polystyrene | do |None |Widely soluble.
Other plastics: | | |
Shellac compound |Deteriorates|Deteriorates|Attacked by
| | | some.
Cold molded: | | |
Nonrefractory |Decomposes |Decomposes | do
Refractory |None |None |None.
Rubber compounds: | | |
Chlorinated rubber |Resistant |Resistant |Soluble in
| | | aromatic
| | | hydrocarbons.
Modified isomerized rubber| do | do |Attacked by
| | | some.
Hard rubber | do | do | do
| | |
Casein |Softens |Decomposes |Resistant.
Cellulose compounds: | | |
Ethyl cellulose |None |None. |Widely soluble.
Cellulose acetate sheet |Slight |Decomposes |([7]).
Cellulose acetate molding | do | do |([7]).
Cellulose nitrate | do | do |([7]).
------------------------------+------------+------------+---------------
[1] ASTM D48-33.
[2] Decomposed by oxidizing acids; reducing and organic acids no
effect.
[3] On bleed-proof materials.
[4] Resists alcohols, aliphatic hydrocarbons, and oils. Soluble
in ketones and esters; swells in aromatic hydrocarbons.
[5] Soluble in ketones, esters, and aromatic hydrocarbons.
[6] 48 hours.
[7] Soluble in ketones and esters; softened by alcohols; little
affected by hydrocarbons.
NOTE.—The values for the properties in this table are based upon
maximum and minimum figures submitted to Modern Plastics by a
number of manufacturers of each type of material. Differences in
test procedure and sizes of test specimens may lead to erroneous
conclusions in some cases if direct comparisons are attempted.
Special grades of materials are often available which excel in
one particular property.
Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October
1937.
15. SYNTHETIC RESINS IN OTHER COUNTRIES
Large-scale production of synthetic resins is confined principally to
the United States, Germany, and Great Britain. There is small production
in many other countries, of which the most important are France, Italy,
Czechoslovakia, Canada, and Japan.
In 1934 the world output was estimated at 135 million pounds, of which
the United States produced about 44 percent, Germany 26 percent, and
Great Britain 24 percent. In 1937 world output was estimated at 360
million pounds, the United States’ share of the total being almost
50 percent, followed by 27 percent for Germany, 20 percent for Great
Britain, and the remaining 3 percent scattered.
European estimates indicate that about 40 percent of the output goes into
surface coatings and that 60 percent of the surface-coating resins are
tar-acid and 40 percent alkyds. The Tariff Commission found that in 1937
50 percent of the United States production of all synthetic resins went
into surface coatings, 27 percent into molded articles, and the remaining
23 percent into laminating and miscellaneous uses. Approximately
three-fourths of the surface-coating resins were alkyds and one-fourth
tar-acid resins.
GERMANY
Production.
In recent years Germany’s production of synthetic resins has increased
rapidly, each succeeding year registering the attainment of a new record.
In 1933 production totaled 17,500,000 pounds and by 1935 had increased to
55,000,000 pounds. A further expansion of about 30 percent to 70,000,000
pounds in 1936 and present production trends indicate a gain of about 40
percent more in 1937, to an estimated total of 100,000,000 pounds.
Although tar-acid resins comprise the bulk of the German output,
considerable gains are shown for other types, notably injection molding
resins of the polystyrene and vinyl types. The development of completely
automatic injection molding machinery has given an impetus to these
types. While technical progress, including improvement of molding
equipment, has contributed to the expanded production, the use of
synthetic resins in Germany has had a strong stimulus because they are
made almost wholly of domestic materials. Under the “Four-Year Plan” for
the greatest possible national economic independence, synthetic resins
are replacing imported materials, such as the heavier nonferrous metals,
iron, hardwoods, cork, and natural gums and resins in many uses. This
displacement of materials has also affected such domestic products as
glass and porcelain, which caused the Government to intervene and impose
restrictions upon the use of resins for purposes adequately served by
other materials of German origin.
Germany’s expanding production of synthetic resin has also been aided by
a sharp increase in exports, which have increased well over 100 percent
since 1932.
_Tar-acid resins._—German output of tar-acid resins has been estimated
at 35 million pounds in 1934, at 49 million pounds in 1935, and at 63
million pounds in 1936. Such resins comprise the bulk of the German
production of molding resins.
There are at least seven producers of tar-acid resins in Germany and nine
producers of molding powders and pellets. Tar-acid resins for surface
coatings are produced by a number of these concerns. Among the important
makers in Germany are The Bakelite Gesellschaft (organized in 1910 to
operate under the Baekeland patents); the explosives and munitions firm
of Dynamit A.G.; Dr. Kurt Albert G.m.b.H.; the I.G. Farbenindustrie;
Beckacite Kunstharzfabrik G.m.b.H.; and Rohm & Haas A.G. The Beckacite
firm has associates in the United States and in the United Kingdom, and
Rohm & Haas, an associate in the United States.
_Alkyd resins._—The manufacture of alkyd resins has developed in
Germany in the past few years. Demand for these resins has been given a
marked impetus by the development of a new standardized substitute for
linseed-oil varnish known as El Varnish, the use of which is required by
the Control Board for Industrial Fats for certain interior and exterior
painting.
There are five makers of resins for paints, varnishes, and lacquers.
The output of alkyd resins has increased sharply since 1934, probably
reaching 10 million pounds in 1936.
_Urea resins._—The output of urea resins in Germany is relatively small;
two of the more important types are known as Locron and Pollopas.
_Polystyrene and vinyl resins._—In 1936 Germany’s production of
thermoplastic resins exceeded 1 million pounds, principally of the
polystyrene and vinyl types. Among the vinyl resins are Acronal and
Mowilith, both of which are manufactured by the I.G. Farbenindustrie.
This combine also produces several types of polystyrene resins known as
Mollit and Metastyrol. Dynamit A.G. produces a polystyrene resin known as
Trolitul.
Uses of synthetic resins.
The original and most important use of synthetic resins in Germany was
for electrical insulation. This use was so extensive that the industry
was organized in 1924 into an association known as non-rubber insulation
materials industry. Materials were standardized and classified into 14
types, of which 5 were tar-acid resins and 1 was a urea resin. Every
type must meet certain specifications in order to be recognized by the
Reich Testing Institute. More than 100 firms produce insulating materials
meeting the institute’s specifications.
Radio panels of the popular sets sponsored by the Government are made of
synthetic resins. Consumption in the automobile industry is increasing
for such parts as instrument panels, electrical equipment, steering
wheels, gear-shift knobs, and numerous others. The latest airplanes show
increased use of synthetic resins, where they contribute light weight,
great strength, and resistance to corrosion.
In cameras and moving-picture equipment, wood and metal have been in part
replaced by synthetic resins. Other applications of resins in Germany
include bearings for rolling mills, goggles and spectacles (including the
lens), and perfume and medicine bottles.
Resins for surface coatings are undergoing rapid development in Germany,
owing to the shortage of linseed oil. Alkyd resins in coatings are being
promoted by the Government, which prohibits or limits the use of the
older oil-type coatings for certain uses so as to decrease the use of
linseed oil and other paint oils that must be imported and hence require
outlays of foreign exchange. Penalties have been imposed for violating
the regulations.[13]
Organization.
The synthetic-resin industry in Germany is a unit within the national
industrial organization. It is a subdivision of the industrial chemical
group, called Fachgruppe Kunststoffe, or Group 13 of the 19 trade groups
in the chemical division. This subdivision controls casein and cellulose
plastics as well as synthetic resins, and is further divided as follows:
(1) Casein plastics, (2) cast phenolic resins, (3) molding compositions,
(4) resins for lacquers, (5) celluloid and zellon, (6) transparent
sheeting, (7) linoleum, and (8) miscellaneous (such as vulcanized fiber,
bottle caps, and die-casting resins).
There are two cartels distinct from the national organization, which
expressly excludes all functions and activities of cartels. One cartel
represents the firms interested in molding compositions and the other
those interested in synthetic resins for other purposes. Some of the
producers are members of both cartels.
Foreign trade.
Imports of synthetic resins are negligible, although the duty of 4.6
cents per pound (25 marks per 100 kilograms) on imports into Germany is
not prohibitive. Exports have increased practically every year since
1930, when they were first recorded separately.
Table 23 shows the quantity and value of exports in recent years.
TABLE 23.—_Synthetic resins: German exports, 1930-37_
-------+----------------------+----------------------
| Hardening resins | Nonhardening resins
+------+---------------+------+---------------
Year | | Value | | Value
|1,000 +-------+-------+1,000 +-----+---------
|pounds|1,000 | 1,000 |pounds|1,000|1,000
| |marks |dollars| |marks|dollars
-------+------+-------+-------+------+-----+---------
| | | | | |
1930 | 2,549| 1,973| 472| | |
1931 | 3,775| 2,757| 651| | |
1932 | 3,162| 2,112| 501| | |
1933 | 4,009| 2,625| 801| 6,628|3,566| 1,088
1934 | 4,924| 3,162| 1,246| 7,076|3,415| 1,346
1935 | 4,948| 2,993| 1,206| 6,921|3,445| 1,388
1936 | 6,392| 3,501| 1,411| 7,764|3,820| 1,539
1937[1]| 8,706| 4,402| 1,770|10,866|5,389| 2,117
-------+------+-------+-------+------+-----+----------
[1] Preliminary.
Source: Consular reports.
German exports of synthetic resins are, for the most part, destined
to European countries, most of which have increased their purchases
considerably in recent years. Exports to Latin American countries have
increased recently, especially to Brazil. Table 24 shows the distribution
of exports in recent years.
TABLE 24.—_Synthetic resins: German exports, by countries, 1934-37_
[Thousands of marks]
------------------------------+-----+-----+-----+-------
Destination |1934 |1935 |1936 |1937[1]
------------------------------+-----+-----+-----+-------
Austria | 259| 352| 446| 593
Belgium | 215| 259| 297| 420
Czechoslovakia | 347| 345| 604| 825
Denmark | 316| 391| 473| 540
France | 626| 651| 680| 734
Great Britain |1,247| 563| 596| 844
Hungary | 240| 135| 182|([2])
Italy | 252| 359| 523| 615
Netherlands | 530| 572| 645|1,031
Spain | 225| 302| 178| 57
Sweden | 415| 457| 463| 691
Switzerland | 721| 705| 714| 749
Other European countries | 370| 618| 706|([2])
Argentina | 250| 207| 194|([2])
Brazil | 46| 77| 109|([2])
Other Latin American countries| 17| 18| 75|([2])
All other countries | 501| 427| 436|2,692
+-----+-----+-----+-----
Total |6,577|6,438|7,321|9,791
------------------------------+-----+-----+-----+-----
[1] Preliminary.
[2] Included in all other countries.
Source: Official German statistics.
GREAT BRITAIN[14]
As in most other countries, the history of the synthetic-resin industry
in Great Britain begins with the acquisition of rights by a British
concern to manufacture under the original Bakelite patents. The Damard
Lacquer Co., Ltd. was probably the pioneer maker of phenolic resins in
England. The principal product was a baking lacquer sold under the trade
name Damarda, marketed for and used principally as a coating to prevent
corrosion on brass. The outbreak of the World War created such an urgent
demand for laminated materials that this firm started production of
them for the British Government. In 1926 this concern was merged with
Mouldesite, Ltd. and Redmanol, Ltd., under the name of Bakelite, Ltd.
Production.
Statistics of production of synthetic resins in Great Britain are
available only for 1934 and 1935. They are given in table 25.
TABLE 25.—_Synthetic resins: Production in Great Britain, 1934 and 1935_
-------------------------------------------+---------------------
Type | 1934 | 1935
-------------------------------------------+----------+----------
| _Pounds_ | _Pounds_
Solid, liquid, cured, uncured, and hardened|25,558,400|13,283,200
Molding powder, 50 percent or more resin | |25,872,000
Laminated sheets, rods, blocks, tubes | 1,164,800| 1,646,400
+----------+----------
Total |26,723,200|40,801,600
-------------------------------------------+----------+----------
Source: Great Britain. Board of Trade, Census of Production.
Capital invested in the British industry is reported as 15,000,000 pounds
sterling and direct employment as 20,000 people.
_Tar-acid resins._—Many large moldings are made in England, such as large
radio cases, desk files, trays, and drain boards. Cast phenolic resin
production has just been started in England.
Among the novelties recently produced in England is a toy railway molded
of tar-acid resin. The trains and track spacers are of nonconducting
resin; the molded rails are made conductive by a thin covering of metal
which is pressed in and secured at the ends. Two trains may be run on the
same set of rails at different speeds, or one can go forward and another
backward, since the two outer rails are separate conductors, the third
rail acting as a common return.
Molded piano parts are being tried in an attempt to solve the troubles
hitherto encountered with wood, owing to variations in humidity. Resins
have long been used in facing the keys, but the production of piano
action parts has presented many technical difficulties. The secret of
success with molded resin parts lies in molding the joints in position
when the main body is molded. There are 88 sections in each piano.
_Urea resins._—British Cyanides, Ltd., well-known makers of synthetic
resins in England, acquired the Pollopas patents for the manufacture
of urea resins in the United Kingdom, in certain continental European
countries, and in the British Empire except Canada. The agreement called
for a full exchange of patents and other information with the other
licensees of the Pollopas patents. These arrangements were made for
the purpose of consolidating the patent position and for the pooling
of technical data already existing on manufacture, with the object of
improving quality.
_Acrylate resins._—An outstanding development in Great Britain has been
the production of the thermoplastic resins known as Diakon and Perspex.
These are made from methyl methacrylate and are developments of the
Imperial Chemical Industries, Ltd. Diakon is for molding powders and
Perspex is in the form of cast sheets, rods, tubes, and optical forms.
These new commercial resins are considered the best combination thus far
obtained of strength, transparency, and light weight. Applications in
England include fittings for aircraft, transparent inspection covers for
machinery, medical equipment, instrument windows, lenses and prisms in
optical systems, and aircraft windscreens. They are used in subways for
lenses for deflecting and diffusing light and in battery cases and coil
forms.
The general properties of the acrylate resins include transparency
to both visible and ultraviolet light, almost unlimited color range,
resistance to acids and alkalies, and superior electrical properties.
_Aniline resin._—Panilax is an aniline-formaldehyde condensation
product made in England. It has high electrical and thermal insulating
properties, great mechanical strength, is odorless and odor repelling,
and practically unaffected by water, oil, and alkalies.
Organization.
Most of the British producers of synthetic resins are members of the
British Plastics Federation, Ltd.
Several years ago a 10-year contract was made between the Imperial
Chemical Industries, Ltd. and the Toledo Synthetic Products Co. (now
Plaskon Co.) of Toledo, Ohio. This agreement provides for an exchange
of all technical and commercial information on urea-resin products and
processes and the granting of free licenses under present or future
patents.
Agreements probably also exist between the British Bakelite Co. and the
American firm on tar-acid resins; between Nobel Chemical Finishes, Ltd.
and E. I. du Pont de Nemours & Co. on alkyd resins; between British
Thompson Houston Co., Ltd., and the General Electric Co. on alkyd resins;
between Imperial Chemical Industries, Ltd. and du Pont on acrylate
resins; and between Beetle Products Co. and American Cyanamid Co. on urea
resins.
Foreign trade in resins.
British imports of synthetic resins, by principal sources, are shown in
table 26.
TABLE 26.—_Synthetic resins: Imports into the United Kingdom, in selected
years, 1930-36_
[1,000 pounds]
--------------------+------+-------+-------+-------+-------+------
Source | 1930 | 1931 | 1933 | 1934 | 1935 | 1936
--------------------+------+-------+-------+-------+-------+------
British countries. | 1 | ([1]) | 5 | 2 | 19 | 24
Germany | 508 | 1,621 | 2,267 | 2,259 | 1,476 | 914
Netherlands | 679 | 667 | 151 | 114 | ([2]) | ([2])
UNITED STATES | 119 | 229 | 656 | 902 | 986 | 1,056
All other countries | 65 | 281 | 246 | 257 | 323 | 435
+------+-------+-------+-------+-------+------
Total |1,372 | 2,798 | 3,470 | 3,534 | 2,804 | 2,429
--------------------+------+-------+-------+-------+-------+------
[1] Less than 500.
[2] Included in “All other countries.”
Source: Official statistics of the United Kingdom.
British exports of synthetic resins to principal countries are shown in
table 27.
TABLE 27.—_Synthetic resins: Exports from the United Kingdom, in selected
years, 1930-36_
[1,000 pounds]
--------------------+------+-------+-------+-------+-------+------
Source | 1930 | 1931 | 1933 | 1934 | 1935 | 1936
--------------------+------+-------+-------+-------+-------+------
British countries | 138 | 170 | 992 | 1,350 | 1,788 | 2,732
Sweden | 40 | 69 | 242 | 452 | 558 | 650
Denmark |([1]) | ([1]) | 99 | 140 | 159 | 150
Belgium |([1]) | ([1]) | 104 | 205 | 237 | 203
Italy |([1]) | ([1]) | 49 | 95 | ([1]) | ([1])
Argentina |([1]) | ([1]) | 28 | 198 | 156 | 238
All other countries | 104 | 171 | 366 | 505 | 735 | 1,084
+------+-------+-------+-------+-------+------
Total | 282 | 410 | 1,880 | 2,945 | 3,633 | 5,057
--------------------+------+-------+-------+-------+-------+------
[1] Not available; included in “All other countries.”
Source: Official statistics of the United Kingdom.
FRANCE[15]
Producers.
Statistics of French production and sales of synthetic resin are not
available. Larousse Commercial Illustré describes the French synthetic
resin industry as not important and estimates the output in 1930 at
2,000,000 pounds. The Revue Général des Matières Plastiques, most
important technical review in France, estimates the production in 1931 as
about 3,500,000 pounds.
The comparatively few French companies producing synthetic resins
are, for the most part, under British or German control. The types of
synthetic resin made in France, the trade names, and the names of the
manufacturers, follow:
_Bakelite._—Tar-acid molding compounds and laminating materials; cast
phenolic resins; Cie La Bakelite, Bezous, Seine.
_Plastose and Ferodo._—Tar-acid molding compounds; Société
Ferodo-Plastose, Saint Ouen, Seine.
_Pollopas._—Urea molding compounds and laminating materials;
Établissements Kuhlmann, Paris.
Foreign trade.
French imports of synthetic resins are classified under tariff item No.
0376 bis: Synthetic resins (solid or resinous products of the Bakelite,
Albertol, Plastose types, etc.) derived from the condensation of
aldehydes with phenols, amines, and amides. Several subclassifications
are shown: (_a_) Soluble in oil and not polymerizable, (_b_) which may be
rendered insoluble and infusible, and (_c_) infusible. Imports in recent
years, from principal sources, are shown in table 28.
TABLE 28.—_Synthetic resins: French imports, by types and by countries,
1931 and 1933-37_
[Pounds]
--------------+-------+---------+---------+---------+---------+----------
Source | 1931 | 1933 | 1934 | 1935 | 1936 | 1937[1]
--------------+-------+---------+---------+---------+---------+----------
|
| Soluble in oil
+-------+---------+---------+---------+---------+----------
Germany |563,860|1,003,860|1,359,600|1,164,470|1,085,766| ([2])
UNITED STATES |174,900| 126,280| 185,680| 284,458| 162,699| ([2])
United Kingdom|184,800| 131,120| 80,520| 109,789| 18,960| ([2])
Austria | | 35,640| 162,580| 193,564| 575,180| ([2])
Netherlands | | 49,720| | 16,755| ([2]) | ([2])
All other | | | | | |
countries | 4,620| 5,720| 3,080| 11,023| 33,069| ([2])
+-------+---------+---------+---------+---------+----------
Total |928,180|1,352,340|1,791,460|1,744,059|1,875,894|1,794,985
+-------+---------+---------+---------+---------+----------
| Molding compounds
+-------+---------+---------+---------+---------+----------
United Kingdom| 21,780| 71,060| 10,340| 11,243| 23,589| ([2])
Germany |248,600| 49,060| 20,460| 68,563| 39,242| ([2])
Switzerland | | 13,200| 31,900| 11,464| ([2]) | ([2])
UNITED STATES | 11,220| 18,920| 22,660| 20,062| 66,799| ([2])
Belgium | | 31,240| 49,500| 7,716| ([2]) | ([2])
All other | | | | | |
countries | 3,080| | 4,840| 6,173| 5,732| ([2])
+-------+---------+---------+---------+---------+----------
Total |284,680| 183,480| 139,700| 125,221| 135,362| 105,380
+-------+---------+---------+---------+---------+----------
| Molded, cast, and laminated articles
+-------+---------+---------+---------+---------+----------
Germany | 12,980| 7,700| 4,840| 9,039| 17,857| ([2])
Netherlands | | | | 220| | ([2])
Austria | 4,840| 440| 220| | | ([2])
United Kingdom| | | 220| | | ([2])
UNITED STATES | | 220| | 220| | ([2])
All other | | | | | |
countries | 1,320| | | | 1,984| ([2])
+-------+---------+---------+---------+---------+----------
Total | 19,140| 8,360| 5,280| 9,479| 19,841| 8,377
--------------+-------+---------+---------+---------+---------+----------
[1] Preliminary.
[2] Not separately reported.
Source: Consular reports.
Exports of synthetic resins from France, by principal markets, are shown
in table 29.
TABLE 29.—_Synthetic resins: French exports 1931 and 1933-37_
[Pounds]
--------------+-------+---------+---------+---------+---------+---------
Destination | 1931 | 1933 | 1934 | 1935 | 1936 | 1937
--------------+-------+---------+---------+---------+---------+---------
Belgium |203,060| 224,180 | 186,780 | 113,757 | 165,565 | ([1])
Argentina | | 69,080 | 91,300 | ([1]) | ([1]) | ([1])
Switzerland | | | 16,940 | 12,787 | 37,258 | ([1])
Italy | 12,980| | | ([1]) | ([1]) | ([1])
All other | | | | | |
countries | 4,840| 29,260 | 15,180 | 54,895 | 36,376 | ([1])
+-------+---------+---------+---------+---------+---------
Total |220,880| 322,520 | 310,200 | 181,439 | 239,199 | 417,772
--------------+-------+---------+---------+---------+---------+---------
[1] Not separately reported.
Source: Consular reports.
CZECHOSLOVAKIA
Production of phenolic resins in Czechoslovakia has increased rapidly in
recent years and is ample to supply domestic requirements. Most of the
raw materials are imported from Germany, Great Britain, and France, but
formaldehyde is produced locally in sufficient quantities.
The principal makers of synthetic resins in Czechoslovakia are:
(1) Bratislavska tovarna na kable Bratislava.
(2) Schreiber & Co. Lipnik
(3) Ing. Alex Reiber Sered
(4) J. Elias Prague
(5) Mathias Oechsler & Sohn Riegersdorf
(6) J. Batistello, Jr. Gablonz
Resin products are widely used by the electrical industries for wall
plates, plugs, switches, fuse boxes, etc. Other articles made of
synthetic resins are: handles and knobs for furniture and kitchen
equipment, bottle caps, fountain pens and pencils, clock and radio
housings, tableware, cutlery handles, trays, buttons, toilet ware and
toys.
Imports of synthetic resins in 1934 totaled 1,270,500 pounds; Germany
supplied 46 percent and Great Britain 22 percent of this total. Exports
of synthetic resins during the same year amounted to 166,540 pounds and
went principally to Poland, Yugoslavia, Germany, and Argentina.
ITALY
The Societa Italiana Resine, an affiliate of the important chemical firm,
Chimiche Forestali, is a leading maker of tar-acid resins in Italy. A new
and modern plant is located at Milan in close proximity to the electrical
and textile industries, both important markets for resins.
In 1936 the Ministry of Corporations granted Montecatini Societe Generale
per l’Industria Mineraria, Milan, a permit to develop a factory for alkyd
resins; and also Societe Italiana Ebonite and Sostituti, Milan, one to
produce tar-acid resins. In 1937 a permit was granted to Montecatini S.A.
for a plant to manufacture acrylic acid resins at the Villadossola works
of the Soc. Elletrochimica del Toce.
JAPAN[16]
The history of the synthetic resin industry in Japan goes back to 1913
when Dr. Jokichi Takamine, discoverer of adrenalin and takadiastase,
acquired the right to manufacture and sell tar-acid resin Products in
Japan. The business was financed by the Sankyo Co., Ltd., and a factory
was built at Shinagawa, near Tokyo. In 1923 a subsidiary company known
as the Japan Bakelite Co., Ltd., was formed with a paid-in capital of
1,200,000 yen. This firm considers itself an affiliate of the Bakelite
Corporation of the United States and, according to an existing agreement,
cannot export to the United States. Its territory includes the Japanese
Empire and Manchukuo. China is considered an open market.
The original plant at Shinagawa was partially destroyed by fire in 1919,
and the following year was moved to Mukojima, Tokyo. The firm makes
tar-acid resins, and a full line of products covered by the patents of
the American concern. Included are laminated sheets, molding compounds,
molded articles, surface coating resins, laminated resin gears and
spindles for rayon mills. An interesting development is the adaption of
tar-acid resin lacquers to the production of Japanese lacquer ware such
as bowls, vases, etc.
Since the establishment of the Japan Bakelite Co., several other firms
have started the production of synthetic resins. The Tokyo Electric Co.,
an affiliate of the General Electric Co., makes tar-acid resins under
the trade name Tecolite. Products are used principally for insulation,
although molding compositions and molded articles such as are used by the
electrical trade are commercially produced.
The Matsushita Electrical Works at Osaka are producers of tar-acid
resins and articles made therefrom. The output is used largely for
radio and electrical equipment. The Nissholite Manufacturing Co., Ltd.,
with a factory at Yasui-cho, Uzumasa, Kyoto specializes in decorative
laminated material sold under the trade name Nissholite. The Japan
Nitrogenous Fertilizer Co. (Nippon Chisso Hirijo Kabushiki Kaisha) is an
important maker of tar-acid resins, marketing them under the trade names
Chissolite, Safeloid, and Minaloid. The Yokahama Resin Co., a relatively
small company, produces tar-acid resins and markets them in the form of
molding powders. The firms listed account for practically all of the
Japanese production of synthetic resins and for about 50 percent of the
molded articles made from them. The remaining 50 percent of the output of
molded articles is made by a large number of small firms, the majority
being household industries. It is reported that there are about 2,000 of
these so-called plants already engaged in this relatively new industry.
Production.
The Japanese production of manufactures of tar-acid resin reported by
the Department of Commerce and Industry is shown in table 30. These data
include the output of plants employing more than five operators and
apparently account for only half of the total.
TABLE 30.—_Manufactures of tar-acid resins: Production in Japan, 1929-35_
------------+-----------+----------------------------------------
| | Value
| +-------------+---------------+----------
Year | Quantity | | |
| | Of quantity | Additional[1] | Total
| | reported | |
------------+-----------+-------------+---------------+----------
| _Pounds_ | | |
1929 | 28,681 | $46,594 | $125,404 | $171,998
1930 | 607,800 | 52,409 | 442,583 | 494,992
1931 | 744,119 | 99,907 | 268,594 | 368,501
1932 | 286,422 | 36,584 | 367,220 | 403,804
1933 | 229,854 | 26,747 | 516,903 | 543,650
1934 | 1,435,977 | 193,857 | 926,951 | 1,120,808
1935 | 3,176,441 | 477,526 | 923,546 | 1,401,072
------------+-----------+-------------+---------------+----------
[1] Quantity not reported.
Source: Factory statistics of Department of Commerce and
Industry, Japan.
Estimates from other sources of Japanese productions of tar-acid resins
indicate an output of 2,600,000 pounds of resin and 3,600,000 pounds
of molded resin articles in 1933, and of 4,900,000 pounds of resin and
7,500,000 pounds of resin articles in 1935.
It was recently announced that the Gosei Chemical Co. will manufacture
vinyl resins in Japan. This firm’s principal interest is in acetate fiber
and rayon manufacture. Later in 1936 the Showa Fertilizer Co. announced
the successful development of a process for making urea. Urea resins
are in commercial production by the Toyo Gosei Kagaku Kogyo K.K., an
affiliate of Chugoku Toyo K.K.
The resin industry in Japan is expected to undergo considerable
development in the near future. Raw materials are available in sufficient
quantities and the art of molding is fairly well developed.
CANADA
The producers of synthetic resins in Canada are:
Bakelite Corporation of Canada, Ltd. Toronto.
Shawinigan Chemicals, Ltd. Shawinigan Falls.
Canadian General Electric Co. Toronto.
Canadian Industries, Ltd. Toronto.
The Bakelite Corporation of Canada, Ltd., an affiliate of the firm of
the same name in the United States, was formed in 1925. This plant
makes molding materials, laminating materials, and an extensive line of
technical varnishes. Molded parts were made at this factory until 1932.
Shawinigan Chemicals, Ltd. is the pioneer organic chemical maker in
Canada. A modern plant at Shawinigan Falls, Quebec, produces synthetic
acetic acid, acetaldehyde, vinyl acetate, vinyl resins, and other
chemicals. The vinyl resins manufactured by this firm have already been
described (see p. 44). Appreciable quantities of these resins have been
exported to the United States in the past but the construction of a
factory (jointly owned by Shawinigan Chemicals, Ltd., and the Fiberloid
Corporation) at Indian Orchard, Mass., for the manufacture of vinyl
resins will probably result in a decrease of exports from Canada to the
United States.
The Canadian General Electric Co. makes alkyd resins for use in surface
coatings. Phthalic anhydride and other raw materials are imported from
the United States. Canadian Industries, Ltd., produces alkyd resins at a
plant in Toronto, Ontario.
There are about 14 molders of synthetic resins in Canada, of which all
but 3 are in Ontario. These firms make a general line of molded articles
including electrical articles, closures, costume jewelry, and smokers’
accessories. Appreciable quantities of molded articles are imported from
the United States and smaller quantities from Germany.
UNION OF SOVIET SOCIALIST REPUBLICS
The synthetic resin industry in the Union of Soviet Socialist
Republics is concentrated in two public departments, known as Public
Commissariates: (a) Public Department for Heavy Industry and (b) Public
Department for Light Industry.
The Department for Heavy Industry, known as Soyuzchemplastmass, controls
the following plants:
1. Karbolit-pawod in Ljubatschani, producing tar-acid resin laminated
fabric known as Textolite.
2. Karbolit-stroj in Ljubatschani, making cast phenolic resins.
3. Karbolitni-pawer in Dubrowka, making tar-acid resin molding compounds.
This plant has at least 350 molding presses producing electrical parts
and automotive parts. The number of presses was to have been increased to
1,000 in 1937.
4. Komsomolskaja prawda in Leningrad manufactures articles, including
phone sets, from cast phenolic resins.
5. Ochtenski Chimkombinat in Ochta. This plant makes nitrocellulose
plastics. No information could be obtained by our Chargé d’Affaires at
Moscow concerning its production of synthetic resins, although it is
believed to be considerable.
The Department for Light Industry has a resin section known as
Mosplastmass producing casein plastics only.
THE NETHERLANDS
There has been no production of synthetic resins in the Netherlands;
but a plant is under construction (October 1937) at Groningen for the
manufacture of alkyd resins. The manufacture of surface coating and
electrical parts from imported resins is carried on, chiefly by N. V.
Philips’ Gloeilampenfabrieken, Afdeeling Inkoop, Eindhaven, manufacturers
of radios, filament lamps, and electrical appliances. Efforts are being
made to employ resins for other purposes, such as the bonding of plywood
and the manufacture of closures and novelties, but little has been
accomplished thus far. The relatively high cost of the resins is the
principal difficulty. Molding compounds and laminated sheets, rods, and
tubes are imported from Germany, Great Britain, Austria, and the United
States.
The paint, varnish, and lacquer industry in the Netherlands has been
experimenting with synthetic resins for several years. Alkyd resins
of the glycerol phthalate type are being used by Dutch paint makers,
imported principally from Germany and Austria. In spite of high cost,
they have been found to have many advantages, especially better and more
uniform quality. The prices of gums and resins in the Netherlands during
the latter part of 1936 are shown in table 31.
TABLE 31.—_Prices of gums and resins in the Netherlands, 1936_
--------------------------------------+------------
|Florins per
Type | 100 kilos
--------------------------------------+------------
Damar |37.
Congo copal (various qualities) |12 to 45.
Indian copal (various qualities) |20 to 35.
Kauri (various qualities) |25 to 200.
Shellac (various qualities) |37 to 52.
Pine resin (rosin) (various qualities)|13 to 14.
Synthetic resins |80 to 120.
--------------------------------------+------------
The Dutch aviation industry is using tar-acid resins to bond plywood for
wing surfacing on Fokker-type wooden planes. The advantages obtained
are excellent adhesiveness and resistance to moisture and temperature
changes. In this application they have replaced casein.
Germany supplies more than 85 percent of the Netherland imports of
synthetic resins, as shown in table 32.
TABLE 32.—_Synthetic resins: Netherland imports by countries, 1931 and
1933-37_
[Pounds]
---------------+---------+---------+---------
Source | 1931 | 1933 | 1934
---------------+---------+---------+---------
Germany |1,203,393|1,257,568|1,207,857
United Kingdom | 8,520| 47,843| 64,458
Austria | 63,758| 7,297| 30,886
UNITED STATES | 3,168| 24,193| 27,434
Belgium | 2,640| 3,923|
France | | 3,120| 4,129
Czechoslovakia | 3,326| 4,948|
Switzerland | 1,789| 4,193|
Other countries| 1,450| 1,027| 2,629
+---------+---------+---------
Total |1,288,044|1,354,112|1,337,393
---------------+---------+---------+---------
[Pounds]
---------------+---------+---------+---------
Source | 1935 | 1936 | 1937[1]
---------------+---------+---------+---------
Germany |1,351,581|1,490,310|2,449,311
United Kingdom | 94,565| 335,099|1,223,553
Austria | 63,642| ([2]) | 132,276
UNITED STATES | 50,888| ([2]) | ([2])
Belgium | 1,514| ([2]) | ([2])
France | 616| ([2]) | ([2])
Czechoslovakia | | ([2]) | ([2])
Switzerland | | ([2]) | ([2])
Other countries| 1,573| 216,051| 207,232
+---------+---------+---------
Total |1,564,379|2,041,460|4,012,372
---------------+---------+---------+---------
[1] Preliminary.
[2] Not separately reported.
Source: Consular reports.
DENMARK
The annual output of synthetic resins in Denmark is about 500,000 pounds,
almost entirely of the tar-acid type.
Bakelite is produced by the Nordiske Kabel and Traadfabrikker A. S.
Fabrikvej at Copenhagen. Other brands made in Denmark are Nokait,
Helomit, and Etronit. There are 14 manufacturers of finished products,
making electrical equipment principally.
POLAND
Production of synthetic resins in Poland in 1936 totaled 660,000 pounds,
entirely of the tar-acid type.
16. RAW MATERIALS FOR ALKYD RESINS
The alkyd resins are made chiefly from phthalic anhydride and glycerin.
Phthalic anhydride in turn is made from naphthalene. Polybasic acids
such as maleic, succinic, etc., may also be used with glycerin to form
alkyd resins. Naphthalene, phthalic anhydride, maleic and other polybasic
acids, and glycerin are discussed in the order named.
NAPHTHALENE
The discovery of naphthalene in coal tar was made simultaneously by
Garden and Brande in 1819, and its composition was determined by Faraday
in 1826 and later by Laurent in 1832. Naphthalene is almost invariably
a constituent of the products obtained when organic matter is heated
to comparatively high temperatures. For example, it is formed in small
quantities when acetylene, alcohol, acetic acid, benzene, or toluene are
heated to high temperatures. Together with certain aromatic hydrocarbons
it is formed in the cracking of petroleum and in the hydrogenation of
petroleum fractions. Naphthalene is a constituent of the principal
varieties of tar produced from coal in the manufacture of gas and coke
under ordinary conditions, but not of low-temperature tar. It is present
in coal gas although its presence must be kept as low as possible to
avoid blocking service pipes in cold weather. The proportion in gas
tar varies with the kinds of coal used and is greater the higher the
temperature used during carbonization; it usually amounts to 4 to 6
percent but is sometimes as much as 10 percent. In tars obtained from
byproduct coke ovens the proportion of naphthalene and other aromatic
hydrocarbons depends on the type of oven used. Byproduct coke-oven tar
averages 10 to 11 percent naphthalene; blast-furnace tar contains only
very small amounts.
Processes to synthesize naphthalene were described as early as 1873 by
Aronheim, in 1876 by Wroden and Znatowicz, and in 1884 by Baeyer and
Perkin. English Patent No. 26,061 of 1898 claims that it may be obtained
by heating barium carbide with barium hydroxide to a high temperature.
None of these processes has become of commercial importance.
Recovery of naphthalene.
Naphthalene is recovered in the distillation of coal tar, in the fraction
boiling at 180° to 250° C., in the creosote oil fraction boiling at 240°
to 270° C. and most abundantly in the carbolate or middle oil fraction
boiling at 200° to 250° C. When these fractions are allowed to cool most
of the naphthalene crystallizes out and is separated by draining and
hot-pressing. This crude material is partially purified by washing with
hot caustic soda solution to remove tar acids and then with mineral acid
to remove basic substances. Refined naphthalene is obtained by subliming,
or preferably by distilling the crude product.
Description and uses.
The Tariff Act of 1930 defines crude naphthalene as naphthalene
solidifying under 79° C. after the removal of all water present; and
refined naphthalene as that having a solidifying point at or above 79° C.
after the removal of all water present.
Crude grades, melting between 70° and 78.5° C., are found in commerce as
yellow, red, or brown crystalline solids. These grades are used in the
manufacture of phthalic anhydride and other coal-tar intermediates; in
the manufacture of lampblack; to enrich illuminating gas and sometimes
motor fuel; in synthetic tanning materials; and in certain insecticides.
Probably its most important outlets are as a raw material for phthalic
anhydride (see p. 98) and refined naphthalene.
Refined grades, melting above 79° C., are marketed as white, crystalline
lumps or flakes. Their principal uses are in the manufacture of
intermediates, dyes, medicinals, solvents, and textile assistants; as
moth repellants; as a lubricant when mixed with rapeseed oil; to remove
the “bloom” from lubricating oils; as a preservative for rubber goods
and animal skins; and in explosives (trinitro naphthalene). In 1936 more
than 75 coal-tar intermediates made from naphthalene were commercially
produced in the United States. Of the 75 million pounds of these
intermediates produced in that year, 31 million pounds were phthalic
anhydride, an important component of synthetic resins of the alkyd type.
United States production.
Crude naphthalene is produced in the United States by byproduct coke-oven
operators, gas works that produce their own coal tar, and also by firms
that purchase coal tar and distill it. Statistics of production by groups
are shown in table 33.
TABLE 33.—_Crude naphthalene: United States production, 1918-37_
----+-----------------------------+------------------------------
| By producers of tar | By purchasers of tar
----+----------+---------+--------+----------+----------+--------
| Quantity | | Unit | Quantity | | Unit
| | Value | value | | Value | value
----+----------+---------+--------+----------+----------+--------
| _1,000 | | _Per | _1,000 | | _Per
| pounds_ | | pound_ | pounds_ | | pound_
1918| | | | 40,138|$1,281,440| $0.032
1919| | | | 12,612| 327,201| .030
1923| 11,872| $201,824| $0,017| 41,453| 652,148| .016
1925| 9,239| 92,389| .010| 34,135| 519,773| .015
1926| 7,747| 100,709| .013| 45,166| 494,986| .011
1927| 8,303| 91,331| .011| 45,298| 470,806| .010
1928| [1]12,182| 146,186| .012| 35,180| 395,059| .011
1929| [1]19,761| 316,182| .016| 19,502| 366,491| .020
1930| [1]12,640| 151,681| .012| 18,617| 304,574| .020
1931| [1]7,623| 76,229| .010| 13,311| 199,665| .015
1932| [1]4,632| 41,690| .09| 8,961| 125,453| .014
1933| [1]6,618| 66,181| .010| 24,003| 360,040| .015
1934| [1]10,743| 139,665| .013| 27,179| 489,222| .018
1935| [1]12,937| 168,185| .013| 34,716| 624,890| .018
1936| [1]37,552| 600,836| .016| 51,984| 1,195,632| .023
1937| [1]60,797|1,215,942| .020| 55,182| 1,545,100| .028
----+----------+---------+--------+----------+----------+--------
----+------------------------------
| Total production
----+----------+----------+--------
| Quantity | | Unit
| | Value | value
----+----------+----------+--------
| _1,000 | | _Per
| pounds_ | | pound_
1918| 40,138|$1,281,440|$0.032
1919| 12,612| 327,201| .026
1923| 53,325| 853,972| .016
1925| 43,374| 612,162| .014
1926| 52,913| 595,695| .011
1927| 53,601| 562,137| .010
1928| 47,362| 541,245| .011
1929| 39,263| 682,673| .017
1930| 31,257| 456,255| .015
1931| 20,934| 275,894| .013
1932| 13,593| 167,143| .012
1933| 30,621| 426,221| .014
1934| 37,922| 628,887| .016
1935| 47,653| 793,075| .017
1936| 89,536| 1,796,468| .020
1937| 115,979| 2,667,522| .023
----+----------+----------+--------
[1] Crude and refined. Refined naphthalene included here is
probably small so that the figures here and those for total
production are substantially accurate.
Source: Bureau of Mines and U.S. Tariff Commission.
Refined naphthalene is obtained from domestic crude, imported crude,
and recently from petroleum cracking and hydrogenation. Table 34 shows
the annual production and sales of refined naphthalene since 1916. The
difference between the figures for the quantity produced and that sold
represents the amount used by refiners in the manufacture of other
products.
TABLE 34.—_Refined naphthalene: United States production and sales,
1917-37_
------+-------------------------------+--------------------------------
| Production | Sales
Year +----------+-----------+--------+----------+-----------+---------
| Quantity | Value | Value | Quantity | Value | Value
------+----------+-----------+--------+----------+-----------+---------
| _1,000 | _1,000 | _Per | _1,000 | _1,000 | _Per
| pounds_ | dollars_ | pound_ | pounds_ | dollars_ | pound_
1917 | 35,343 | 2,334 | $0.07 | | |
1918 | 28,112 | 2,163 | .08 | | |
1919 | 17,625 | 1,161 | .07 | | |
1920 | 30,231 | 2,309 | .08 | | |
1921 | 13,554 | | | 13,183 | 741 | $0.056
1922 | 17,420 | | | 14,060 | 794 | .057
1923 | 28,184 | | | 21,871 | 1,271 | .058
1924 | 15,324 | | | 11,961 | 603 | .050
1925 | 17,581 | | | 12,508 | 610 | .049
1926 | 18,072 | | | 12,456 | 576 | .046
1927 | 21,233 | | | ([1]) | |
1928 | 24,992 | | | ([1]) | |
1929 | 31,144 | | | 21,120 | 1,027 | .049
1930 | 31,956 | | | 20,171 | 949 | .047
1931 | 34,959 | | | 21,260 | 829 | .039
1932 | 25,825 | | | 18,877 | 783 | .041
1933 | 42,708 | | | 28,658 | 1,065 | .037
1934 | 38,730 | | | 21,257 | 1,100 | .052
1935 | 46,564 | | | 28,761 | 1,212 | .042
1936 | 52,694 | | | 30,499 | 1,841 | .060
1937 | 52,194 | | | 29,657 | 1,893 | .060
------+----------+-----------+--------+----------+-----------+---------
[1] Not publishable.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
_Organization of the industry._—There are 10 domestic producers of crude
naphthalene, operating 52 tar-distilling plants in the following States:
Ohio (7), Pennsylvania (6), Illinois and New York (5 each), Alabama,
Minnesota, and New Jersey (3 each), Missouri, Rhode Island, Wisconsin,
Utah, West Virginia (2 each), and Michigan, Massachusetts, Maryland,
Kentucky, Oregon, Connecticut, Tennessee, Indiana, Virginia, and
Washington (1 each). Although these plants do not all recover naphthalene
as such, they are equipped to recover a crude mixture of naphthalene and
tar acids for shipment to a central extracting and refining plant. The
principal producing plants are located in Pennsylvania (2), New Jersey
(2), Illinois (1), Indiana (1), and West Virginia (1).
The purchasers of tar produced 77 percent of the total output of crude
naphthalene in 1935 and 58 percent in 1936.
There are 8 producers of refined naphthalene located in the following
States: New Jersey (3), Pennsylvania (2), California, Indiana, and Ohio
(1 each).
_Trend of production._—Although the United States is the largest producer
of coal tar, the limited demand for the main products of tar distillation
(creosote oil and pitch) has tended to restrict the amount distilled,
thereby reducing the output of naphthalene and the tar acids to a point
where the domestic output was not sufficient to meet our requirements. As
a result, large quantities of these products have been imported. In 1936
we produced 560 million gallons of coal tar, containing from 400 million
to 500 million pounds of naphthalene.[17] In the same year we distilled
about 300 million gallons of tar, containing 230 million to 270 million
pounds of naphthalene,[17] and our actual recovery of crude naphthalene
was 89,536,000 pounds.
Early in 1935 the price of crude naphthalene was about 1.5 cents per
pound or 15 cents per gallon, at which level there was little incentive
to isolate it from the various fractions of tar distillation. Late in
1935 and in 1936 a serious shortage in naphthalene prevailed, largely
because of increased demand by synthetic resin makers but also because
of restrictions on exports from certain European countries. The price
of the crude then advanced in domestic markets to from 2.5 to 3 cents
per pound, with the demand greatly exceeding the supply. Between 1930
and 1936 the apparent consumption of crude naphthalene (production plus
imports) increased from 59 million to 129 million pounds, or more than
100 percent. During the same period production increased from 31 million
to 89 million pounds; and imports increased from 27 million pounds in
1930 to 48 million pounds in 1935 but declined to 40 million pounds in
1936.
Domestic producers of naphthalene are increasing their output, and they
state that continued prices of 2.5 to 3 cents per pound for naphthalene
solidifying at about 75° C. or slightly higher will stimulate production
sufficiently to meet all present and near-future requirements. Estimates
obtained in the summer of 1936 from the large tar distillers and a
petroleum refiner indicate that production was appreciably greater in
1937 than in 1935. These estimates included the potential output of two
new tar distillation plants under construction, the topping of large
quantities of tar (hitherto used as fuel without removing any of the
products), the recovery of appreciable quantities of naphthalene by
several petroleum refiners, and increased output by other producers.
Imports of crude naphthalene in 1937 amounted to 52,664,277 pounds valued
at $1,133,157, or 2.2 cents per pound.
World production.
The output of naphthalene in the principal producing countries, in 1933
and 1935, is shown in table 35. Most of these statistics were estimated
from the output of tar or of other distillation products given in
official reports of the countries or in consular reports.
The figures in table 35 indicate that the output in 1935 was an increase
of about 100 million pounds over 1933 or 41 percent. Notwithstanding
this sharp increase in world production, consumers had difficulty in
obtaining their requirements. It is believed that the world output in
1937 substantially exceeded that in 1935.
TABLE 35.—_Naphthalene (all grades): World production, by countries, 1933
and 1935_
[In thousands of pounds]
--------------+---------+---------
Country | 1933 | 1935
--------------+---------+---------
Germany | 109,148| 145,530
Great Britain | 45,750|[1]55,000
UNITED STATES | 30,620| 47,653
France | 30,000|[1]33,000
Netherlands |[1]15,000|[1]15,000
Belgium | 11,025|[1]25,000
Czechoslovakia| 6,835| 10,805
U. S. S. R. |[1]10,000|[1]15,000
Poland | [1]5,000| [1]8,000
Spain | [1]1,250| [1]2,000
Italy | [1]2,500| [1]3,000
Canada | [1]2,000| [1]3,000
Total | 269,128| 362,988
--------------+---------+---------
[1] Estimated.
Source: Official statistics of the several countries and consular
reports.
_Germany._—Germany is the largest producer of naphthalene and the third
largest producer of coal tar. With increased production of coal tar and
intensive efforts to recover the maximum of naphthalene there has been a
larger output of naphthalene in recent years, but increased consumption
has created a scarcity in Germany as in all other important producing
countries. As a result, greatly reduced quantities are available for
export, a situation that is in marked contrast to earlier periods when
superabundant production created a marketing problem. The manufacture of
phthalic anhydride for alkyd resins is requiring increased quantities of
naphthalene.
The demand for alkyd resins has been given a marked impetus by the
development of a new standardized linseed oil varnish substitute known
as El Varnish, the use of which is required by the Control Board for
Industrial Fats in Germany for certain interior and exterior painting
(see p. 77). Increased requirements for other important purposes such as
intermediates, dyes, black pigments, and explosives have also contributed
to the scarcity of naphthalene. In order to conserve domestic supplies,
the Reich Government, from December 1935 until late in 1937 prohibited
its export without special permit. The prospect of continued strong
domestic demand apparently will curtail for an indefinite period the
quantities available for export.
The international scarcity of naphthalene resulted in a sharp increase
in its price in Germany as elsewhere. The export embargo augmented the
domestic German supply, although a shortage still existed and large
consumers found it difficult to secure adequate amounts. The shortage of
foreign exchange greatly curtailed imports of naphthalene from nearby
countries.
The German Government issued a decree requiring that beginning July 1,
1936, the entire national output of coal tar should be delivered to
plants equipped for the recovery of tar products distilling up to 240° C.
(naphthalene boils at 218° C.). This measure assured maximum recovery of
benzol, toluol, xylol, solvent naphtha, phenol, cresol, xylenol, other
tar acids, and naphthalene. The decree contemplated an official list of
distillation units, and all tar producers were required to report to
the official trade control board for mineral oil their monthly output,
quantities distilled, and quantities delivered to other distillation
plants.
German production, imports, exports, and apparent consumption of
naphthalene are shown in table 36. Production increased from 108 million
pounds in 1928 to 146 million pounds in 1935; imports decreased from 9
to 4 million pounds; exports decreased from 48 to 22 million pounds; and
apparent consumption increased from 69 to 128 million pounds in the same
years.
TABLE 36.—_Naphthalene: German production, imports, exports, and apparent
consumption, 1928-37_
[In thousands of pounds]
----+----------+-------+-------+---------------
Year|Production|Imports|Exports| Apparent
| | | | consumption[1]
----+----------+-------+-------+---------------
1928| 108,173| 9,471| 48,332| 69,312
1929| 124,362| 8,032| 39,739| 92,655
1930| 103,194| 3,892| 34,614| 72,472
1931| 92,169| 2,403| 39,077| 55,495
1932| 90,626| 952| 29,720| 61,852
1933| 109,148| 7,483| 31,842| 84,783
1934| 132,300| 8,641| 35,044| 105,891
1935| 145,530| 4,246| 22,169| 127,603
1936| ([2]) | 493| 8,153| ([2])
1937| ([2]) | 33| 24,966| ([2])
----+----------+-------+-------+---------------
[1] Production plus imports, minus exports.
[2] Not available.
Sources: Consular reports (production); Der auswartige Handel
(imports and exports).
Imports of naphthalene into Germany in past years have been supplied by
nearby countries, notably the Saar (which became an integral part of
Germany in February 1935), Belgium, Czechoslovakia, Poland, the Soviet
Union, and others. The United States has been the most important foreign
market for German naphthalene, taking from 50 to 75 percent of the total
quantity exported. Other important buyers were Belgium, Italy, Japan, and
France. Table 92 (see p. 144) shows the quantity and value of imports and
exports by countries in recent years.
_Great Britain._—The recovery and distillation of coal tar in Great
Britain is highly developed. The annual output of tar, principally
gas-works tar, is somewhat smaller than in the United States, although
the quantities distilled for the recovery of separate components exceed
the quantities distilled in the United States. In 1935 the tar distilled
in England and Wales totaled 330 million gallons and in Scotland, 31
million gallons, or a combined total of 361 million gallons as compared
with about 280 million distilled in this country.
Production of naphthalene in Great Britain is shown in table 37.
TABLE 37.—_Naphthalene: Production in Great Britain, in specified years_
-------+--------------
Year | Production
-------+--------------
|_1,000 pounds_
1924 | 13,730
1930 | 41,400
1933 | 45,750
1935[1]| 55,000
1936[1]| 70,000
-------+------------
[1] Estimated.
Source: Consular reports.
Table 38 shows exports of naphthalene from Great Britain in recent years.
The United States has been the best customer, in most recent years taking
50 percent or more of the total exported. Our imports from Great Britain
have been entirely crude naphthalene, duty-free.
Imports of naphthalene into Great Britain are not shown separately in
official statistics. It is known that the Netherlands exported small
quantities to Great Britain in 1929 and 1933.
TABLE 38.—_Naphthalene: Exports from the United Kingdom_
----+-------------------+---------------------------------------
| Quantity | Value
+---------+---------+-------------------+-------------------
Year| | | To all countries | To United States
| To all |To United+--------+----------+--------+----------
|countries| States | Pounds |Dollars[1]| Pounds |Dollars[1]
| | |sterling| |sterling|
----+---------+---------+--------+----------+--------+----------
| _1,000 | _1,000 | | | |
| pounds_| pounds_| | | |
1928| 5,132| ([2]) | 20,607| 100,278| ([2]) | ([2])
1929| 9,185| 4,312| 32,348| 157,110| 12,558| 60,993
1932| 11,132| 7,514| 26,869| 94,205| 14,274| 50,046
1933| 14,718| 10,480| 38,172| 161,728| 19,604| 83,059
1934| 11,955| 6,492| 35,226| 177,514| 13,025| 65,637
1935| 14,490| 7,999| 49,939| 244,789| 18,413| 90,256
1936| 26,332| 13,412| 120,372| 598,357| 46,158| 229,447
----+---------+---------+--------+----------+--------+----------
[1] Conversion to dollars at annual average quotations of the
Federal Reserve Board.
[2] Not available.
Source: The Trade of the United Kingdom, 1929 and 1936.
_Belgium._—The distillation of coal tar is one of the oldest and most
important branches of the Belgian chemical industry. Approximately 90
batteries of byproduct-coke ovens, with a total of 3,000 ovens are in
operation. Practically all of the coal tar produced in these operations
is distilled for the recovery of the several products. The output of
naphthalene is shown in table 39.
TABLE 39.—_Naphthalene: Belgian production, 1928-35_
-------+--------------
Year | Quantity
-------+--------------
|_1,000 pounds_
1928 | 26,000
1929 | 26,500
1930 | 24,200
1931 | 22,000
1933 | 12,000
1935[1]| 25,000
-------+------------
[1] Estimated.
Source: Consular reports.
Belgian imports and exports of naphthalene, by countries, are shown in
tables 93 and 94 (see pp. 146, 147). Belgium is a net importer of crude
naphthalene and a net exporter of refined naphthalene. In 1937, it
imported 9 million pounds and exported 6.7 million of crude; it imported
only 19 thousand pounds and exported 14 million pounds of refined.
_Czechoslovakia._—The annual output of naphthalene in Czechoslovakia is
shown in table 40.
TABLE 40.—_Naphthalene: Czechoslovak production, in specified years,
1928-35_
----+--------------
Year| Quantity
----+--------------
|_1,000 pounds_
1928| 5,733
1930| 6,174
1931| 2,205
1932| 1,543
1933| 6,835
1934| 9,040
1935| 10,805
----+-------------
Source: Consular reports.
_France._—Naphthalene is produced in France by a number of manufacturers,
most of whom consume their production in their own factories. The
French output is said to be insufficient to meet domestic requirements.
Estimated production is given as approximately 30 million pounds
annually. Appreciable quantities are imported from nearby countries.
Imports from Belgium in recent years average between 1 million and 3
million pounds.
_Poland._—Production of crude naphthalene in Poland is shown in table 41.
TABLE 41.—_Crude naphthalene: Polish production, 1928-36_
----+--------------
Year| Quantity
----+--------------
|_1,000 pounds_
1928| 4,708
1929| 5,257
1930| 3,925
1931| 3,486
1932| 3,704
1933| 4,795
1934| 7,705
1935| 5,021
1936| 2,836
----+--------------
Source: Consular reports.
_The Netherlands._—Statistics of production are not available. Exports in
recent years, however, have averaged about 10 million pounds annually. It
is believed that the production of crude naphthalene exceeds 15 million
pounds a year.
Table 95 (see p. 148) shows Netherland imports and exports of naphthalene
by countries in recent years. Imports in 1937 amounted to 2 million
pounds and exports to 15 million pounds.
_Canada._—Statistics of production are not available. The annual output
of crude naphthalene is estimated at 2 to 3 million pounds.
Imports of refined naphthalene are usually about 1 million pounds (see
table 96, p. 150). Exports are probably small, although in 1929 and 1934
those to the United States alone were over 1 million pounds.
_The Soviet Union._—Statistics of production of naphthalene in the
Soviet Union are not available. The annual output has been estimated at
10 million pounds in 1933 and 15 million pounds in 1935. Exports have
increased substantially in recent years, those to the United States from
1 million pounds in 1934 to 6 million pounds in 1935. Exports to Germany
were 361 thousand pounds in 1933; 1 million pounds in 1934; and 531
thousand pounds in 1935.
_Japan._—Japanese production of naphthalene has been small compared with
the output of other tar products. The output of crude naphthalene in 1934
was reported to have been 381 thousand pounds. Expansion of the byproduct
coking industry in Japan and Manchuria has increased the production
of coal tar, byproduct ammonia, and benzol. Japan has imported large
quantities of naphthalene in recent years, principally from Germany and
Belgium. The increased consumption in Europe may so reduce supplies from
these sources as to cause Japan to increase the recovery at home.
Japanese imports of naphthalene from principal sources, are shown in
table 97 (see p. 150). In 1936, 12.6 million pounds were imported.
United States imports.
_Rates of duty._—Prior to September 8, 1916, all grades of naphthalene
were imported free of duty. Since that time crude naphthalene has
remained free but refined naphthalene has been subject to the tariff
treatment shown in table 42.
TABLE 42.—_Naphthalene: Rates of duty upon imports into the United
States, 1916-38_
-------------------+------------------------+----------------------------
| Rate of duty |
+------+-----------------+
Period | | | Authority
|Crude | Refined |
-------------------+------+-----------------+----------------------------
To Sept. 8, 1916 | Free | Free | Free under par. 452 of the
| | | act of 1913 and
| | | under previous acts.
| | |
Sept. 9, 1916, to | do. | 15 percent ad | Revenue Act of 1916.
Sept. 8, 1921. | | valorem and |
| | 2½ cents |
| | per pound. |
| | |
Sept. 9, 1921, to | do. | 15 percent ad | Emergency Tariff Act of
Sept. 21, 1922. | | valorem and | 1921. (Title V,
| | 2 cents | prohibited imports for
| | per pound. | 3 months except when
| | | not obtainable in
| | | sufficient quantities
| | | or on reasonable terms
| | | as to quality, price,
| | | and terms of delivery).
| | |
Sept. 22, 1922, to | do. | 55 percent ad | Crude, free under par. 1549
Sept. 21, 1924. | | valorem and | and refined dutiable
| | 7 cents | under par. 27 of the
| | per pound.[1] | Tariff Act of 1922.
| | |
| | |
Sept. 22, 1924, to | do. | 40 percent ad | Ad valorem rate on refined
June 17, 1930. | | valorem and | reduced as provided for
| | 7 cents | in Tariff Act of 1922.
| | per pound.[1] |
| | |
June 18, 1930, to | do. | do. | Crude, free under par. 1651
Apr. 30, 1935. | | | and refined dutiable
| | | under par. 27 Tariff Act
| | | of 1930.
| | |
May 1, 1935, to— | do. | 20 percent ad | Refined reduced under
| | valorem and | trade agreement
| | 3½ cents | with Belgium.[2]
| | per pound.[1] |
-------------------+------+-----------------+----------------------------
[1] Ad valorem based on American selling price or United States
value.
[2] Generalized to all countries which do not discriminate
against United States products.
Under the Tariff Act of 1930, crude naphthalene is on the free list[18]
and refined naphthalene is dutiable at 7 cents per pound and 40
percent ad valorem on the basis of American selling price, since it is
competitive with refined naphthalene produced in this country.[19] Under
the trade agreement with Belgium, effective May 1, 1935, the duty on
refined naphthalene was reduced to 20 percent[20] ad valorem and 3½ cents
per pound on imports from that country. Under the Trade Agreements Act
this reduction applies also to imports from all other countries which
do not discriminate against commerce of the United States. In July 1938
Germany was the only one not receiving the reduced rate, exports from
that country being subject to the rates specified under the Tariff Act of
1930.
_Import statistics._—Table 43 shows imports of crude naphthalene
(solidifying at less than 79° C.) and table 44 of refined naphthalene
(solidifying at or above 79° C.) The unit invoice values of imports of
refined naphthalene in 1924, 1926, 1927, 1928, and 1935 indicate that the
imported product was probably not naphthalene as recorded but one of its
derivatives provided for elsewhere in paragraph 27.
TABLE 43.—_Crude naphthalene (solidifying at less than 79° C.): United
States imports for consumption, in specified years, 1919-37_
--------------+--------------+--------------+----------+-----------
Calendar year | Rate of duty | Quantity | Value | Value per
| | | | pound
--------------+--------------+--------------+----------+-----------
| |_1,000 pounds_| |
1919 | Free | 3,239 | $92,265 | $0.028
1920 | do. | 15,012 | 530,219 | .035
1923 | do. | 20,992 | 575,702 | .027
1924 | do. | 5,267 | 96,491 | .018
1925 | do. | 1,980 | 26,593 | .013
1926 | do. | 6,963 | 126,088 | .018
1927 | do. | 6,576 | 131,436 | .020
1928 | do. | 19,926 | 357,679 | .018
1929 | do. | 35,007 | 598,718 | .017
1930 | do. | 27,667 | 397,292 | .014
1931 | do. | 30,971 | 318,578 | .013
1932 | do. | 27,002 | 234,557 | .009
1933 | do. | 42,786 | 451,019 | .010
1934 | do. | 47,995 | 669,383 | .014
1935 | do. | 48,455 | 643,249 | .013
1936 | do. | 39,806 | 785,396 | .020
1937[1] | do. | 52,664 |1,133,157 | .022
--------------+--------------+--------------+----------+-----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 44.—_Refined naphthalene (solidifying at or above 79° C): United
States imports for consumption, in specified years, 1919-37_
---------------+---------------------+---------+-------+------+---------
| | | | |Computed
Calendar year | Rate of duty |Quantity | Value |Unit | ad
| | | |value |valorem
| | | | | rate
---------------+---------------------+---------+-------+------+---------
| | _Pounds_| | |_Percent_
1919 |15 percent + 2½ cents| 7,650| $384|$0.050| 64.8
| per pound | | | |
1920 | do. |3,697,562|416,172| .112| 37.2
1923 |55 percent + 7 cents | 9,605| 194| .020| 401.6
| per pound | | | |
1924 | do. | 4,549| 1,147| .252| 82.8
1925 | do. | | | |
1926 |40 percent + 7 cents | 424| 125| .295| 63.7
| per pound | | | |
1927 | do. | 18,668| 3,077| .165| 82.5
1928 | do. | 27| 6| .222| 71.5
1929 | do. | ⎫ | | |
1930 | do. | ⎪ | | |
Jan. 1-June 17 | do. | ⎪ | | |
June 18-Dec. 31| | ⎬ None | | |
1931 | do. | ⎪ | | |
1932 | do. | ⎪ | | |
1933 | do. | ⎭ | | |
1934 | do. | 66| 6| .091| 116.7
1935 | do.[1] | 99| 31| .313| 62.4
1936 |20 percent + 3½ cents| 30| 20| .667| 50.5
| per pound[2] | | | |
1937[3] | do.[2] | 5,055| 1,085| .215| 36.3
---------------+---------------------+---------+-------+------+---------
[1] From Germany. No imports under trade agreement rate.
[2] Belgo-Luxemburg trade agreement rate.
[3] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 45 shows the principal sources of our imports of crude naphthalene
in recent years. Germany was the principal source until 1936; the United
Kingdom, previously the next most important source, was first in 1936 and
1937. In the last three years appreciable quantities have been received
from Poland, Czechoslovakia, and the Soviet Union, hitherto unimportant
sources.
TABLE 45.—_Crude naphthalene (solidifying under 79° C.): United States
imports for consumption from principal sources, in specified years_
-------------------+---------+---------+---------+---------
Source | 1929 | 1931 | 1933 | 1934
-------------------+---------+---------+---------+---------
| Quantity in thousands of pounds
-------------------+---------+---------+---------+---------
Germany | 21,931 | 17,444 | 20,797 | 22,219
Belgium | 2,531 | 253 | 4,970 | 7,314
United Kingdom | 8,096 | 11,339 | 15,704 | 6,968
Poland and Danzig | | | | 5,766
Canada | 1,488 | 331 | 223 | 1,073
Netherlands | 44 | 937 | 1,092 | 621
Czechoslovakia | | | | 2,984
U. S. S. R. | | | | 1,050
All other countries| 918 | 667 | |
+---------+---------+---------+---------
Total | 35,007 | 30,971 | 42,786 | 47,995
+---------+---------+---------+---------
| Value
+---------+---------+---------+---------
Germany |$382,078 |$170,463 |$242,501 |$326,607
Belgium | 48,508 | 2,506 | 57,243 | 90,424
United Kingdom | 124,427 | 123,890 | 135,853 | 78,968
Poland and Danzig | | | | 89,002
Canada | 23,344 | 3,808 | 2,729 | 18,703
Netherlands | 614 | 11,837 | 12,693 | 8,739
Czechoslovakia | | | | 44,371
U. S. S. R. | | | | 12,569
All other countries| 19,747 | 6,074 | |
+---------+---------+---------+---------
Total | 598,718 | 318,578 | 451,019 | 669,383
+---------+---------+---------+---------
| Value per pound
+---------+---------+---------+---------
Germany | $0.017 | $0.010 | $0.012 | $0.015
Belgium | .019 | .010 | .012 | .012
United Kingdom | .015 | .011 | .009 | .011
Poland and Danzig | | | | .015
Canada | .016 | .011 | .012 | .017
Netherlands | .014 | .013 | .012 | .014
Czechoslovakia | | | | .015
U. S. S. R. | | | | .012
All other countries| .022 | .009 | |
+---------+---------+---------+---------
Average | .017 | .010 | .011 | .014
+---------+---------+---------+---------
| Percent of total quantity
+---------+---------+---------+---------
Germany | 62.7 | 56.3 | 48.6 | 46.3
Belgium | 7.2 | .8 | 11.6 | 15.3
United Kingdom | 23.1 | 36.6 | 36.7 | 14.5
Poland and Danzig | | | | 12.0
Canada | 4.3 | 1.1 | .5 | 2.2
Netherlands | .1 | 3.0 | 2.6 | 1.3
Czechoslovakia | | | | 6.2
U. S. S. R. | | | | 2.2
All other countries| 2.6 | 2.2 | |
+---------+---------+---------+---------
Total | 100.0 | 100.0 | 100.0 | 100.0
-------------------+---------+---------+---------+---------
-------------------+---------+---------+----------
Source | 1935 | 1936 | 1937[1]
-------------------+---------+---------+----------
| Quantity in thousands of pounds
-------------------+---------+---------+----------
Germany | 15,742 | 2,712 | 12,129
Belgium | 2,388 | 2,025 | 1,995
United Kingdom | 10,689 | 16,301 | 17,594
Poland and Danzig | 5,075 | 1,969 | 2,312
Canada | 76 | 255 | 734
Netherlands | 1,344 | 3,794 | 3,359
Czechoslovakia | 6,960 | 6,595 | 6,414
U. S. S. R. | 6,158 | 5,145 | 7,091
All other countries| 22 | 1,010 | 1,038
+---------+---------+----------
Total | 48,455 | 39,806 | 52,664
+---------+---------+----------
| Value
+---------+---------+----------
Germany |$230,820 | $75,314 | $287,901
Belgium | 31,375 | 55,503 | 51,227
United Kingdom | 123,545 | 273,964 | 340,760
Poland and Danzig | 63,992 | 35,439 | 55,184
Canada | 1,169 | 4,093 | 7,941
Netherlands | 19,724 | 105,404 | 93,045
Czechoslovakia | 98,099 | 120,529 | 128,197
U. S. S. R. | 74,354 | 97,815 | 146,331
All other countries| 171 | 17,335 | 22,571
+---------+---------+----------
Total | 643,249 | 785,396 |1,133,157
+---------+---------+----------
| Value per pound
+---------+---------+----------
Germany | $0.015 | $0.028 | $0.024
Belgium | .013 | .027 | .026
United Kingdom | .012 | .017 | .019
Poland and Danzig | .013 | .018 | .024
Canada | .015 | .016 | .011
Netherlands | .015 | .028 | .028
Czechoslovakia | .014 | .018 | .020
U. S. S. R. | .012 | .019 | .021
All other countries| .008 | .017 | .022
+---------+---------+----------
Average | .013 | .020 | .022
+---------+---------+----------
| Percent of total quantity
+---------+---------+----------
Germany | 32.5 | 6.8 | 23.0
Belgium | 14.9 | 5.1 | 3.8
United Kingdom | 22.0 | 41.0 | 33.4
Poland and Danzig | 10.5 | 5.0 | 4.4
Canada | .2 | .6 | 1.4
Netherlands | 2.8 | 9.5 | 6.4
Czechoslovakia | 14.4 | 16.6 | 12.2
U. S. S. R. | 12.7 | 12.9 | 13.4
All other countries| | 2.5 | 2.0
+---------+---------+----------
Total | 100.0 | 100.0 | 100.0
-------------------+---------+---------+----------
[1] Preliminary.
Source: Compiled from official statistics of the United States
Department of Commerce.
United States exports.
Exports are not shown separately; it is doubtful if any naphthalene is
exported. Demand in the United States has exceeded domestic production.
Competitive conditions.
The commercial development and widespread application of surface coatings
and finishes made from alkyd resins, in which phthalic anhydride and
glycerin are the principal components, has resulted in a world-wide
shortage of naphthalene, which is a raw material used in making phthalic
anhydride. In recent years about one-half of domestic requirements
of crude naphthalene have been imported (see table 46) from Europe,
principally Germany and the United Kingdom. Increased demand for the same
purposes, in these countries, has so reduced the quantities available
for export as to create a serious shortage in the United States. Germany
placed an embargo on exports late in 1935 and continued it until late in
1937.
TABLE 46.—_Crude naphthalene: United States production, imports, and
apparent consumption in specified years_
--------+--------------+--------------+--------------+----------------
| | | Apparent |Percent supplied
Year | Production[1]| Imports[2] |consumption[3]| by
| | | | imports
--------+--------------+--------------+--------------+----------------
|_1,000 pounds_|_1,000 pounds_|_1,000 pounds_|
1923 | 53,325 | 20,992 | 74,317 | 28
1927 | 53,601 | 6,577 | 60,178 | 11
1929 | 39,263 | 35,007 | 74,270 | 47
1931 | 20,934 | 30,971 | 51,905 | 60
1932 | 13,593 | 27,002 | 40,595 | 66
1933 | 30,621 | 42,786 | 73,407 | 58
1934 | 37,922 | 47,995 | 85,917 | 56
1935 | 47,653 | 48,455 | 96,108 | 50
1936 | 89,536 | 39,806 | 129,342 | 31
1937[4] | 115,979 | 52,664 | 168,643 | 31
--------+--------------+--------------+--------------+----------------
[1] From table 33.
[2] From table 43.
[3] Production plus imports.
[4] Preliminary.
Vast quantities of naphthalene potentially available in this country were
not recovered because of the low prices prevailing until 1936. Since
then an increase in the price of crude naphthalene from 1.55 cents to
2.5 cents and 3 cents per pound has stimulated production and has led to
additional recovery.
PHTHALIC ANHYDRIDE
Description and uses.
Phthalic anhydride is an aromatic polybasic organic acid anhydride made
from naphthalene by vapor phase catalytic oxidation. It is marketed as
white needle-shaped crystals or flakes having a melting point of 130°
to 131° C. and boiling at 284° to 285° C. It is the cheapest and most
widely used aromatic organic acid. Its most important use is in the
manufacture of synthetic resins of the alkyd type. Other important uses
are in dye intermediates; in phenolphthalein; in benzoic acid; in dyes
such as indigo, phloxines, rhodamines, erythrosines; and in esters such
as dibutyl phthalate (widely used as a plasticizer in nitrocellulose
lacquers and films and of interest as a greaseless lubricant), diethyl
phthalate (used as a perfume fixative and denaturant of alcohol),
dimethyl phthalate (used as a plasticizer in cellulose acetate films),
and diamyl phthalate (used as a plasticizer). Important new processes
using phthalic anhydride as a raw material include the syntheses of
anthraquinone, substituted anthraquinones, and benzoyl benzoic acid.
Before the World War phthalic anhydride was made by heating naphthalene
with sulphuric acid in the presence of mercury; the sulphuric acid acted
as an oxidizer, and sulphur dioxide and carbon dioxide were liberated.
This process was used in Europe and in the United States to produce the
small quantities of phthalic anhydride needed for the manufacture of
certain dyes and intermediates. It proved highly unsatisfactory as to
operation; the yield varying widely from batch to batch. The sales price
of the phthalic anhydride produced at that time was as high as $4.25 per
pound, whereas it is 12 to 14 cents per pound today.
In September 1916, Gibbs and Conover, working in the Color Laboratory
of the Bureau of Chemistry and Soils, United States Department of
Agriculture, developed a process for the synthesis of phthalic anhydride
by the direct vapor phase catalytic oxidation of naphthalene. This work
was done under the United States Government’s wartime investigation of
the manufacture of intermediates and dyes. Gibbs and Conover were granted
United States Patent No. 1,285,117 covering the basic process, and the
invention was assigned to the people of the United States. This process
revolutionized the manufacture of phthalic anhydride, causing the market
price to drop to $2.85 per pound in 1918, to 46 cents per pound in 1920,
and to 13 cents in 1930. With each decline in price new outlets were
found, and domestic production increased practically every year, rising
from 227,000 pounds in 1918 to 23,500,000 pounds in 1935.
By a remarkable coincidence the same basic process was developed
in Germany, by Alfred Wohl, in the laboratories of the Interessen
Gemeinschaft Industrie A. G. (German I. G.), at almost the same time that
Gibbs and Conover made their discovery. In 1920 Wohl applied for a United
States patent covering this process, claiming invention in the summer of
1916. There was some doubt whether his discovery had been made 2 months
earlier or 3 days later than that of Gibbs and Conover, but in July 1934
the United States Court of Customs and Patent Appeals rendered a decision
in favor of the German inventor, allowing Wohl’s claim filed with the
German patent office on June 28, 1916. Therefore, Wohl’s claim covering
the air oxidization process was upheld and he was granted United States
Patent No. 1,971,888, issued August 28, 1934 and assigned to the German
I. G.
Several domestic firms began commercial production of phthalic anhydride
about 1918 under the patent of Gibbs and Conover and have since operated
the process continuously. Such manufacturers are presumably protected
from possible patent litigation and the payment of royalties under the
Wohl patent by section 3 of the so-called Nolan Act of 1921, which
states: “No patent granted or validated ... shall affect the right of any
citizen of the United States or his successor in business to continue
the manufacture, use, or sale commenced before the passage of this Act,
nor shall the continued manufacture, use, or sale by such citizen ...
constitute an infringement.”
United States production.
Table 47 shows the production and sales of phthalic anhydride from 1917
through 1937.
TABLE 47.—_Phthalic anhydride: United States production and sales,
1917-37_
------+------------+------------------------+-----------
| | Sales |
Year | Production +------------+-----------+ Unit value
| | Quantity | Value |
------+------------+------------+-----------+-----------
| _Pounds_ | _Pounds_ | |
1917 | 138,857 | 138,857 | $587,240 | $4.23
1918 | 227,414 | 227,414 | 648,650 | 2.85
1919 | 290,677 | 290,677 | 290,037 | .99
1920 | 796,210 | 796,210 | 362,431 | .46
1921 | 202,471 | 202,471 | 79,162 | .39
1922 | 1,629,182 | 1,317,625 | 461,944 | .35
1923 | 2,343,802 | 2,091,100 | 596,508 | .29
1924 | 2,787,308 | 2,277,073 | 556,265 | .24
1925 | 3,900,332 | 3,560,429 | 701,840 | .20
1926 | 4,379,108 | 3,446,175 | 604,949 | .18
1927 | 4,549,820 | 4,064,476 | 686,946 | .17
1928 | 6,030,854 | 5,445,432 | 888,156 | .16
1929 | 9,168,946 | 7,450,037 | 1,147,953 | .15
1930 | 6,693,001 | 5,614,012 | 724,909 | .13
1931 | ([1]) | | |
1932 | 6,259,000 | 5,695,000 | 663,000 | .12
1933 | 14,075,844 | 11,593,716 | 1,271,887 | .11
1934 | 20,680,379 | 13,511,253 | 1,575,787 | .12
1935 | 23,421,558 | 17,931,662 | 2,105,134 | .12
1936 | 31,244,378 | 22,905,873 | 2,824,471 | .12
1937 | 45,210,784 | 17,565,905 | 2,492,473 | .14
------+------------+------------+-----------+-----------
[1] Not available.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
There are six domestic makers of phthalic anhydride, with producing units
at Bridgeville, Pa., Buffalo, N. Y., Philadelphia, Pa., Deepwater Point,
N. J., Saint Louis, Mo., and Detroit, Mich. Five of these firms have been
producing in commercial quantities continuously for a number of years and
it is therefore believed that these companies may continue to produce
without the payment of royalties. New producers using this process,
however, might be at a disadvantage unless licensed to operate without
the payment of royalties by the owner of the patent.
The production of phthalic anhydride has increased remarkably since the
discovery of the vapor phase catalytic process of manufacture. Until 1922
the only large outlet was the coal-tar dye industry. The development of
new uses for phthalic esters, principally dibutyl phthalate, increased
the demand during the period 1922-28. With the drop in price of phthalic
anhydride, resins made from it and glycerin became of commercial interest
and about 1929 their production began to increase sharply. Most of the
increased output since that year is accounted for by its use in alkyd
resins. As previously stated, surface coatings made from these resins
are now applied to practically all “indoor” surfaces, both wood and
metal, and to “outdoor” use on metal. Largely as a result of the growing
popularity of surface coatings of the alkyd type the domestic production
of phthalic anhydride exceeded 45 million pounds in 1937 and may reach
50 million pounds in 1938. This estimate is based on the present trend
of consumption of alkyd resins and current use therein of phthalic
anhydride. Should other polybasic acids be used in greater proportion the
estimate would have to be revised. Considerable research work is being
done on certain polybasic acids, with very promising results in some
instances. Maleic anhydride is being used commercially, as are adipic
acid, malic acid, and succinic acid. Other possibilities include such
acids as citric, tartaric, sebacic, fumaric, and oxalic.
Production in other countries.
Phthalic anhydride is manufactured in Germany, England, France, Italy,
and Japan, but no statistics of foreign production or of international
trade are available. The output in Germany is known to be increasing
rapidly and is believed to be the principal reason for the German embargo
on exports of naphthalene.
In England there are two makers: Imperial Chemical Industries, Ltd., and
Monsanto Chemicals, Ltd. The latter is a branch of the American firm of
the same name.
In Italy, production was started in 1928 by the A. C. N. A. at Cengio.
Capacity is given as 600,000 pounds annually, and the process is
essentially the same as in this country.
Japanese production is estimated at 6 million pounds a year. Nihon
Seuryo’s plant is the principal one, and the Nishijima mill, at Osaka,
the next in importance.
United States foreign trade.
Imports of phthalic anhydride are dutiable under paragraph 27 at 7 cents
per pound and 40 percent ad valorem based on American selling price.
There were practically no imports since the World War until 1937, when
223,431 pounds were imported from England to relieve a temporary shortage.
Exports, if any, are not shown separately in official statistics.
Competitive conditions.
Phthalic anhydride is the cheapest polybasic organic acid and therefore
the most widely used in the production of alkyd resins. The rapid
rise in consumption of surface coatings and finishes made from these
resins presages greater demand for phthalic anhydride (and glycerin)
in the future, particularly if this type of outdoor finish for wood is
successful.
The world-wide shortage of naphthalene, with attendant sharp increases
in price, raises the question of whether there may not be partial or
complete replacement of phthalic anhydride by other polybasic acids
in certain types of alkyd resins. The probability of such replacement
seems remote unless the use of other polybasic acids, at present much
higher priced, so improves the properties of the resins as to give a
superior product. Approximately 100 pounds of naphthalene are required
to produce 109 pounds of phthalic anhydride. Naphthalene at 3 cents per
pound gives phthalic anhydride a raw material cost of 2.75 cents per
pound as compared with 1.45 cents per pound when naphthalene was 1.55
cents per pound. In other words, the increase of 1.5 cents per pound in
naphthalene, meant an increase of only about 1⅓ cents per pound in the
raw material cost of phthalic anhydride, and only approximately ¼ cent
per pound in the raw material cost of an alkyd resin surface coating
containing about 20-percent phthalic anhydride.
POLYBASIC ACIDS OTHER THAN PHTHALIC ANHYDRIDE
Maleic acid and anhydride.
Maleic anhydride is obtained as a byproduct in the manufacture of
phthalic anhydride and as a major product by the vapor phase catalytic
oxidation of benzene. Domestic production, still small compared with
phthalic anhydride, has increased many fold during the past two or three
years. In 1937 there were three producers of maleic anhydride, with an
output totaling 2,114,176 pounds. The uses of maleic acid derivatives
other than in making resins are minor.
Malic acid and malomalic acid.
Malic acid is widely distributed in the vegetable kingdom, occurring
especially in unripe apples. Commercially it is obtained by synthesis.
Domestic production was reported for the first time in 1935. Malomalic
acid is formed by heating malic acid. United States Patent No. 1,091,627
covers a resin made from malic acid and glycerin which will increase
the toughness of phthalate resins. United States Patent No. 1,667,198
suggests the use of malomalic acid to form resins of glass-like
appearance.
Adipic acid.
Adipic acid is made by oxidation of cyclohexanol. When condensed with
glycerin it yields an alkyd resin which is soft and rubbery and which
does not harden when heated. Numerous patents have been granted on the
preparation of adipic acid and its resins. Commercial production of
adipic acid was first reported in 1935, and the output increased in 1936
and in 1937.
Succinic acid and anhydride.
Succinic acid is a white crystalline powder melting at 185° C. and
boiling at 234° C., with decomposition to succinic anhydride. It may be
obtained by the reduction of maleic acid. Condensation with glycerin
gives a resin tougher and more flexible than is obtained with phthalic
anhydride.
In 1937 there were two commercial producers of succinic acid. It is
believed that small quantities are used in combination with phthalic
anhydride in alkyd resins.
Fumaric acid.
Fumaric acid is a white crystalline powder obtained by the prolonged
heating of or by the action of mineral acids on maleic acid. Fumaric acid
and maleic acid are structurally identical and the former decomposes at
about 280° C., forming the latter. In 1937 there was one domestic maker
of fumaric acid.
GLYCERIN
Description and uses.
Glycerin (glycerol) is a clear, colorless or almost colorless, odorless,
syrupy, hygroscopic liquid. It is obtained as a byproduct of the soap and
fatty acid (oleic acid or red oil and stearic acid) industries. Other
sources are insignificant; glycerin can be produced by the fermentation
of carbohydrates such as molasses, but when glycerin prices are low this
process is not profitable. The chief commercial grades of crude glycerin
are “soap lye” glycerin, a byproduct of the soap industry, containing
about 80 percent glycerin, and “saponification” grade, a byproduct of the
fatty acid industry, containing about 88 percent glycerin. Chemically
pure grades contain about 95 percent and dynamite grades about 98.5
percent glycerin. Other grades include “30° yellow distilled” containing
about 96 percent glycerin.
The uses of glycerin are extremely varied, the most important being in
the manufacture of alkyd resins and ester gums; in the manufacture of
nitroglycerin and dynamite; as a moistening, antiseptic, and sweetening
agent in tobacco; in pharmaceutical and medicinal preparations; and in
certain soft drinks, soaps, and inks.
United States production.
The output of both the crude and the refined has increased in recent
years, reaching new highs in 1937. Chemically pure glycerin constitutes
about 60 percent of the total refined output and dynamite and other
grades about 40 percent. In the production statistics shown in table 48,
grades such as yellow distilled are included with the dynamite grade.
Since large soap makers refine their own crude glycerin, the sale of
crude is only a small part of the total output.
Table 48 shows domestic production of glycerin by grades and table 49
production for sale.
TABLE 48.—_Glycerin: United States production by grades, in specified
years, 1919-37_
[In thousands of pounds]
-------------+---------------+--------------------------------
| | Refined
Census year | Crude 80 +------------+----------+--------
| percent basis | Chemically | Dynamite |
| | pure grade | grade | Total
-------------+---------------+------------+----------+--------
1919 | 61,793 | 36,693 | 25,655 | 62,348
1920 | 54,688 | 32,860 | 31,571 | 64,431
1923 | 99,579 | 47,992 | 52,369 | 100,361
1924 | 95,154 | 53,243 | 37,368 | 90,611
1925 | 103,407 | 55,448 | 52,658 | 108,106
1926 | 116,369 | 64,460 | 49,579 | 114,039
1927 | 128,209 | 59,126 | 49,266 | 108,392
1928 | 130,499 | 66,419 | 46,622 | 113,041
1929 | 140,080 | 66,791 | 58,981 | 125,772
1930 | 138,675 | 69,654 | 50,974 | 120,628
1931 | 140,002 | 70,528 | 43,366 | 113,894
1932 | 133,919 | 63,624 | 41,539 | 105,163
1933 | 119,812 | 58,585 | 45,534 | 104,119
1934 | 153,115 | 80,359 | 48,553 | 128,912
1935 | 141,185 | 74,705 | 48,685 | 123,390
1936 | 154,096 | 85,386 | 47,535 | 132,921
1937 | 167,882 | 92,889 | 51,794 | 144,683
-------------+---------------+------------+----------+--------
Source: Bureau of the Census, U. S. Department of Commerce.
TABLE 49.—_Glycerin: United States production for sale, in specified
years, 1919-35_
--------+-------------------------------+--------------------------------
| Crude[1] | Refined
+----------+------------+-------+----------+-------------+-------
Year | | | Value | | | Value
| Quantity | Value | per | Quantity | Value | per
| | | pound | | | pound
--------+----------+------------+-------+----------+-------------+-------
| _1,000 | | | _1,000 | |
| pounds_ | |_Cents_| pounds_ | |_Cents_
1919 | 18,228 | $2,482,779 | 13.6 | 47,377 | $11,461,213 | 24.2
1923 | 27,444 | 3,124,470 | 11.4 | 74,105 | 12,214,012 | 16.5
1925 | 30,735 | 4,258,351 | 13.9 | 94,303 | 16,991,213 | 18.0
1927 | 27,000 | 3,942,991 | 14.6 | 89,585 | 19,184,806 | 21.4
1929 | 28,790 | 2,358,031 | 8.2 | 113,140 | 12,715,641 | 11.2
1931 | 27,530 | 1,673,733 | 6.1 | 102,510 | 10,316,347 | 10.1
1931[2]| 25,964 | 1,551,573 | 6.0 | 101,615 | 10,222,850 | 10.1
1933 | 22,161 | 1,191,000 | 5.4 | 107,853 | 7,915,000 | 7.3
1935 | 24,042 | 2,366,481 | 9.8 | 121,262 | 12,984,684 | 10.7
[1] By chemical and soap manufacturing plants only.
[2] Adjusted for comparison with 1933.
Source: Bureau of the Census, U. S. Department of Commerce.
Crude glycerin is produced by about 200 soap makers and by about 12
producers of fatty acids. Soap factories are located in more than half
the States, the principal ones being in Ohio, New York, Massachusetts,
New Jersey, Illinois, California, and Pennsylvania; the fatty acid plants
are located in five or six States, Ohio being of chief importance. Most
of the smaller producers sell their output of crude glycerin. Refiners of
glycerin are few in number compared to the producers of crude. The larger
soap plants refine their own crude glycerin and in addition purchase
crude from other plants for refining.
The process of recovering glycerin consists of chemically treating weak
glycerin solutions separated from the soap or fatty acids, and then
concentrating and distilling under reduced pressures. The average yield
is less than 10 percent but varies from about 9 to 12 percent, depending
upon the kinds of oils and fats used. When prices are high every effort
is made to recover the maximum yield of glycerin; when prices are low,
cost of chemical treatment and distillation makes it advisable to allow
more glycerin to remain in the soap or to discard the weak solutions.
Production in other countries.
As in the United States, glycerin is produced in foreign countries, as
a byproduct of the soap and fatty acid industries. The United Kingdom,
Germany, and France, and recently the Soviet Union, are the leading
producers. The output in each of these countries is estimated to be less
than a third of the output in the United States. The British Census of
1930 reports the production of crude glycerin in the United Kingdom at
44 million pounds. Authentic statistics on production in other leading
countries are not available, but most estimates show lower figures than
for the United Kingdom. In some European countries the normal production
of soap results in more glycerin than can be utilized.
International trade.
France is the principal net exporter of crude glycerin and the United
Kingdom of refined glycerin. The Netherlands, Germany, and France are
also net exporters of refined glycerin. The international trade of
certain of the more important producing countries in crude and refined
glycerin is shown in table 50.
TABLE 50.—_Glycerin: Imports and exports of principal countries, 1931 and
1933-37_
[In thousands of pounds]
--------------------+---------------+---------------+---------------
| 1931 | 1933 | 1934
+-------+-------+-------+-------+-------+-------
|Imports|Exports|Imports|Exports|Imports|Exports
--------------------+-------+-------+-------+-------+-------+-------
Crude: | | | | | |
UNITED STATES[1]| 8,782| ([2]) | 4,988| ([3]) | 13,722| ([3])
United Kingdom | 1,702| 2,662| 4,778| 2,951| 472| 2,825
Germany | 4,120| 2,313| 5,232| 2,939| 4,746| 1,599
France | 1,269| 7,962| 426| 3,488| | ([2])
Netherlands | 5,133| 859| 3,027| 2,300| 2,605| 3,796
Refined: | | | | | |
UNITED STATES | 1,966| 328| 2,776| ([3]) | 2,214| ([3])
United Kingdom | 2,519| 9,926| 822| 19,834| 230| 19,134
Germany | 102| 10,092| 57| 3,562| 224| 3,818
France | 178| 3,989| 109| 1,246| 51| 12,249
Netherlands | 618| 8,337| 1,144| 6,620| 1,008| 5,955
Belgium | 534| 758| 1,193| 429| 1,206| 2,360
+-------+-------+-------+-------+-------+-------
| 1935 | 1936 | 1937[4]
+-------+-------+-------+-------+-------+-------
|Imports|Exports|Imports|Exports|Imports|Exports
+-------+-------+-------+-------+-------+-------
Crude: | | | | | |
UNITED STATES[1]| 4,092| ([2]) | 8,686| ([2]) | 10,171| ([2])
United Kingdom | 1,119| 2,365| 2,322| 3,070| ([2]) | ([3])
Germany | 4,091| 326| 8,247| 122| 13,567| 578
France | 862| ([2]) | 1,176| ([2]) | 164| ([2])
Netherlands | 5,441| 4,912| 7,185| 5,644| 9,127| 6,865
Refined: | | | | | |
UNITED STATES | 69| 3,354| 3,448| 1,146| 7,535| 1,375
United Kingdom | 2| 15,032| | 12,991| ([3]) | 16,029
Germany | 108| 1,571| 30| 1,155| 71| 100
France | 4| 12,118| 10| 9,269| 9| 17,750
Netherlands | 694| 5,516| 739| 8,885| 500| 10,961
Belgium | 998| 1,945| 188| 1,981| 651| 1,858
--------------------+-------+-------+-------+-------+-------+-------
[1] Imports from Cuba and the Philippines not included in the
United States statistics. These imports, consisting of crude
glycerin, averaged about 2,200,000 pounds annually for the period
1931-37.
[2] Included, if any, with refined.
[3] Not separately reported.
[4] Preliminary.
Source: Official statistics of each country.
United States imports.
Under the Tariff Act of 1922, paragraph 43, imports of crude glycerin
were dutiable at 1 cent per pound and refined glycerin at 2 cents per
pound. The Tariff Act of 1930, paragraph 42, carries the same rates.
Imports of crude glycerin from Cuba enjoy a preferential rate; they were
dutiable at 0.8 cent per pound up to September 3, 1934, and at 0.4 cent
per pound thereafter. Under the trade agreement with the Netherlands,
effective February 1, 1936, the rate on refined glycerin was reduced from
2 cents to 1⅔ cents per pound (⅔ cent plus regular rate on crude, but not
more than 1⅔ cents). Under the trade agreement with France, effective
June 15, 1936, the rate on crude glycerin was reduced from 1 cent to 0.8
cent, which automatically further reduced the rate on refined glycerin
to 1¹⁴⁄₃₀ (approximately 1.47) cents per pound. The rates under these
last two trade agreements are generalized to all countries which do not
discriminate against our commerce.
The amount of glycerin supplied by imports has greatly declined. Prior
to the World War, imports of crude glycerin ranged from 30 million to
40 million pounds annually. After the war imports were less and after
1929 declined to comparatively small quantities, except in 1934. Imports
of refined glycerin were relatively unimportant until 1924, except in
1920. They amounted to almost 11 million pounds in 1926, but declined
thereafter. Some of the imports are reexported with benefit of drawback.
In 1930, 1,006,164 pounds of imported crude glycerin and 396,792 pounds
of imported refined were thus reexported, chiefly in the refined grades.
Corresponding figures in 1932 and 1933 were 197,331 and 111,753 pounds of
crude, and 40,011 and 10,056 pounds of refined.
Statistics of imports other than from Cuba and the Philippines are given
in table 51. Table 52 shows imports of crude from Cuba and table 53
imports of crude from the Philippines.
TABLE 51.—_Glycerin: United States imports[1] for consumption 1919-20 and
1923-37_
-------------+-------------+---------+---------+----------+-------------
| |Quantity,| | | Computed
Calendar year| Rate of | 1,000 | Value |Unit value| ad valorem
| duty | pounds | | |rate, percent
-------------+-------------+---------+---------+----------+-------------
| Crude
+-------------+---------+---------+----------+-------------
1919 | 1 cent per | 3,564| $417,774| $0.117| 8.5
| pound | | | |
1920 | do | 22,272|2,912,430| .131| 7.7
1923 | do | 14,120|1,382,249| .098| 10.2
1924 | do | 13,659|1,413,593| .103| 9.7
1925 | do | 18,624|2,161,413| .116| 8.6
1926 | do | 26,729|3,849,222| .144| 6.9
1927 | do | 13,666|2,026,175| .148| 6.7
1928 | do | 3,889| 282,615| .073| 13.8
1929 | do | 13,681| 786,598| .058| 17.4
1930 | do | 10,022| 577,406| .058| 17.4
1931 | do | 8,782| 446,897| .051| 19.7
1932 | do | 3,952| 145,329| .037| 27.2
1933 | do | 4,988| 176,080| .035| 28.3
1934 | do | 13,722| 932,389| .068| 14.7
1935 | do | 4,092| 353,925| .086| 11.4
1936 | Various[2] | 8,686| 936,312| .108| 7.7
1937[3] | do | 10,171|1,716,351| .169| 4.8
+-------------+---------+---------+----------+-------------
| Refined
+-------------+---------+---------+----------+-------------
1919 | 2 cents per | 39| 4,471| .114| 17.5
| pound | | | |
1920 | do | 5,382|1,170,030| .217| 9.2
1923 | do | 586| 76,994| .131| 15.2
1924 | do | 1,501| 229,897| .153| 13.1
1925 | do | 2,044| 305,796| .150| 13.4
1926 | do | 10,839|2,328,936| .215| 9.3
1927 | do | 8,289|1,697,330| .205| 9.8
1928 | do | 4,218| 450,247| .107| 18.7
1929 | do | 5,358| 489,575| .091| 21.9
1930 | do | 3,137| 265,093| .085| 23.7
1931 | do | 1,966| 140,975| .072| 27.9
1932 | do | 2,348| 142,359| .061| 33.0
1933 | do | 2,776| 166,991| .060| 33.2
1934 | do | 2,214| 208,989| .094| 21.2
1935 | do | 69| 8,277| .121| 16.6
1936 |Various[2] | 3,447| 594,036| .172| 8.5
1937[3] | do | 7,535|1,827,189| .242| 6.2
-------------+-------------+---------+---------+----------+-------------
[1] Does not include products of Cuba (duty less 20 percent) and
the Philippine Islands (free).
[2] For changes in rates, see p. 105.
[3] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 52.—_Crude glycerin: United States imports (for consumption) from
Cuba, in specified years, 1919-37_
-------------+-------------------+--------+-------+----------+----------
| | | | | Computed
Calendar year| Rate of duty |Quantity| Value |Unit value|ad valorem
| | | | | rate
-------------+-------------------+--------+-------+----------+----------
| | _1,000 | | |
| | pounds_| | |_Percent_
1919 |⁸⁄₁₀ cent per pound| 249|$27,023| $0.108| 7.4
1920 | do | 139| 21,941| .158| 5.1
1923 | do | 429| 47,438| .111| 7.2
1924 | do | 768| 85,971| .112| 7.2
1925 | do | 624| 73,538| .118| 6.8
1926 | do | 835|134,893| .162| 5.0
1927 | do | 1,119|170,723| .153| 5.2
1928 | do | 690| 48,963| .071| 11.3
1929 | do | 921| 60,158| .065| 12.2
1930 | do | 843| 53,905| .064|
1931 | do | 1,171| 67,709| .058| 13.8
1932 | do | 1,232| 50,147| .041| 19.7
1933 | do | 1,216| 56,737| .047| 17.2
1934 |Various[1] | 1,178| 92,692| .079|
1935 |⁴⁄₁₀ cent per pound| 2,551|228,011| .089| 4.5
1936 | do | 2,160|230,340| .107| 3.8
1937[2] | do | 2,477|381,683| .154|
-------------+-------------------+--------+-------+----------+----------
[1] Trade agreement of ⁴⁄₁₀ cent per pound, effective Sept. 3,
1934.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 53.—_Crude glycerin: United States imports (for consumption) from
Philippine Islands 1925-37_
-------------+-------------+--------------+-------+----------
Calendar year| Rate of duty| Quantity | Value |Unit value
-------------+-------------+--------------+-------+----------
| |_1,000 pounds_| |
1925 |Free | 16| $1,418| $0.089
1926 | do | 95| 12,115| .128
1927 | do | 159| 18,261| .115
1928 | do | 337| 24,327| .072
1929 | do | 250| 16,796| .067
1930 | do | 279| 18,805| .067
1931 | do | 180| 10,993| .061
1932 | do | 198| 9,150| .046
1933 | do | 268| 14,078| .052
1934 | do | 181| 14,984| .083
1935 | do | 1,579| 74,798| .047
1936 | do | 304| 32,708| .108
1937[1] | do | 793|145,348| .183
-------------+-------------+--------------+-------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
France has usually been the principal source of imports of crude
glycerin, but since 1935 Cuba has ranked first. Cuban imports enter at a
preferential rate of duty (0.8 cent per pound on crude until September 3,
1934, when it was reduced to 0.4 cent). Receipts from the Philippines are
duty-free. Imports by countries for recent years are given in table 98,
page 151.
The Netherlands has generally been the chief source of imports of refined
glycerin, although the United Kingdom was first in 1934 and 1935 and
France first in 1937. Imports by countries for recent years are given in
table 99, page 152.
United States exports.
Exports of glycerin are insignificant compared with production and are
small compared with imports. They go chiefly to Mexico and Canada,
and, at times, also to Cuba, the Philippines, and Chile. Geographic
propinquity is probably the principal factor accounting for these
exports, although it is possible that some exports are destined to
foreign branch factories of an American company for making dynamite.
Crude and refined grades were not separately distinguished in export
statistics, but it is known that exports consist principally, if not
entirely, of the refined. In 1933 and 1934 glycerin exports were not
reported. Statistics of exports are given in table 54.
TABLE 54.—_Glycerin: United States exports, in specified years, 1919-37_
-------+---------+-----------+----------
Year | Quantity| Value |Unit value
-------+---------+-----------+----------
| | |_Cents per_
|_Pounds_ | | _pound_
1919 |3,963,392| $1,190,984| 30.0
1920 |1,742,708| 429,116| 24.6
1923 |1,767,407| 318,765| 18.0
1924 |1,415,882| 237,639| 16.8
1925 |1,367,191| 282,078| 20.6
1926 | 767,698| 192,220| 25.0
1927 | 693,144| 143,700| 20.7
1928 |2,051,937| 259,100| 12.6
1929 |1,373,605| 197,986| 14.4
1930 | 607,690| 102,892| 16.9
1931 | 328,143| 48,095| 14.7
1932 | 260,339| 28,609| 11.0
1933 | ([1]) | ([1]) |
1934 | ([1]) | ([1]) |
1935 |3,353,625| 450,248| 13.4
1936 |1,146,026| 182,592| 15.9
1937[2]|1,375,036| 338,148| 24.6
-------+---------+-----------+----------
[1] Not reported separately.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
Glycerin occurs in chemical combination in animal and vegetable oils
and fats. Since it is obtained as a byproduct, the output is dependent
primarily upon the output of the major products, soaps and fatty acids,
and its production is largely independent of demand. At low prices,
however, less glycerin is recovered.
The United States usually consumes more glycerin than it produces (see
table 55), whereas leading European producing nations produce more than
they consume. In recent years the domestic production has apparently been
approaching domestic requirements. A factor tending to decrease demand
is the increasing resort to substitutes in various uses, particularly
ethylene glycol, ethyl alcohol, and methyl alcohol. On the other hand,
the demand in the resin industry is expanding rapidly.
TABLE 55.—_Refined glycerin: United States production, imports, exports,
and apparent consumption, in specified years_
-------+-------------+----------+----------+--------------
Year |Production[1]|Imports[2]|Exports[3]| Apparent
| | | |consumption[4]
-------+-------------+----------+----------+--------------
| _Pounds_ | _Pounds_ | _Pounds_ | _Pounds_
1927 | 108,392| 8,289| 693| 115,987
1929 | 125,772| 5,358| 1,374| 129,757
1931 | 113,894| 1,966| 328| 115,531
1932 | 105,163| 2,348| 260| 107,250
1933 | 104,120| 2,776| ([5]) | 106,895
1934 | 128,912| 2,214| ([5]) | 131,126
1935 | 123,390| 69| 3,354| 120,105
1936 | 132,922| 3,447| 1,146| 135,223
1937[6]| ([5]) | 7,535| 1,375| ([5])
-------+-------------+----------+----------+--------------
[1] From table 48 (refined basis).
[2] From table 51 (refined).
[3] From table 54 (grade not specified, but chiefly refined).
[4] Production plus imports minus exports.
[5] Not available.
[6] Preliminary.
Up to 1924 (except 1920) imports consisted principally of crude glycerin,
much of which was refined in the United States and included in United
States production; thereafter imports of refined glycerin became
important relative to the crude. Exports are insignificant compared to
either production or imports.
17. RAW MATERIALS FOR TAR-ACID RESINS
The first tar-acid resins were made from phenol and formaldehyde. As a
result this group of resins is frequently spoken of as phenolic resins.
This is true despite the fact that coal-tar acids other than phenol,
particularly the cresols and xylenols, are used in large volume today.
THE TAR ACIDS
The term coal-tar acids is applied to certain organic compounds either
obtained from or known to be present in coal tar. Probably the best known
is phenol or carbolic acid, produced in large quantities in the United
States and abroad. Others of commercial importance are ortho, meta,
and para cresol and the xylenols. All of these are definite chemical
compounds available as such or in mixture with other tar acids. Cresylic
acid is a term widely used in commerce for almost any mixture of tar
acids. Formerly it was used to designate a mixture of ortho, meta, and
para cresols in the proportions in which they are found in coal tar. The
higher boiling tar acids (listed in table 56 below the xylenols) have
little or no commercial importance at this time.
Table 56 lists the tar acids by commercial name, chemical name, boiling
point of the pure compound, and average percentage present in coal
tar. Boiling point is shown because the several tariff classifications
covering tar acids under the acts of 1922 and 1930 (pars. 27 and 1651)
depend upon distillation range (boiling points) for classification and
assessment of duty (see pp. 119 and 124).
TABLE 56.—_Tar acids: Commercial and chemical names, boiling points and
average percentage present in coal tar_
--------------------+-----------------------+---------+----------
| | | Average
Commercial name | Chemical name | Boiling |percent in
| |point ° C| coal tar
--------------------+-----------------------+---------+----------
Phenol |Phenol | 181.5| 0.7
Orthocresol |2-methyl phenol | 190.8| .4
Metacresol |3-methyl phenol | 202.8| .4
Paracresol |4-methyl phenol | 201.8| .3
2-3 Xylenol |2-3-dimethyl phenol | 218.0| ⎫
2-4 Xylenol |2-4-dimethyl phenol | 211.5| ⎪
2-5 Xylenol |2-5-dimethyl phenol | 211.5| ⎬ .2
2-6 Xylenol |2-6-dimethyl phenol | 212.0| ⎪
3-4 Xylenol |3-4-dimethyl phenol | 225.0| ⎪
3-5 Xylenol |3-5-dimethyl phenol | 220.0| ⎭
Ortho ethylphenol |2-ethyl phenol | 206.5| ⎫
Meta ethylphenol |3-ethyl phenol | 217.0| ⎪
Para ethylphenol |4-ethyl phenol | 218.5| ⎪
s-methyl ethylphenol|3-methyl-5-ethyl phenol| 232.5| ⎬ .5
Iso pseudocumenol |2-3-5-trimethyl phenol | 233.0| ⎪
Mesitol |2-4-6-trimethyl phenol | 219.5| ⎪
Pseudocumenol |2-4-5-trimethyl phenol | 234.0| ⎭
--------------------+-----------------------+---------+----------
Source: Ellis, Chemistry of Synthetic Resins.
Since the quantities of tar acids present in coal tar are small (see
table 56), it is usually uneconomical to distill coal tar completely
unless the creosote oil and pitch can be marketed profitably. Beginning
in 1936, production of tar acids in the United States was increased by
the practice of topping. Topping is the recovery in tar distillation of
the light fractions only, leaving a residual thin enough to flow through
the pipe lines to supply fuel to open hearth and other type furnaces.
These light fractions contain the naphthalene and tar acids. The practice
permits recovery of these products from tar to be used as fuel, thus
providing a new alternative intermediate between the two older practices
of either complete distillation or using the undistilled tar as fuel.
In the United States, consumption of most of the tar acids greatly
exceeds the quantities extracted from tar, necessitating large production
of synthetic phenol and importation of large quantities of the cresols
and xylenols. The calculated amount of these tar acids present in the tar
produced in this country vastly exceeds present day requirements. Table
57 shows the approximate amounts of the several tar acids contained in
the coal tar produced and distilled in 1936. These estimates are based on
a 1936 production of coal tar of 560,385,578 gallons and a distillation
of 292,140,249 gallons. The calculation is made by using the percentage
of tar acids in tar shown in table 56 and converting the gallons to
pounds in accordance with the specific weights of the pure tar acids.
Actual production of all tar acids in the United States in 1936 was about
29 million pounds.
TABLE 57.—_Tar acids available in coal tar produced and distilled in 1936_
-----------+--------------+--------------
| Available in | Available in
Tar acid | tar produced | tar distilled
| in 1936[1] | in 1936[2]
-----------+--------------+--------------
|_1,000 pounds_|_1,000 pounds_
Phenol | 34,912 | 18,200
Orthocresol| 19,277 | 10,050
Metacresol | 19,277 | 10,050
Paracresol | 14,290 | 7,450
Xylenols | 10,200 | 5,316
Others | 25,200 | 13,290
-----------+--------------+--------------
[1] 560,385,578 gallons.
[2] 292,140,249 gallons.
The several tar acids are discussed in detail under the following heads:
(_a_) Phenol.
(_b_) The cresols, xylenols, and cresylic acid.
(_c_) Synthetic tar acids other than phenol.
PHENOL
Description and uses.
Phenol (commonly called carbolic acid) is a tar acid obtained from two
sources: (_a_) From one of the fractions recovered in the distillation
of coal tar, a byproduct resulting from the manufacture of coke in
byproduct ovens, and from the manufacture of coal gas; (_b_) from
benzol, by synthesis. The second source has been the more important
since 1923. Phenol, when pure, is a colorless substance of interlaced
or separate needle-shaped crystals with a characteristic aromatic odor.
It is corrosive to the skin and to mucous membrane. When pure it is
water white, melts at about 42° C., and boils at about 181.5° C. It was
discovered in 1834 by Runge.
Phenol is used today chiefly as a component of tar-acid resins. It is
also widely used as an antiseptic and disinfectant, in the manufacture of
explosives (picric acid and ammonium picrate), and as an intermediate for
certain dyes and medicinals. Salicylic acid and its derivatives—aspirin,
salol, and methyl salicylate (artificial oil of wintergreen)—are
important medicinals made from phenol. Another use is in the extraction
of lubricating oils. The relative importance of these various uses in
recent years is indicated by table 58, which gives the estimated domestic
consumption of phenol by uses in 1936-37.
TABLE 58.—_Phenol: Estimated consumption by industries, 1936-37_
------------------------------+-----------------
Use |Percent of
|total consumption
------------------------------+-----------------
Synthetic resins | 60-65
Extraction of lubricating oil | 5
Insecticides and disinfectants| 10
Dyes and intermediates | 5
Other | 15-20
------------------------------+-----------------
United States production.
Prior to 1914 United States production of phenol averaged about a
million pounds a year and was entirely the natural product obtained from
distillates of coal tar. Increased demand during the World War was met
by several synthetic phenol processes, which utilized in part the vast
quantities of benzol available. Our output of phenol reached 64 million
pounds in 1917 and 107 million pounds in 1918. When the armistice was
signed stocks on hand in the United States totaled between 35 million and
40 million pounds, estimated at three times the annual consumption at
that time for nonmilitary purposes. As a result the price dropped from
about 45 cents to 6 cents a pound, and the synthetic plants were closed.
The limited quantities of phenol available to synthetic resin makers
prior to and during the World War caused much concern to that industry
and led to research work for substitutes, work resulting in the
development of many new and modified types of resins in which tar acids
other than phenol were used. But notwithstanding the use of these
other tar acids the increased demand for synthetic resins used up the
accumulated stocks of phenol sooner than was expected.
Of the phenol produced in the United States from 1919 through 1923 a
large part was natural phenol but the rapid increase in demand and the
improvement of processes for synthetic phenol had by 1923 resulted
in four companies beginning production of the synthetic article. The
rapid increase in output, from about 3 million pounds in 1923 to about
15 million pounds in 1925, was almost entirely in synthetic phenol.
Since then a large part of the domestic production has continued to be
synthetic, although the production of natural phenol since 1935 has been
about four times that of 1929.
Adequate quantities of coal tar are usually available to produce
sufficient natural phenol to meet a substantial part of our requirements,
if it were all recovered, but the quantity actually produced is
determined in part by the demand for other coal-tar products, and in part
by the value of the tar as fuel. More than 50 percent of the tar produced
has been burned as fuel, principally at the coke ovens or nearby steel
mills.
The domestic production and sales of phenol, natural and synthetic
combined, are shown in table 59.
TABLE 59.—_Phenol: United States production and sales, in specified
years, 1918-37_
-----------+----------+--------------------------------+---------------
|Production| Sales |
| | | Ratio of sales
Census year+----------+----------+----------+----------+ to total
| Quantity | Quantity | Value |Unit value| production
-----------+----------+----------+----------+----------+---------------
| _1,000 | _1,000 | _1,000 | | _Percent_
| pounds_ | pounds_ | dollars_ | |
1918 | 106,794 | 106,794 | 37,270 | $0.35 |
1919 | 1,544 | 1,544 | 156 | .10 |
1923 | 3,311 | 2,180 | 590 | .27 | 66
1925 | 14,734 | 8,524 | 1,771 | .21 | 58
1926 | 8,691 | 5,480 | 988 | .18 | 63
1927 | 8,041 | 4,595 | 684 | .15 | 57
1928 | 10,227 | 7,746 | 912 | .12 | 76
1929 | 24,178 | 19,939 | 2,248 | .11 | 83
1930 | 21,147 | 17,715 | 1,976 | .11 | 84
1931 | 17,981 | 14,002 | 1,446 | .10 | 78
1932 | 13,965 | 12,181 | 1,269 | .10 | 87
1933 | 33,220 | 27,923 | 2,881 | .10 | 84
1934 | 44,935 | 36,241 | 3,887 | .11 | 81
1935 | 43,419 | 34,575 | 3,431 | .10 | 80
1936 | 48,724 | 40,942 | 4,235 | .10 | 84
1937 | 65,690 | 57,176 | 6,153 | .11 | 87
-----------+----------+----------+----------+----------+---------------
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
_Grades produced for resins._—Increased production of phenol in recent
years is largely due to the demand from makers of synthetic resins. A
number of grades are regularly produced for this purpose, though it is
believed that the technical grade is the principal one used in resins.
The several grades are as follows:
(1) USP.—Either natural or synthetic. This grade contains not less than
98 percent phenol.
(2) Technical.—Various grades containing from 80 to 95 percent phenol, of
which the two most important are 82-84 percent and 90-92 percent.
(3) Mixtures.—Containing from 30 percent to 80 percent phenol and the
remainder of the isomeric cresols.
_Producers._—Natural phenol is obtained in the distillation of coal tar
and to a smaller extent in the purification of ammonia liquors in coke
and gas plants. In 1937 there were four producers of natural phenol with
plants located at Philadelphia, Pa., Follansbee, W. Va., Indianapolis,
Ind., and Pittsburgh, Pa. All these are tar distillers recovering
creosote oil, pitch, cresylic acid, naphthalene, and other crudes from
coal tar.
Synthetic phenol is made from benzene, either by sulfonation followed
by alkaline fusion, or by chlorination and subsequent heating under
pressure with caustic soda. It is produced in large quantities by two
firms, one at Midland, Mich., and the other at St. Louis, Mo. A third
producer is building a plant at North Tonawanda, N. Y., using a process
recently developed in Germany. Operation of this unit will probably start
late in 1938.
World production.
Natural phenol is recovered in practically all European countries and
in Japan. Germany and the United Kingdom are the principal producers
and have also been the leading exporters. Synthetic phenol was made in
Germany as early as 1900, and during the World War. Plants for synthetic
phenol recently installed are now in operation in Germany, Great Britain,
Belgium, and Italy.
Table 60 shows the average annual world production of phenol in recent
years by countries. Half of the total was produced in the United States.
TABLE 60.—_Phenol: Estimated average annual production, by countries,
1933-35_
--------------+-----------------
| Estimated
Produced in— |annual production
--------------+-----------------
| _1,000 pounds_
UNITED STATES | 41,000
United Kingdom| 18,000
Germany | 10,000
Poland | 3,000
Japan | 3,000
Czechoslovakia| 1,000
Belgium | 2,000
France | 2,000
Italy | 1,500
Spain | 700
+-----------------
Total | 82,200
--------------+-----------------
Source: Consular reports.
In the United Kingdom, where tar distillation is a well developed and
highly organized industry, large quantities of gas-works tar, rich in
phenol and other tar acids, are available. Prior to the World War the
United Kingdom was the principal source of phenol, and of the other
products of tar distillation. During the war several synthetic processes
of commercial importance were developed, but they were discontinued after
its close. A new synthetic unit has recently been installed in England
and is now in operation. Increasing consumption of phenol in synthetic
resins during the last decade, particularly in the last several years,
has changed the United Kingdom from an exporter to an importer of phenol.
Estimated consumption of phenol in the United Kingdom is given as 20
million pounds annually—principally in synthetic resins, and in lesser
quantities in dyes, intermediates, antiseptics, and disinfectants.
In Germany the phenol recovered in 1936 amounted to about 20 million
pounds, and recently three commercial units have been installed for the
production of synthetic phenol, one with a reported daily output of
11,000 pounds.
Natural phenol is also recovered in Belgium, France, the Netherlands,
Czechoslovakia, Poland, Italy, and Spain. Synthetic phenol has recently
been produced for the first time in Belgium and Italy. The quantities
normally produced in these countries are small and are supplemented by
imports from Great Britain and Germany.
The production of phenol in Japan has increased rapidly and has been
sufficient since 1930 to meet domestic requirements. The estimated output
increased from 300,000 pounds in 1927 to more than 3 million pounds
annually in recent years. The Miike Dyestuffs Works is reported to be
producing synthetic phenol.
United States imports.
_Rates of duty._—Prior to September 6, 1916, phenol was imported free of
duty. Since that date it has been dutiable at the various rates shown in
table 61. Under the act of 1930 the rate of duty is 3½ cents per pound
and 20 percent ad valorem on the American selling price (the wholesale
price of a similar competitive article manufactured in the United
States).[21]
TABLE 61.—_Phenol: Rates of duty upon imports into the United States,
1916-37_
------------------+------------------------+----------------------------
Period | Rate of duty | Authority
------------------+------------------------+----------------------------
To Sept. 8, 1916 |Free |Free under Tariff Act of
| | 1913 and previous acts.
| |
Sept. 9, 1916, to |2½ cents per pound plus |Under Revenue Act of 1916.
Sept. 21, 1922. | 15 percent ad valorem |
| on foreign value. |
| |
Sept. 22, 1922, to|7 cents per pound plus |Under par. 27 of Tariff Act
Sept. 21, 1924. | 55 percent ad valorem | of 1922; special provision
| on American selling | for first 2 years.
| price[1] or United |
| States value.[2] |
| |
Sept. 22, 1924, to|7 cents per pound plus |Under par. 27 of Tariff Act
Nov. 29, 1927. | 40 percent ad valorem | of 1922, rate provided
| on American selling | for period after the
| price[1] or United | first 2 years.
| States value.[2] |
| |
Nov. 30, 1927, to |3½ cents per pound plus |By Presidential proclamation
June 17, 1930. | 20 percent ad valorem | following a cost of
| on American selling | production investigation
| price[1] or United | under sec. 315 of Tariff
| States value.[2] | Act of 1922.
| |
June 18, 1930 |3½ cents per pound plus |Under par. 27 (b) of Tariff
| 20 percent ad valorem | Act of 1930.
| on American selling |
| price[3] or United |
| States value.[4] |
------------------+------------------------+----------------------------
[1] As defined in subdivision (f) of section 402, title IV, act
of 1922.
[2] As defined in subdivision (d) of section 402, title IV, act
of 1922.
[3] As defined in subsection (g) of section 402, title IV, act of
1930.
[4] As defined in subsection (e) of section 402, title IV, act of
1930.
_Import statistics._—Imports for consumption are shown in tables 62
and 63. Table 62 shows imports of phenol or carbolic acid and table 63
imports of “all distillates of tars yielding below 190° C. an amount of
tar acids equal to or more than 5 percent.” Imports under the latter
classification prior to 1928 were probably chiefly phenol. Phenol imports
consist entirely of the natural product.
TABLE 62.—_Phenol: United States imports for consumption, 1910-37_
-------+----------------------+---------+--------+----------+----------
| | | | | Computed
Year | Rate of duty | Quantity| Value |Unit value|ad valorem
| | | | | rate
-------+----------------------+---------+--------+----------+----------
| | _Pounds_| | | _Percent_
1910[1]|Free |4,507,693|$275,600| $0.061|
1911[1]| do |4,371,014| 265,780| .061|
1912[1]| do |5,686,704| 521,457| .092|
1913[1]| do |8,345,631| 688,771| .083|
1914[1]| do |8,393,216| 531,535| .063|
1915[1]| do |3,106,445| 179,685| .058|
1916[1]|([2]) |2,246,256| 154,841| .069|
1917[1]|15 percent + 2½ cents | 265,519| 17,168| .065| 53.7
| per pound | | | |
1918 | do | 283,337| 62,497| .221| 26.3
1919 | do | 2,061| 264| .128| 34.5
1920 | do | 1,040| 244| .235| 25.8
1921 | do | 250| 142| .568| 19.4
1922 |([3]) |} 280,224| 30,414| .109| 38.0
| |} 69,310| 16,102| .230| 85.1
1923 |55 percent + 7 cents | 126,618| 21,389| .169| 96.4
| per pound [4] | | | |
1924 |([5]) | 176,081| 46,786| .266| 81.4
1925 |40 percent + 7 cents | 256,126| 58,958| .230| 70.4
| per pound [4] | | | |
1926 | do | 218,437| 47,351| .217| 72.3
1927 |([6]) | 500| 100| .200| 75.0
1928 |20 percent + 3½ cents | 1,653| 298| .180| 39.4
| per pound [4] | | | |
1929 | do | 433,385| 44,226| .102| 54.3
1930 | do | 500| 115| .230| 39.4
1931 | do | 2,365| 639| .270| 33.0
1932 | do | None| | |
1933 | do | 3,440| 641| .186| 38.8
1934 | do | None| | |
1935 | do | 2,605| 211| .081| 63.0
1936 | do | 71,429| 8,302| .116| 50.1
1937[7]| do | 32,238| 3,767| .117| 50.0
-------+----------------------+---------+--------+----------+---------
[1] Fiscal year.
[2] 15 percent ad valorem and 2½ cents per pound effective Sept.
9, 1916.
[3] 55 percent ad valorem and 7 cents per pound, effective Sept.
22, 1922.
[4] Ad valorem based on American selling price or United States
value under acts of 1922 and 1930.
[5] Ad valorem reduced to 40 percent effective Sept. 22, 1924.
[6] Duty reduced to 20 percent ad valorem and 3½ cents per pound
effective Nov. 30, 1927.
[7] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 63.—_All distillates of tar yielding below 190° C. an amount of
tar acids equal to or more than 5 percent: United States imports for
consumption, 1918-37_
---------+----------------------+--------+------+----------+----------
| | | | | Computed
Calendar | Rate of duty |Quantity| Value|Unit value|ad valorem
year | | | | | rate
---------+----------------------+--------+------+----------+----------
| |_Pounds_| | | _Percent_
1918 |15 percent + 2½ cents | 1,550|$2,008| $1.30| 16.93
| per pound | | | |
1919 | do | 3,170| 4,587| 1.45| 16.73
1920 | do | 85,474|36,041| .422| 20.93
1921 | do | 16,240|11,811| .727| 18.43
1922 |([1]) | 350,764|42,912| .122| 46.27
1923 |55 percent + 7 cents | 245,119|30,328| .124| 111.58
| per pound[2] | | | |
1924 |([3]) | 662,938|49,380| .074| 134.43
1925 |40 percent + 7 cents | 252,382|15,441| .061| 154.41
| per pound[2] | | | |
1926 | do | 1,102| 5,236| 4.75| 41.47
1927 |([4]) | 2| 16| 8.00| 40.88
1928-37 | | None| | |
---------+----------------------+--------+------+----------+----------
[1] 55 percent ad valorem and 7 cents per pound, effective Sept.
22, 1922.
[2] Ad valorem based on American selling price or United States
value under acts of 1922 and 1930.
[3] Ad valorem reduced to 40 percent, effective Sept. 22, 1924.
[4] Duty reduced to 20 percent ad valorem and 3½ cents per pound,
effective Nov. 30, 1927.
Source: Foreign Commerce and Navigation of the United States.
United States exports.
Exports of phenol have not been separately shown in official statistics
since 1924. In that year they went chiefly to Panama, Japan, Cuba, and
Mexico. Table 64 shows exports from 1918 to 1924, inclusive, as furnished
by the Department of Commerce.
TABLE 64.—_Phenol: United States exports, 1918-24_
----+---------+----------+----------
Year| Quantity| Value |Unit value
----+---------+----------+----------
| _Pounds_| |
1918|6,477,841|$2,666,634| $0.412
1919|1,243,841| 363,744| .292
1920|2,151,475| 388,047| .180
1921| 249,658| 35,994| .144
1922| 223,146| 23,223| .104
1923| 232,830| 34,389| .148
1924| 51,364| 8,016| .156
----+---------+----------+----------
Source: Commerce and Navigation of the United States.
Appreciable quantities of phenol have been exported in recent years to
Japan and China, and to Great Britain and other European countries.
Export statistics, collected by the U. S. Tariff Commission from the
several domestic producers, show the following quantities exported in
recent years.
TABLE 65.—_Phenol: United States exports, 1934-36_
----+---------+--------+----------
Year| Quantity| Value |Unit value
----+---------+--------+----------
| _Pounds_| |
1934|2,622,900|$329,269| $0.126
1935|2,921,835| 322,933| .111
1936|1,258,244| 148,501| .118
----+---------+--------+----------
Source: Data obtained by the U. S. Tariff Commission through
questionnaires.
In 1934, the principal destinations in order of importance were China,
Italy, and Canada; in 1935 Germany, China, Japan, and Belgium; and in
1936 China, Belgium, and the Netherlands.
Competitive conditions.
Before the World War our average annual consumption of phenol was 5
million pounds, of which about 80 percent was imported from Great
Britain and Germany. These countries produced phenol in excess of their
consumption, and phenol was on the free list in the United States.
In September 1916 phenol became dutiable. The demand was increasing
rapidly because of the use of phenol in the manufacture of picric acid,
an explosive. To meet the wartime demand at home and abroad large scale
production of synthetic phenol sprang up in the United States. But the
end of the war not only shut off the largest part of the demand but left
the producers with large stocks on hand. The price dropped sharply and
the production of synthetic phenol ceased.
Since 1922 there has been a gradually increasing demand for phenol in the
United States, chiefly for use in the manufacture of synthetic resins,
and production has increased to meet this demand as shown in table 66.
TABLE 66.—_Phenol: United States production, imports, exports, and
apparent consumption in specified years, 1918-37_
[In thousands of pounds]
----+-------------+----------+----------+---------------
Year|Production[1]|Imports[2]|Exports[3]| Apparent
| | | |consumption[4]
----+-------------+----------+----------+---------------
1918| 106,794| 285| 6,478| ([5])
1919| 1,544| 5| 1,244| ([5])
1923| 3,311| 372| 233| 3,450
1925| 14,734| 919| ([6]) | ([7])
1926| 8,691| 220| ([6]) | ([7])
1927| 8,041| 1| ([6]) | ([7])
1928| 10,227| 2| ([6]) | ([7])
1929| 24,178| 433| ([6]) | ([7])
1930| 21,147| 1| ([6]) | ([7])
1931| 17,981| 2| ([6]) | ([7])
1932| 13,965| | ([6]) | ([7])
1933| 33,220| 3| ([6]) | ([7])
1934| 44,935| | 2,623| 42,312
1935| 43,419| 3| 2,922| 40,500
1936| 48,724| 71| 1,258| 47,537
1937| 65,690| 32| ([6]) | ([7])
----+-------------+----------+----------+---------------
[1] From table 59.
[2] From tables 62 and 63.
[3] From tables 64 and 65.
[4] Production plus imports minus exports.
[5] Not calculated because of importance of stocks on hand.
[6] Not available.
[7] Not available because of absence of export figures. Exports
probably negligible up to 1929; substantial in 1933.
The manufacture of synthetic phenol was revived about 1923. Imports were
quite small as compared with production, especially after 1927. At first
this was probably due primarily to the protection given by the duty
which had been increased in 1922.[22] But with the increase in volume of
production in the United States the price decreased and since 1933 the
United States producers have enjoyed a substantial export business. It
may therefore be doubted that in recent years there would have been any
substantial imports even if phenol had been free of duty.
THE CRESOLS, XYLENOLS, AND CRESYLIC ACID
Reference to table 56, page 109, will show that, as distillation of coal
tar proceeds and the temperature of distillation is increased, the phenol
fraction is followed in order by the three cresols and then by the six
xylenols. Each of these tar acids is a definite chemical compound with
definite physical properties. Consideration of them as raw materials
for synthetic resins is complicated by the fact that they are generally
used in mixtures and that the commercial term, cresylic acid, applied
to many of these mixtures has no definite relationship to the precise
chemical terminology. Yet since the term cresylic acid is so widely used
in commerce, since the tariff provides for imports under that name, and
since the statistics available are in part in terms of cresylic acid and
in part in terms of cresols and xylenols it is impossible to present the
complete picture on the basis of the correct chemical terminology.
Description and uses.
_The cresols._—The cresols are isomeric tar acids obtained from coal
tar by fractional distillation. Their combined content averages about
1 percent of domestic coal tar. The total cresol content is divided in
about the following proportions: 40 percent metacresol, 35 percent
orthocresol, and 25 percent paracresol. The cresols are marketed in a
number of types and grades including mixtures of ortho, meta, and para;
mixtures of meta and para; separated ortho, meta, and para; and also in
mixtures with phenol and the xylenols.
_Metacresol_ (chemically, 3-methyl phenol) is a colorless to yellow
liquid with a phenol-like odor. When pure, it melts at 11° C., boils
at 202.8° C., and has a specific gravity of 1.03. It is used in the
manufacture of synthetic resins, photographic developers, explosives,
disinfectant soaps, paint and varnish removers, to remove ink from
newsprint, to soften and reclaim rubber, and in intermediates for dyes
and perfume materials.
_Orthocresol_ (chemically, 2-methyl phenol) is a colorless, crystalline
product with a phenol-like odor, melting at 30° C., boiling at 190.8° C.,
and having a specific gravity of 1.04. It is used in the manufacture of
coumarin (flavor), antiseptics, disinfectants, and fumigants. It is not
used to any extent in synthetic resins.
_Paracresol_ (chemically, 4-methyl phenol) is a colorless, crystalline
substance with a phenol-like odor, melting at 35° C., boiling at 201.8°
C., and having a specific gravity of 1.03. It is used in the manufacture
of intermediates, dyes, disinfectants, and fumigants, in medicine, and
in mixture with metacresol in synthetic resins. Domestic production
of synthetic paracresol was announced early in 1938 by Swann & Co.,
Birmingham, Ala.
_Metaparacresol_ is a combination of approximately 60 percent meta
and 40 percent para cresol obtained in the fractional distillation of
mixed cresols. The ortho isomer is distilled off, leaving a residue of
metaparacresol. It is widely used in the manufacture of synthetic resins.
_Cresol._—The term cresol used without further qualification indicates
a mixture of the three isomers in substantially the same proportions
in which they are found in coal tar. The United States Pharmacopoeia
describes cresol, a mixture of isomeric cresols obtained from coal tar,
as a colorless or yellowish to brownish-yellow or a pinkish, highly
refractive liquid, becoming darker with age and on exposure to light. It
is widely used in synthetic resins, antiseptics and disinfectants, and in
medicine.
_The xylenols._—Shortly after the original patents on Bakelite resins
expired extensive research was begun for raw materials that would give
different properties to the resultant resins. This work led to a study of
the high-boiling tar acids, and methods of recovery for some of them were
commercially developed. Among those obtained from coal tar are the six
isomeric xylenols, methylethyl phenol, and one of the trimethyl phenols
(see table 56). Coal tar contains about 0.2 percent xylenols and 0.5
percent other high-boiling tar acids.
The principal uses for these products have been in the preparation of
high-phenol coefficient disinfectants, and recently in the replacement
of phenol and cresols in synthetic resins. It was found, for example,
that 3: 5 xylenol reacts with formaldehyde faster than either metacresol
or phenol. Numerous patents have been granted on the use of these
high-boiling acids in the production of synthetic resins.
The xylenols, when pure, are colorless, crystalline substances boiling
between 211° and 225° C. They are usually marketed in mixtures containing
from 50 to 80 percent xylenols and 20 to 50 percent cresols. There is
commercial production of at least one of the separated xylenols (3: 5).
An appreciable part of our imports of crude cresylic acid and of our
production of cresylic acid contains high percentages of the xylenols.
_Other high-boiling tar acids._—The other high-boiling tar acids
are ortho ethylphenol, meta ethylphenol, para ethylphenol, methyl
ethylphenol, and the three isomeric trimethyl phenols. Several of these
have been isolated from coal tar. All of them, when pure, are crystalline
compounds with boiling points ranging between 206° and 235° C. There
has been little, if any, commercial production of this group up to this
time. They are known, however, to have very high phenol coefficients, a
property which would make them suitable for use in disinfectants. Little
is known as yet concerning their application in synthetic resins.
_Cresylic acid._—Cresylic acid is a generic term now applied to mixtures
of tar acids in widely varying proportions. As defined in the literature
and as formerly used in commerce the term identified a mixture of
ortho, meta, and para cresols in the proportions in which they occur in
coal tar. This proportion is approximately 40 percent metacresol, 35
percent orthocresol, and 25 percent paracresol. But in recent years the
designation cresylic acid has been applied to all sorts of mixtures of
tar acids boiling above 190° C. Practically every maker of synthetic
resins, antiseptics, and disinfectants has his own specifications for
cresylic acid; it may be any mixture in almost any proportions of the
three cresols, the six isomeric xylenols, and the higher boiling tar
acids. Imports of crude cresylic acid are understood to be largely
xylenol mixtures containing low percentages of the cresols. This loose
application of cresylic acid in recent years is due to the increased
commercial application of the high-boiling tar acids, especially the
xylenols.
Under the Tariff Act of 1930 refined cresylic acid, that having a purity
of 75 percent or more, is dutiable under paragraph 27 at 3½ cents per
pound and 20 percent ad valorem based on American selling price or United
States value; while crude cresylic acid, that having a purity of less
than 75 percent, is free under paragraph 1651. The provision in paragraph
27 reads, “cresylic acid which on being subjected to distillation
yields in the portion distilling below two hundred and fifteen degrees
centigrade, a quantity of tar acids equal to or more than 75 per centum
of the original distillate.” Under this provision cresylic acid may
include an endless number of combinations of tar acids and may or may not
contain any of the isomeric cresols. Of the 17 or more tar acids known
to exist in coal tar (see table 56), only 8 have boiling points above
215° C. It would seem to be more accurate and more in line with present
day usage to have the tariff drop the designation cresylic acid in favor
of more definite terms based on composition, such as cresols and cresol
mixes, xylenol and xylenol mixes, etc.
About 60 percent of our consumption of cresylic acid is in synthetic
resins and the remainder in the manufacture of insecticides, antiseptics,
disinfectants, and other coal-tar products, such as intermediates for
dyes, plasticizers for nitrocellulose, etc.
United States production.
_The cresols._—There is large production of cresol, metaparacresol, and
orthocresol in the United States. Commercial production of paracresol was
reported for the first time in 1934, and of metacresol in 1935.
Statistics of domestic production and sales are publishable only for the
year 1934 because of the small number of producers. The output in that
year is shown in table 67. Production has increased appreciably since
then.
TABLE 67.—_Meta, ortho, and para cresols: United States production and
sales, 1934_
----------------+------------+-----------------------------------
| | Sales
Type | Production +-----------+----------+------------
| | Quantity | Value | Unit value
----------------+------------+-----------+----------+------------
| _Pounds_ | _Pounds_ | |
Cresol | 8,929,836 | 8,559,048 | $572,738 | $0.07
Metaparacresol | 2,033,424 | 1,692,149 | 101,324 | .06
Orthocresol | 835,016 | ([1]) | ([1]) |
Paracresol | ([1]) | ([1]) | ([1]) |
----------------+------------+-----------+----------+------------
[1] Not publishable; figures would reveal operations of
individual firms.
Source: Dyes and Other Synthetic Organic Chemicals in the United
States. U. S. Tariff Commission.
The trend of domestic production of the several cresols is upward. In
1937 the output of all grades and types of cresols was 13,745,271 pounds
with sales of 13,251,345 pounds, valued at $1,071,965. The practice of
topping coal tar will greatly increase the output of the cresols as well
as of other tar acids and naphthalene.
There are five domestic producers of cresol, three each of orthocresol
and metaparacresol, and two of metacresol and paracresol. All except one
of these makers recover natural phenol, cresylic acids, and other tar
acids. Refining plants are located at Pittsburgh, Pa., Philadelphia,
Pa., Indianapolis, Ind., and Follansbee, W. Va. Domestic production of
synthetic paracresol was first announced in 1938.
_The xylenols._—There has been a large domestic production of mixed
xylenols in recent years. These mixtures, containing from 50 to 80
percent xylenols, are marketed as cresylic acid. Statistics of domestic
production, and sales are therefore included in table 68. It is estimated
that the output of xylenols and xylenol mixtures in 1935 exceeded 750,000
pounds and exceeded 1,250,000 pounds in 1937. At least one of the
separated xylenols (1: 3: 5) has been produced commercially in the United
States since 1935, but statistics of its production are not publishable.
_Other high-boiling tar acids._—There was no reported domestic production
of the other high-boiling acids prior to 1935 and the data obtained for
that year are probably incomplete. Estimated output was 200,000 pounds in
1935, 250,000 pounds in 1936, and 300,000 pounds in 1937. These estimates
are based on production of mixtures of high-boiling acids.
_Cresylic acid._—Domestic production and sales statistics for so-called
crude cresylic acid are not publishable. It is known, however, that
production of the crude is small compared with our output of refined
cresylic acid. It is usually more economical for the producer to prepare
the mixture of tar acids to the specifications of the purchaser, rather
than to leave part of the refining operations to be performed by the
latter. The fact that imports of cresylic acid are chiefly of crude is
largely due to the different tariff treatment of crude and refined.
Domestic production of refined cresylic acid was confined to one or two
firms until 1928, when there were four makers. Statistics of production
and sales are not publishable for the years prior to 1929, though it may
be stated that the annual domestic output increased each year to supply
the increased demand. Table 68 shows production and sales from 1929 to
1934, inclusive. Data for later years are not publishable.
TABLE 68.—_Refined cresylic acid: United States production and sales,
1929-37_
-----+------------+-------------------------------------
| | Sales
Year | Production +------------+------------+-----------
| | Quantity | Value | Unit value
-----+------------+------------+------------+-----------
| _Pounds_ | _Pounds_ | | _Per pound_
1929 | 14,601,534 | | | $0.10
1930 | 17,305,308 | 16,026,407 | $1,267,155 | .08
1931 | 10,994,000 | 10,305,000 | 652,000 | .06
1932 | 8,060,000 | 4,805,000 | 251,000 | .05
1933 | 13,813,941 | 11,975,441 | 626,496 | .05
1934 | 10,949,860 | 9,230,255 | 489,231 | .05
1935 | ([1]) | ([1]) | ([1]) |
1936 | ([1]) | ([1]) | ([1]) |
1937 | ([1]) | ([1]) | ([1]) |
-----+------------+------------+------------+-----------
[1] Not publishable; figures would reveal operations of
individual firms.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
As previously stated, the composition of cresylic acid has gradually been
changed from a mixture of the isomeric cresols to mixtures of cresols,
xylenols, and high-boiling tar acids. The cresols, formerly included
under cresylic acid statistics, are now shown separately. For this reason
the data in table 68 do not fully reflect the increased output of these
tar acids in recent years. Statistics for years prior to 1931 probably
include all of the tar acids except phenol, while those for subsequent
years do not include the separated cresols. In 1934 the production of
refined cresylic acid was 10,949,860 pounds, and in addition recovery
of the several cresols amounted to 11,798,276 pounds making a total of
22,748,136 pounds as compared with a total of 14,601,534 pounds in 1929
and 17,305,308 pounds in 1930.
During 1936 and the first part of 1937 a serious shortage of cresylic
acid existed in the domestic market owing to increased demand by
synthetic resin makers. The output in 1936 exceeded that in 1935 and
the production in 1937 was appreciably higher than in 1936. These
increases are due to the recovery of appreciable quantities at several
new distillation plants, the topping of large amounts of tar hitherto not
processed, and increased production by present recovery units.
There are many grades of cresylic acid, most of which are prepared by
mixing or blending to individual specifications. Every large consumer
apparently has his own specifications. In addition to these special
mixtures there are the following standard blends:
(1) Ninety-nine percent high-boiling, straw color.
(2) Low-boiling, straw color.
(3) Special resin grade, high-boiling.
There are four domestic producers of cresylic acid with recovery and
refining units at Pittsburgh, Pa., Philadelphia, Pa., Indianapolis,
Ind., and Follansbee, W. Va. The last three mentioned are refining
plants operated in conjunction with a number of tar distillation units
widely scattered throughout the country. These units usually recover
crude tar-acid fractions in the distillation of tar and ship them to
these refining plants for separation and refining. All in this group are
purchasers of coal tar. The fourth producer operates a byproduct recovery
unit in connection with the company’s coke-oven operations. Part of the
coal tar produced is distilled to recover the several products, including
creosote oil, tar acids, and naphthalene, and the residual pitch is mixed
with the remaining undistilled tar and used for fuel. The shortage of tar
acids and naphthalene in 1936 caused this producer to begin the topping
of tar.
Foreign production.
The cresols are produced in the United Kingdom, Germany, France, the
Netherlands, Belgium, and other European countries. Coal tar recovered
in the United Kingdom is principally gas tar, which is much richer in
tar acids than coke-oven tar, the principal source in the United States.
This is true because low temperature carbonization of coal yields greater
quantities of tar acids than are obtained in the tar from byproduct coke
ovens. Exports to the United States are chiefly mixtures which can enter
as crude cresylic acid.
Production of cresol in Germany in recent years is shown in table 69.
TABLE 69.—_Cresol: German production, in specified years_
-------+------------
Year |1,000 pounds
-------+------------
1929 | 23,814
1931[1]| 15,435
1933 | 11,780
1934 | 10,476
-------+------------
[1] Includes 2,866,000 pounds of separated ortho, meta, and para
cresols.
Source: Consular reports.
German imports and exports of cresol, in recent years, are shown in table
70.
TABLE 70.—_Cresol: German imports and exports, in specified years_
----+--------+--------
Year|Imports |Exports
----+--------+--------
|_1,000 |_1,000
| pounds_| pounds_
1929| 2,037 | 8,494
1930| 1,277 | 6,712
1931| 1,874 | 7,980
1932| 1,541 | 3,669
1933| 1,832 | 4,970
1934| 1,960 | 6,345
1935| 2,117 | 8,528
1936| 3,737 | 4,531
1937| 1,787 | 4,423
----+--------+--------
Source: Consular reports (1929-33) and official German statistics
(1934-37).
The output of cresols in Czechoslovakia in recent years is shown in table
71.
TABLE 71.—_Cresol: Production in Czechoslovakia, in specified years_
-----+----------
Year | Quantity
-----+----------
| _1,000
| pounds_
1928 | 1,984
1931 | 1,477
1932 | 1,102
1933 | 1,599
1934 | 1,918
-----+----------
Source: Consular reports.
Cresylic acid is recovered in all the countries of Europe, Great Britain
and Germany being the leading producers and the principal exporters.
Increasing demand in these countries for synthetic resins made from
cresylic acid has greatly reduced the quantities available for export in
recent years.
Great Britain is probably the world’s largest producer of cresylic acid,
and for many years has been the principal exporter to the United States.
This position is due to the large available supply of gas-house tar, and
to an ample market for all the products of tar distillation. In 1935
the tar distilled in England, Wales, and Scotland totaled 360 million
gallons, of which 55 percent was gas-house tar.
British production of all grades of cresylic acid averages between 35
million and 42 million pounds annually, of which from 12 million to 20
million pounds are exported. Many British producers market their tar
products through pools and associations. There is a cresylic acid pool, a
phenol pool, and at least two creosote oil export associations, a pitch
marketing association, and a benzol association. One of the principal
grades of cresylic acid produced in Great Britain is “American duty-free
specification.”
Table 72 shows British exports of cresylic acid, by countries, in recent
years.
TABLE 72.—_Cresylic acid: British exports, by countries, 1933-37_
-------------------+------+------+------+------+------
Destination | 1933 | 1934 | 1935 | 1936 | 1937
-------------------+------+------+------+------+------
| Quantity (in thousands of pounds)
+------+------+------+------+------
UNITED STATES | 3,616| 5,783| 6,116|11,296|([1])
Chile | 1,381| 2,958| 2,814| 662|([1])
France | 358| 87| 214| 189|([1])
Japan | 632| 203| 685| 2,002|([1])
All other countries| 5,464| 6,965| 7,333| 9,250|([1])
+------+------+------+------+------
Total |11,451|15,997|17,162|23,399|26,697
+------+------+------+-------------
| Value (in thousands of dollars)
+------+------+------+------+------
UNITED STATES | 147| 277| 255| 620|([1])
Chile | 28| 89| 87| 31|([1])
France | 21| 5| 20| 14|([1])
Japan | 38| 20| 43| 118|([1])
All other countries| 189| 307| 330| 537|([1])
+------+------+------+------+------
Total | 422| 698| 734| 1,321| 2,262
-------------------+------+------+------+------+------
[1] Not available.
Source: Official British statistics.
Imports into the United States.
_Rates of duty._—Prior to September 8, 1916, the cresols were imported
free of duty. Since that date they have been subject to the tariff
treatment shown in table 73.
TABLE 73.—_The cresols: Rates of duty upon United States imports, 1916-37_
------------------+------------------------------------+-----------------
| Rate of duty |
Period +----------+-------------+-----------+ Authority
|Less than | 75 to 90 | 90 percent|
|75 percent| percent | or more |
| pure | pure | pure |
------------------+----------+-------------+-----------+-----------------
To Sept. 8, 1916. |Free |Free |Free |Free under par.
| | | | 452, Tariff Act
| | | | of 1913, and
| | | | under previous
| | | | acts.
| | | |
Sept. 9, 1916, to | do | do |15 percent |Revenue Act of
Sept. 8, 1921. | | | ad | 1916.
| | | valorem |
| | | and 2½ |
| | | cents per|
| | | pound. |
| | | |
Sept. 9, 1921, to | do | do |15 percent |Emergency Tariff
Sept. 21, 1922. | | | ad | Act of 1921.
| | | valorem | From May 28,
| | | and 2 | 1921, to Sept.
| | | cents per| 21, 1922,
| | | pound. | imports
| | | | prohibited
| | | | except when
| | | | not obtainable
| | | | in sufficient
| | | | quantities or
| | | | on reasonable
| | | | terms as to
| | | | quality, price,
| | | | and terms of
| | | | delivery.
| | | |
Sept. 22, 1922, to| do |55 percent ad|55 percent |Free under par.
Sept. 21, 1924. | | valorem and| ad | 1549 and
| | 7 cents per| valorem | dutiable under
| | pound.[1] | and 7 | par. 27 of
| | | cents per| Tariff Act of
| | | pound.[1]| 1922.
| | | |
Sept. 22, 1924, to| do |40 percent ad|40 percent |Same; ad valorem
June 17, 1930. | | valorem and| ad | reduced to 40
| | 7 cents per| valorem | percent under
| | pound.[1] | and 7 | provisions of
| | | cents per| the Tariff Act
| | | pound.[1]| of 1922.
| | | |
June 18, 1930, to | do | do |20 percent |Free under par.
date. | | | and 3½ | 1651 and
| | | cents per| dutiable under
| | | pound.[1]| par. 27 of the
| | | | Tariff Act of
| | | | 1930.
------------------+----------+-------------+-----------+-----------------
[1] Ad valorem based on American selling price or United States
value.
Under the Tariff Act of 1930 metacresol, orthocresol, and paracresol as
such or in mixture, if less than 75 percent pure, would be imported free
under paragraph 1651.[23] If from 75 to 90 percent, they are dutiable
under paragraph 27 at 7 cents a pound and 40 percent based upon American
selling price.[24] And if 90 percent pure or more, they are dutiable
under paragraph 27 at 3½ cents per pound and 20 percent, based upon
American selling price.[25]
The duties on cresylic acid in recent years are shown in table 74. Under
the Tariff Act of 1930, cresylic acid less than 75 percent pure is free
under paragraph 1651.[23] If more than 75 percent pure it is dutiable
under paragraph 27 (b) at 3½ cents per pound and 20 percent, based on
American selling price.[26]
TABLE 74.—_Cresylic acid: Rates of duty upon United States imports,
1916-37_
------------------+----------------------------+------------------------
| Rate of duty |
+----------+-----------------+
Period | Less than| | Authority
|75 percent| 75 percent pure |
| pure | or more |
------------------+----------+-----------------+------------------------
To Sept. 8, 1916. |Free |Free |Free under par. 452 of
| | | Tariff Act of 1913
| | | and previous acts.
| | |
Sept. 9, 1916, to | do |15 percent ad |Revenue Act of 1916.
Sept. 8, 1921. | | valorem and |
| | 2½ cents per |
| | pound. |
| | |
Sept. 9, 1921, to | do |15 percent ad |Emergency Tariff Act of
Sept. 21, 1922. | | valorem and | 1921. From May 28,
| | 2 cents per | 1921, to Sept. 21,
| | pound. | 1922, imports
| | | prohibited except
| | | when not obtainable
| | | in sufficient
| | | quantities or on
| | | reasonable terms as
| | | to quality, price,
| | | and terms of delivery.
| | |
Sept. 22, 1922, to| do |55 percent ad |Free under par. 1549
Sept. 21, 1924. | | valorem and | and dutiable under
| | 7 cents per | par. 27 of the Tariff
| | pound.[1] | Act of 1922.
| | |
Sept. 22, 1924, to| do |40 percent ad |Same; ad valorem
Aug. 18, 1927. | | valorem and | reduced to 40 percent
| | 7 cents per | under provisions of
| | pound.[1] | the Tariff Act of
| | | 1922.
| | |
Aug. 19, 1927, to| do |20 percent ad |Duty reduced by
June 17, 1930. | | valorem and | Presidential
| | 3½ cents per | proclamation.
| | pound.[1] |
| | |
June 18, 1930, to | do |20 percent ad |Free under par. 1651 and
date. | | valorem and | dutiable under par. 27
| | 3½ cents per | of the Tariff Act of
| | pound.[1] | 1930.
------------------+----------+-----------------+------------------------
[1] Ad valorem based on American selling price or United States
value.
_Import statistics._—Imports of the separated and mixed cresols are
combined in official statistics. Table 75 shows imports of the cresols
“90 percent pure or more.” There have been no recorded imports of less
pure grades.
Tables 76, 77, and 78 show, by principal sources, imports of metacresol,
orthocresol, and paracresol, as obtained from invoice analyses by the
United States Tariff Commission. The sum of the three tabulations does
not equal the total shown for all cresols in table 75. The difference
in 1934 of 38,744 pounds valued at $12,906 is accounted for by mixed
cresols. Undoubtedly the differences in other years may be similarly
accounted for.
TABLE 75.—_Metacresol, orthocresol, and paracresol, 90 percent pure or
more: United States imports for consumption, 1920, and 1923-37_
-----------------+-------------------+--------+------+------+----------
| | | | Unit | Computed
Calendar year | Rate of duty[1] |Quantity| Value| value|ad valorem
| | | | | rate
-----------------+-------------------+--------+------+------+----------
| |_Pounds_| | | _Percent_
| | | | |
1920 |2½ cents per pound | 2,444|$2,230|$0.912| 17.7
| + 15 percent | | | |
1923 |7 cents per pound | 8,754| 5,410| .618| 66.3
| + 55 percent | | | |
1924 |} do | 15,326| 1,995| .130| 108.8
|}7 cents per pound | 1,000| 663| .663| 50.6
| + 40 percent | | | |
1925 | do | 34,874| 5,741| .165| 82.5
1926 | do | 105,238|15,040| .143| 89.0
1927 | do | 174,094|35,054| .201| 74.8
1928 | do | 207,897|33,638| .162| 83.3
1929 | do | 227,974|32,098| .141| 89.8
1930: | | | | |
Jan. 1-June 17 | do | 131,134|14,973| .114| 101.3
June 18-Dec. 31|3½ cents per pound | 71,183|11,762| .165| 41.2
| + 20 percent | | | |
| +--------+------+------+----------
Total, 1930 | | 202,317|26,735| .132| 74.9
1931 | do | 151,571|26,901| .177| 39.7
1932 | do | 83,848|18,530| .221| 35.8
1933 | do | 48,511|16,205| .334| 30.5
1934 | do | 124,598|34,361| .276| 32.7
1935 | do | 65,468|18,290| .279| 32.5
1936 | do | 83,273|27,686| .332| 30.5
1937[2] | do | 167,278|36,227| .217| 36.2
-----------------+-------------------+--------+------+------+----------
[1] Ad valorem rate based on American selling price or United
States value under the Tariff Acts of 1922 and 1930.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 76.—_Metacresol: United States imports for consumption by principal
sources, in specified years_
----------------------------+-----+------+------+------+------+---------
Imported from | 1929 | 1931| 1933 | 1934 | 1935 | 1936 | 1937[1]
-------------------+--------+-----+------+------+------+------+---------
| Quantity (pounds)
+--------+-----+------+------+------+------+---------
United Kingdom | 113,057| 916|15,769|21,054| 6,500| 6,800| 40,878
Germany | 3,235| | 4,432| | | |
All other countries|[2]1,106| | | | | |[3]11,025
+--------+-----+------+------+------+------+---------
Total | 117,398| 916|20,201|21,054| 6,500| 6,800| 51,903
+--------+-----+------+------+------+------+---------
| Invoice value
+--------+-----+------+------+------+------+---------
United Kingdom | ([4]) |([4])|$5,264|$8,400|$2,645|$2,589| $6,951
Germany | ([4]) |([4])| 1,548| | | |
All other countries| ([4]) |([4])| | | | | [3]4,200
+--------+-----+------+------+------+------+---------
Total | | | 6,812| 8,400| 2,645| 2,589| 11,151
+--------+-----+------+------+------+------+---------
| Invoice unit value
+--------+-----+------+------+------+------+---------
United Kingdom | ([4]) |([4])|$0.334|$0.399|$0.407|$0.380| $0.170
Germany | ([4]) |([4])| .349| | | |
All other countries| ([4]) |([4])| | | | | .381
+--------+-----+------+------+------+------+---------
Average | | | .337| .399| .407| .380| .215
+--------+-----+------+------+------+------+---------
| Percent of total quantity
+--------+-----+------+------+------+------+---------
United Kingdom | 96.30|100.0| 78.06| 100.0| 100.0| 100.0| 78.76
Germany | 2.76| | 21.94| | | |
All other countries| 2.94| | | | | | [3]21.24
+--------+-----+------+------+------+------+---------
Total | 100.00|100.0|100.00| 100.0| 100.0| 100.0| 100.00
-------------------+--------+-----+------+------+------+------+---------
[1] Preliminary.
[2] Netherlands.
[3] Switzerland.
[4] Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
TABLE 77.—_Orthocresol: United States imports for consumption, by
principal sources, in specified years_
-------------------+-------+------+------+------+------+------+-------
Imported from— | 1929 | 1931 | 1933 | 1934 | 1935 | 1936 |1937[1]
-------------------+-------+------+------+------+------+------+-------
| Quantity (pounds)
+-------+------+------+------+------+------+-------
United Kingdom |105,790|79,198|19,548|25,855|29,120|33,816|112,108
Germany | 82,859| 5,914| | 10| 10| |
France | | | | | | 4,480|
All other countries| 30,600| | | | | |
+-------+------+------+------+------+------+-------
Total |219,249|85,112|19,548|25,865|29,130|38,296|112,108
+-------+------+------+------+------+------+-------
| Invoice value
+-------+------+------+------+------+------+-------
United Kingdom |([2]) |([2]) |$1,591|$2,707|$2,529|$3,178|$14,940
Germany |([2]) |([2]) | | 4| 4| |
France | | | | | | 336|
+-------+------+------+------+------+------+-------
Total | | | 1,591| 2,711| 2,533| 3,514| 14,940
+-------+------+------+------+------+------+-------
| Invoice unit value
+-------+------+------+------+------+------+-------
United Kingdom |([2]) |([2]) |$0.081|$0.105|$0.087|$0.094| $0.133
Germany |([2]) |([2]) | | .400| .400| |
France | | | | | | .075|
+-------+------+------+------+------+------+-------
Average | | | .081| .105| .087| .092| .133
+-------+------+------+------+------+------+-------
| Percent of total quantity
+-------+------+------+------+------+------+-------
United Kingdom | 48.25| 93.05| 100.0| 99.96| 99.97| 88.30| 100.00
Germany | 37.79| 6.95| | .04| .03| |
France | | | | | | 11.70|
All other countries| 13.96| | | | | |
+-------+------+------+------+------+------+-------
Total | 100.00|100.00| 100.0|100.00|100.00|100.00| 100.00
-------------------+-------+------+------+------+------+------+-------
[1] Preliminary.
[2] Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
TABLE 78.—_Paracresol: United States imports for consumption, by
principal sources, in specified years_
---------------+-----+------+------+------+------+-------+-------
Imported from— | 1929| 1931 | 1933 | 1934 | 1935 | 1936 |1937[1]
---------------+-----+------+------+------+------+-------+-------
| Quantity (pounds)
+-----+------+------+------+------+-------+-------
United Kingdom |2,587| 458| 6,972|16,889|16,625| 32,666| 14,338
Netherlands | |11,243| | | | |
Germany | | | | 8,818|11,023| 6,076|
France | | | |13,228| 5| 6| 4
+-----+------+------+------+------+-------+-------
Total |2,587|11,701| 6,972|38,935|27,653| 38,748| 14,342
+-----+------+------+------+------+-------+-------
| Invoice value
+-----+------+------+------+------+-------+-------
United Kingdom |([2])|([2]) |$2,652|$4,797|$4,485|$10,739| $5,415
Netherlands |([2])|([2]) | | | | |
Germany |([2])|([2]) | | 1,921| 3,090| 3,079|
France |([2])|([2]) | | 3,626| 7| 7| 3
+-----+------+------+------+------+-------+-------
Total | | | 2,652|10,344| 7,582| 13,825| 5,418
+-----+------+------+------+------+-------+-------
| Invoice unit value
+-----+------+------+------+------+-------+-------
United Kingdom |([2])|([2]) |$0.380|$0.284|$0.270| $0.329| $0.378
Netherlands |([2])|([2]) | | | | |
Germany |([2])|([2]) | | .218| .280| .506|
France |([2])|([2]) | | .274| 1.400| 1.167| .750
+-----+------+------+------+------+-------+-------
Average | | | .380| .266| .274| .357| .378
+-----+------+------+------+------+-------+-------
| Percent of total quantity
+-----+------+------+------+------+-------+-------
United Kingdom |100.0| 3.92| 100.0| 43.38| 60.12| 84.30| 99.97
Netherlands | | 96.08| | | | |
Germany | | | | 22.65| 39.86| 15.68|
France | | | | 33.97| .02| .02| .03
+-----+------+------+------+------+-------+-------
Total |100.0|100.00| 100.0|100.00|100.00| 100.00| 100.00
---------------+-----+------+------+------+------+-------+-------
[1] Preliminary.
[2] Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
The processes for recovery of the cresols (fractional distillation)
usually yield products more than 75 percent pure and most of the
consumers of mixed or prepared cresols require products of high purity.
This explains why there are no imports less than 75 percent pure,
notwithstanding that they are duty-free under paragraph 1651.
Under the act of 1930 cresols of 90 percent or greater purity are
assessed for duty at 20 percent ad valorem and 3½ cents per pound while
cresols 75.1 to 89.9 percent pure are assessed for duty at 40 percent ad
valorem and 7 cents per pound. Naturally, since the duty on imports below
90 percent pure is double that on imports over 90 percent pure there are
no imports of the former.
Imports of crude cresylic acid are shown in table 79 and those of refined
cresylic acid in table 80. Imports by principal sources are shown in
tables 81 and 82, for crude and refined, respectively.
TABLE 79.—_Crude cresylic acid: United States imports for consumption,
1924-37_
-------+-----------+---------+-------
Year |Quantity[1]| Value | Unit
| | | value
-------+-----------+---------+-------
| _Pounds_ | |
1924 | 2,327,528| $157,643|$0.068
1925 | 2,163,557| 122,742| .057
1926 | 5,702,740| 331,550| .058
1927 | 9,136,516| 567,802| .062
1928 | 10,687,109| 678,177| .063
1929 | 17,856,765| 952,110| .053
1930 | 9,009,674| 501,418| .056
1931 | 4,937,078| 244,631| .050
1932 | 4,077,700| 164,379| .040
1933 | 5,523,733| 178,824| .032
1934 | 7,163,511| 284,051| .040
1935 | 6,849,113| 265,485| .039
1936 | 13,476,427| 722,575| .054
1937[2]| 16,360,213|1,219,268| .075
-------+-----------+---------+-------
[1] Conversion factor—8.5 pounds to gallon.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 80.—_Refined cresylic acid: United States imports for consumption,
in specified years, 1919-37_
------------------+---------------+------------+-------+------+----------
| | | | Unit | Computed
Calendar year | Rate of duty | Quantity | Value | value|ad valorem
| | | | | rate
------------------+---------------+------------+-------+------+----------
| | _Pounds_ | | | _Percent_
1919 |2½ cents per | 2,061| $264|$0.128| 34.5
| pound plus | | | |
| 15 percent. | | | |
1920 | do. | 1,040| 244| .235| 25.7
1923 |7 cents per | 2,815| 257| .091| 131.7
| pound plus | | | |
| 55 percent.[1]| | | |
1924: | +============+=======+======+==========
Jan. 1-Sept. 21 | do.[1] | 62,869| 15,169| .241| 84.0
Sept. 22-Dec. 31|7 cents per | 378,777| 29,066| .077| 131.2
| pound plus | | | |
| 40 percent.[1]| | | |
| +------------+-------+------+----------
Total | | 441,646| 44,235| |
1925 | do.[1] | 98,672| 23,618| .239| 69.2
1926 | do.[1] | 25,932| 4,748| .183| 78.2
1927: | +============+=======+======+==========
Jan. 1-Aug. 18 | do.[1] | 1,322| 978| .740| 49.5
Aug. 19-Dec. 31 |3½ cents per | 610,488| 37,896| .062| 76.4
| pound plus | | | |
| 20 percent.[1]| | | |
| +------------+-------+------+----------
Total | | 611,810| 38,874| |
1928 | do.[1] | 976,180| 70,513| .072| 68.5
1929 | do.[1] |[2]2,343,529|183,324| .078| 64.7
1930 |3½ cents per | 1,275,872| 96,047| .075| 66.5
| pound plus | | | |
| 20 percent.[1]| | | |
1931 | do.[1] | [3]707,105| 42,156| .060| 78.7
1932 | do.[1] | [4]641,899| 37,326| .058| 80.2
1933 | do.[1] | 121,634| 9,164| .075| 66.5
1934 | do.[1] | 23,964| 1,497| .062| 76.0
1935 | do.[1] | 16,602| 1,128| .068| 71.5
1936 | do.[1] | 512| 40| .078| 64.8
1937[5] | do.[1] | 46,479| 5,122| .110| 51.8
------------------+---------------+------------+-------+------+----------
[1] Based on American selling price or United States value.
[2] Drawback paid on 44 percent.
[3] Drawback paid on 80 percent.
[4] Drawback paid on 105,285 pounds.
[5] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 81.—_Crude cresylic acid: United States imports for consumption,
from principal sources, in specified years, 1929-37_
-------------------+----------+---------+---------+---------
Imported from— | 1929 | 1931 | 1933 | 1934
-------------------+----------+---------+---------+---------
| Quantity (pounds)
+----------+---------+---------+---------
United Kingdom |13,981,259|3,809,293|5,060,925|6,927,865
Germany | 3,874,400|1,073,491| 357,034| 217,965
Netherlands | 1,106| 54,294| 22,066|
All other countries| | |[2]83,708| 17,681
+----------+---------+---------+---------
Total |17,856,765|4,937,078|5,523,733|7,163,511
+----------+---------+---------+---------
| Value
+----------+---------+---------+---------
United Kingdom | $739,385| $190,333| $165,986| $276,989
Germany | 212,652| 51,643| 8,666| 6,263
Netherlands | 73| 2,655| 551|
All other countries| | | [2]3,621| 799
+----------+---------+---------+---------
Total | 952,110| 244,631| 178,824| 284,051
+----------+---------+---------+---------
| Unit value
+----------+---------+---------+---------
United Kingdom | $0.0529| $0.0500| $0.0328| $0.0400
Germany | .0549| .0481| .0243| .0287
Netherlands | .0660| .0489| .0250|
All other countries| | | .0432| .0452
+----------+---------+---------+---------
Average | .0533| .0495| .0324| .0396
+----------+---------+---------+---------
| Percent of total quantity
+----------+---------+---------+---------
United Kingdom | 78.3| 77.2| 91.6| 96.7
Germany | 21.7| 21.7| 6.5| 3.0
Netherlands | | 1.1| .4|
All other countries| | | 1.5| .3
+----------+---------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------+----------+---------+---------+---------
-------------------+---------+----------+----------
Imported from— | 1935 | 1936 | 1937[1]
-------------------+---------+----------+----------
| Quantity (pounds)
+---------+----------+----------
United Kingdom |6,753,003|12,344,924|12,704,108
Germany | 95,727| 626,833| 2,499,391
Netherlands | | 17,468|
All other countries| 383|[3]487,202| 1,156,714
+---------+----------+----------
Total |6,849,113|13,476,427|16,360,213
+---------+----------+----------
| Value
+---------+----------+----------
United Kingdom | $262,137| $661,781| $954,953
Germany | 3,325| 33,068| 184,887
Netherlands | | 1,190|
All other countries| 23| [3]26,536| 79,428
+---------+----------+----------
Total | 265,485| 722,575| 1,219,268
+---------+----------+----------
| Unit value
+---------+----------+----------
United Kingdom | $0.0388| $0.0536| $0.0752
Germany | .0347| .0528| .0740
Netherlands | | .0681|
All other countries| .0602| .0545| .0687
+---------+----------+----------
Average | .0388| .0536| .0745
+---------+----------+----------
| Percent of total quantity
+---------+----------+----------
United Kingdom | 98.6| 91.60| 77.65
Germany | 1.4| 4.65| 15.28
Netherlands | | .13|
All other countries| ([4]) | 3.62| 7.07
+---------+----------+----------
Total | 100.0| 100.00| 100.00
-------------------+---------+----------+----------
[1] Preliminary.
[2] Canada.
[3] Canada and France.
[4] Less than one-tenth of 1 percent.
Source: Compiled from official statistics of the United States
Department of Commerce.
TABLE 82.—_Refined cresylic acid: United States imports for consumption,
from principal sources, in specified years, 1929-37_
-------------------+---------+-------+-------+-------
Imported from— | 1929 | 1931 | 1932 | 1933
-------------------+---------+-------+-------+-------
| Quantity (pounds)
+---------+-------+-------+-------
Great Britain |1,855,844|604,404|456,783|121,634
Germany | 212,918|102,701|185,028|
All other countries| 274,767| | 88| 500
+---------+-------+-------+-------
Total |2,343,529|707,105|641,899|121,634
+---------+-------+-------+-------
| Value
+---------+-------+-------+-------
Great Britain | $144,630|$35,041|$24,607| $9,164
Germany | 14,699| 7,115| 12,714|
All other countries| 23,995| | 5|
+---------+-------+-------+-------
Total | 183,324| 42,156| 37,326| 9,164
+---------+-------+-------+-------
| Unit value
+---------+-------+-------+-------
Great Britain | $0.078| $0.058| $0.054| $0.075
Germany | .069| .069| .069|
All other countries| .087| | .057|
+---------+-------+-------+-------
Average | 0.78| .060| .058| .075
-------------------+---------+-------+-------+-------
-------------------+------+------+------+-------
Imported from— | 1934 | 1935 | 1936 |1937[1]
-------------------+------+------+------+-------
| Quantity (pounds)
+------+------+------+-------
Great Britain |23,464|16,602| | 46,379
Germany | | | 512|
All other countries| | | | 100
+------+------+------+-------
Total |23,964|16,602| 512| 46,479
+------+------+------+-------
| Value
+------+------+------+-------
Great Britain |$1,412|$1,128| | $5,101
Germany | | | $40|
All other countries| 85| | | 21
+------+------+------+-------
Total | 1,497| 1,128| 40| 5,122
+------+------+------+-------
| Unit value
+------+------+------+-------
Great Britain |$0.060|$0.068| | $0.110
Germany | | |$0.078|
All other countries| .170| | | .210
+------+------+------+-------
Average | .062| .068| .078| .110
-------------------+------+------+------+-------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
In 1931 practically all imports of refined cresylic acid were from the
United Kingdom and consigned to one importer in New York. In 1932 about
73 percent of the total dutiable imports were consigned to the same
firm. From these data and from a conference with representatives of the
importer it would appear that the imports were not cresylic acid in its
original meaning (a mixture of cresols in their natural proportions), nor
in the broadened commercial meaning (including with the cresols, xylenols
and higher boiling tar acids), but were chiefly a product consisting
largely of a single cresol separated from its two isomers. Treasury
Decision 46146, effective March 11, 1933, closed the classification of
refined cresylic acid to products of this type and imports thereafter
under this head have been much smaller. After 1927 substantial amounts of
the imports were reexported with benefit of drawback.
The imports of crude cresylic acid are also not of the type which the
domestic producer would sell by that name. Far from being a straight run
mixture of the cresol and higher boiling tar acids, they are usually
a mixture of fractions which have been separated, and then chosen and
combined so that they will meet both the tariff requirement (i. e.,
less than 75 percent of the total product will distill over at 215° C.)
and the specifications of the purchasers. Customer’s specifications are
so drawn that the product will fill his special needs or can easily be
broken down by fractional distillation in this country into elements, one
or more of which will be so usable. Thus although imported crude cresylic
acid must keep within the limitations set by the tariff it approaches
as nearly as possible the type of cresylic acid which, if produced in
this country, would be termed refined, since it was produced to meet the
specifications of the consumer.
United States exports.
Exports of the cresols and of cresylic acid are not shown in official
statistics and exports of these products as such are probably negligible,
but there are appreciable exports of antiseptics, insecticides, and
disinfectants in which they are incorporated, as well as of products or
parts of products molded of resins made from cresylic acid.
Competitive conditions.
British coal tar is principally of gas-house origin and contains a higher
percentage of tar acids (cresylic acid and phenol) than coke-oven tar,
the principal kind recovered in the United States. The recovery of these
tar acids from either kind of tar is usually not practicable, unless the
distiller can dispose of the major products, creosote oil and pitch.
British distillers have in the past ordinarily had a market for all
their products; exporting large quantities of creosote oil to the United
States, pitch to continental Europe, and tar acids and naphthalene to
the United States, Germany, and other countries. Domestic distillers
have sold cresylic acid, creosote oil, naphthalene, etc., in local
markets in competition with duty-free imports from the United Kingdom,
the Netherlands, Belgium, and Germany, but have found it difficult to
dispose of pitch. The domestic production of coal tar ordinarily exceeded
600 million gallons, approximately one-half of which has been burned as
fuel. Since the profit in distilling depends upon the markets for all
of the joint products of the distillation, the large amount remaining
undistilled can be understood.
The domestic production of cresylic acid may be expected to increase
substantially, for several reasons: (1) The principal foreign producing
countries have decreased exports because of increased demand for some of
the coal-tar distillation products at home; (2) increased world prices;
and (3) the development of topping, which allows the production of tar
acids and naphthalene from coal tar without complete distillation.
Imports of refined cresylic acid are unimportant because the duty on the
refined is high relative to the duty-free condition of the crude. Most of
the imports of refined are either reexported or used in the manufacture
of one proprietary antiseptic. The principal domestic market for cresylic
acid is as a raw material for synthetic resins, and most of the domestic
refined and most of the duty-free imported crude is now consumed by
this industry. It may therefore be said that practically all imports of
cresylic acid are duty-free and that, while they are sometimes refined by
the consumer, they compete directly with domestic production of refined
grades.
Phenol, already discussed, is closely related to cresylic acid—in
chemical composition, in production by distillation from coal tar, and
in use as a raw material for synthetic resins. To a considerable extent
the proportions of phenol and cresylic acid used in the manufacture of
tar-acid resins can be altered to take advantage of the changing price
differential between the two.
All of the separated or mixed cresols are produced in commercial
quantities in this country. Consumption in the United States, especially
of types and grades used in synthetic resins, has increased appreciably
in recent years, and is supplied chiefly by domestic production. A
comparison of the quantity and value of domestic production and of
imports in 1934 is shown in table 83.
TABLE 83.—_The cresols: Comparison of production and imports, 1934_
---------------+------------------------------+--------------------------
| Production | Imports
Product +----------+--------+----------+--------+------+----------
| Quantity | Value |Unit value|Quantity| Value|Unit value
---------------+----------+--------+----------+--------+------+----------
| _Pounds_ | | |_Pounds_| |
Metacresol | ([1]) | ([1]) | | 21,054|$8,400| $0.399
Paracresol | ([2]) | ([2]) | $0.350| 38,935|10,344| .266
Metaparacresol | 2,033,424|$122,005| .060| ([1]) | ([1])|
Orthocresol | 835,016| 66,801| .080| 25,865| 2,711| .105
Orthometapara | | | | | |
cresol | 8,929,836| 625,088| .070| 38,744|12,906| .333
+----------+--------+----------+--------+------+----------
Total |11,798,276| 813,894| | 124,598|34,361|
---------------+----------+--------+----------+--------+------+----------
[1] None, production reported for first time in 1935.
[2] Not publishable.
Sources: Production, Dyes and Other Synthetic Organic Chemicals
in the United States; imports, invoice analyses, U. S. Tariff
Commission.
SYNTHETIC TAR ACIDS OTHER THAN PHENOL
Certain synthetic tar acids other than synthetic phenol are used
commercially in the manufacture of synthetic resins in the United States.
Among these are para tertiary amyl phenol, para tertiary butyl phenol,
ortho phenyl phenol, para phenyl phenol, and resorcinal.
Para tertiary amyl phenol.
Para tertiary amyl phenol is made by reacting amylene with phenol in
the presence of sulphuric acid as a catalyst. At ordinary temperatures
it is a solid, melting at about 88° C. and boiling between 250°-265° C.
Its use is of increasing importance as a component in tar-acid resins,
especially in oil-soluble varnish resins. Owing to its phenol coefficient
of approximately 60, it is also used as a germicide, fumigant, and
insecticide. Commercial production was reported for the first time
in 1933. Since then the output has increased appreciably each year,
accompanied by material reductions in sales prices.
According to United States Patent No. 1,800,295, dated April 14, 1931, a
resin fast to light and soluble in oils is obtained by heating 82 parts
of p-tertiary amyl phenol with 90 parts of formaldehyde, in the presence
of sodium hydroxide. This substituted phenol resin passes slowly into the
infusible state, thus permitting better control of the reaction.
Para tertiary butyl phenol.
Para tertiary butyl phenol is a white solid with an aromatic odor,
melting at approximately 100° C. It is a new commercial product and is
used in resins for paints and varnishes. It is the most important resin
material in this group.
Phenyl phenols.
Both ortho and para phenyl phenol are commercially produced and are used
to some extent in resins to replace phenol. The ortho isomer is a white
solid boiling at 284° C. and melting at about 56° C. It is used chiefly
as a germicide, though small quantities are used in resins.
Para phenyl phenol is a white solid melting at about 165° C. and boiling
at 322° C. Commercial production was reported for the first time in
1933. The output has increased each year since and the selling price has
gradually declined.
Resorcinol.
Resorcinol, usually obtained by fusing meta benzene disulphonic acid with
caustic soda, is a colorless, crystalline substance with a peculiar odor.
It melts at 119° C. and boils at 276° C. It is used in medicine, in the
manufacture of intermediates and dyes, and to some extent in synthetic
resins. Resorcinol condenses with formaldehyde at such a rapid rate
that some means must be applied to slow up the reaction. It is used to
increase the rate of condensation of tar-acid resins and to reduce the
danger of sticking or undercure.
Domestic production of resorcinol has decreased in recent years. Its
relatively high cost is probably an important factor in limiting its use
in synthetic resins.
FORMALDEHYDE
Description and uses.
At ordinary temperature and pressure formaldehyde is a gas. It enters
commerce as formalin, an aqueous solution containing 40 percent
formaldehyde by volume (37 percent by weight) and from 6 to 14 percent
methyl alcohol. It is generally made by the oxidation of methyl alcohol.
Commercial formalin contains polymers which tend to precipitate in water
solution; these are kept in solution by allowing from 6 to 14 percent
methyl alcohol to remain in the solution.
The principal use of formaldehyde is in the manufacture of synthetic
resins. Other uses are (in the order of their importance): In the
manufacture of synthetic indigo; in the manufacture of hydrosulphite; as
a disinfectant, deodorant, and preservative; as a fungicide; in embalming
fluids; in tanning leather; and in the manufacture of coated paper and
wallpaper.
United States production.
The domestic output of formaldehyde has increased with the increased
demand by resin makers. Production and sales in 1937 were more than
double those in 1930. There are three domestic makers, two of which
produce methyl alcohol, the raw material. Their plants are located in New
Jersey and Oklahoma.
Statistics of production and sales are shown in table 84.
TABLE 84.—_Formaldehyde: United States production and sales, in specified
years_
-------+----------+----------------------------
|Production| Sales
Year +----------+--------+----------+--------
| Quantity |Quantity| Value | Value
| | | |per lb.
-------+----------+--------+----------+--------
| _1,000 |_1,000 | |
| pounds_ |pounds_ | |
1914 | ([1]) | 8,426| $655,174| $0.078
1919 | 25,007| 19,664| 3,928,322| .200
1921 | 9,657| 6,056| 651,681| .108
1922 | 23,958| 16,140| 1,676,401| .104
1923 | 24,081| 18,855| 2,474,506| .131
1924 | 26,155| 20,542| 1,971,053| .096
1925 | 31,456| 23,392| 1,895,913| .081
1926 | 31,953| 22,552| 2,050,967| .091
1927 | 29,920| 24,597| 2,256,534| .092
1928 | 38,718| 27,934| 2,491,615| .089
1929 | 51,786| ([2]) | ([2]) |
1930 | 40,763| ([2]) | ([2]) |
1931 | ([1]) | ([1]) | ([1]) |
1932 | ([1]) | ([1]) | ([1]) |
1933 | 52,236| 46,424| 2,122,925| .046
1934-37| ([2]) | ([2]) | ([2]) |
-------+----------+--------+----------+--------
[1] Not available.
[2] Not publishable; figures would disclose operations of
individual firms.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Production in other countries.
Formaldehyde is produced in England, Germany, France, Czechoslovakia,
Italy, Sweden, the Soviet Union, Japan, and Canada. Production data are
not available but Germany and England are probably the leading foreign
producers. Estimated productive capacity in the Soviet Union is given
as 10 million pounds annually; in Japan 6.5 million pounds; in France 4
million pounds; and in Italy 3 million pounds.
United States imports and exports.
Imports of formaldehyde have been negligible since 1920 when 428,444
pounds, valued at $210,191, were imported. There were no imports from
1928 until 1935, when 375 pounds valued at $72 were imported from Canada.
In 1936 imports amounted to 20 pounds, valued at $14, from Switzerland.
The United States exports about 5 percent of its production of
formaldehyde. Canada is the principal destination of exports, and
prior to 1934 Japan was an important market. Table 85 shows exports of
formaldehyde to principal markets, in recent years.
TABLE 85.—_Formaldehyde: United States exports to principal markets, in
specified years, 1929-37_
-------------------+---------+---------+---------+---------
Exported to— | 1929 | 1931 | 1933 | 1934
-------------------+---------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------+---------
Canada | 19,321| 716,132|1,095,847|1,236,103
Japan |1,464,763| 622,407| 729,875| 11,250
Netherlands Indies | 626,689| 650,875| | 344,725
United Kingdom | 303| 345,896| 305|
China | 29,030| 229,760| 215,050| 572,700
All other countries| 448,063| 339,777| 332,101| 433,068
+---------+---------+---------+---------
Total |2,588,169|2,904,847|2,373,178|2,597,846
+---------+---------+---------+---------
| Value
+---------+---------+---------+---------
Canada | $4,405| $36,471| $46,611| $58,348
Japan | 124,411| 33,395| 43,254| 562
Netherlands Indies | 42,807| 38,462| | 15,536
United Kingdom | 510| 18,629| 192|
China | 3,354| 13,019| 11,998| 27,407
All other countries| 49,742| 22,709| 18,966| 23,444
+---------+---------+---------+---------
Total | 225,229| 162,685| 121,021| 125,297
+---------+---------+---------+---------
| Unit value
+---------+---------+---------+---------
Canada | $0.228| $0.051| $0.043| $0.047
Japan | .085| .054| .059| .050
Netherlands Indies | .068| .059| | .045
United Kingdom | 1.683| .054| .630|
China | .116| .057| .056| .048
All other countries| .111| .067| .057| .054
+---------+---------+---------+---------
Average | .087| .056| .051| .048
+---------+---------+---------+---------
| Percent of total quantity
+---------+---------+---------+---------
Canada | 0.8| 24.7| 46.2| 47.6
Japan | 56.6| 21.4| 30.7| .4
Netherlands Indies | 24.2| 22.4| | 13.3
United Kingdom | | 11.9| |
China | 1.1| 7.9| 9.1| 22.0
All other countries| 17.3| 11.7| 14.0| 16.7
+---------+---------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------+---------+---------+---------+---------
-------------------+---------+---------+---------
Exported to— | 1935 | 1936 | 1937[1]
-------------------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------
Canada |1,493,993|1,105,277|1,187,661
Japan | | |
Netherlands Indies | 71,375| 200| 335,275
United Kingdom | | 2|
China | 598,342| 459,490| 938,700
All other countries| 334,100| 279,289| 403,236
+---------+---------+---------
Total |2,497,810|1,844,258|2,864,872
+---------+---------+---------
| Value
+---------+---------+---------
Canada | $83,805| $53,062| $50,780
Japan | | |
Netherlands Indies | 2,866| 13| 13,411
United Kingdom | | 1|
China | 28,239| 19,258| 34,274
All other countries| 18,676| 16,520| 20,498
+---------+---------+---------
Total | 133,586| 88,854| 118,963
+---------+---------+---------
| Unit value
+---------+---------+---------
Canada | $0.056| $0.048| $0.043
Japan | | |
Netherlands Indies | .040| .065| .040
United Kingdom | | .500|
China | .047| .042| .037
All other countries| .056| .059| .051
+---------+---------+---------
Average | .053| .048| .042
+---------+---------+---------
| Percent of total quantity
+---------+---------+---------
Canada | 59.8| 59.9| 41.4
Japan | | |
Netherlands Indies | 2.8| | 11.7
United Kingdom | | |
China | 24.0| 24.9| 32.8
All other countries| 13.4| 15.2| 14.1
+---------+---------+---------
Total | 100.0| 100.0| 100.0
-------------------+---------+---------+---------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
The competitive situation with respect to formaldehyde is determined
largely by the output and price of the raw material, methanol. The United
States produces large quantities of synthetic and natural methanol and
is a net exporter of that product. Both methanol and formaldehyde are
produced in many foreign countries, and foreign production is expanding.
Although methanol is now the main, if not the sole, raw material utilized
in making formaldehyde, plants for making the latter direct from natural
gas, or from petroleum gas hydrocarbons are contemplated or actually
under construction. Should such processes develop to an appreciable
extent, the competitive situation of the United States may change, but
in such case it is unlikely that this country would be so affected as to
change its position as a moderate exporter.
HEXAMETHYLENETETRAMINE
Description and uses.
Hexamethylenetetramine is a white crystalline powder made by the
interaction of formaldehyde and ammonia. It is used in tar-acid resins
to replace formaldehyde, though its higher cost has limited its use to
small proportions as a finishing or hardening agent. Other uses are as
an internal antiseptic in medicine (marketed under trade names such as
Urotropin, Cystogen, Aminoform, Urisol, and Cystamin), as an accelerator
in the vulcanization of rubber (a declining use), and in artificial
cork. During the World War it was used in gas masks as an absorbent for
phosgene.
United States production.
The domestic production of hexamethylenetetramine declined during the
depression, but has been increasing in the last few years. Production in
1937, however, was still below that of 1929. Statistics of production are
shown in table 86.
TABLE 86.—_Hexamethylenetetramine: United States production and sales,
1923, and 1925-37_
-------+----------+-----------------------------
|Production| Sales
Year |(quantity)+---------+--------+----------
| | Quantity| Value |Unit value
-------+----------+---------+--------+----------
| _Pounds_ | _Pounds_| |
1923 | 1,381,073|1,155,083|$974,877| $0.84
1925 | 1,657,993|1,506,286| 994,458| .66
1926 | 1,495,220| ([1]) | ([1]) |
1927 | 1,315,213| ([1]) | ([1]) |
1928 | 1,661,645| ([1]) | ([1]) |
1929 | 2,368,020| ([1]) | ([1]) |
1930 | 1,871,690| ([1]) | ([1]) |
1931 | ([2]) | | ([2]) |
1932 | ([2]) | | ([2]) |
1933-37| ([1]) | | ([1]) |
-------+----------+---------+--------+----------
[1] Not publishable; figures would disclose operations of
individual firms.
[2] Not available.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Hexamethylenetetramine is made by two firms in New Jersey and by one in
West Virginia. The raw materials utilized are formaldehyde and liquid
or anhydrous ammonia. One company makes its own requirements of both,
and another makes its own formaldehyde. Most of the production of
hexamethylenetetramine is sold, marketed in barrels, drums, kegs, and
cans.
Production in other countries.
Hexamethylenetetramine is made in a number of foreign countries, with
Germany probably the leading foreign producer. Exports from Germany
declined from 445,000 pounds in 1931 to 182,000 pounds in 1934, the
decline being due chiefly to the expansion of production in countries
previously large importers, particularly the United Kingdom, Japan,
Czechoslovakia, and France.
United States imports and exports.
Imports of hexamethylenetetramine to the United States are shown in table
87.
TABLE 87.—_Hexamethylenetetramine: United States imports for consumption,
1923-37_
-----------------+--------------+--------+-------+----------+----------
| | | | | Computed
Calendar year | Rate of duty |Quantity| Value |Unit value|ad valorem
| | | | | rate
-----------------+--------------+--------+-------+----------+----------
| |_Pounds_| | | _Percent_
1923 |25 percent | 47,373|$24,722| $0.522|
1924 | do | 3,826| 3,998| 1.045|
1925 | do | 20,771| 10,453| .503|
1926 | do | 23,481| 10,237| .436|
1927 | do | 3,417| 1,715| .502|
1928 | do | 5,898| 1,643| .279|
1929 | do | 5,562| 1,857| .334|
1930: | | | | |
Jan. 1-June 17 | do | | | |
June 18-Dec. 31| 11 cents | | | |
| per pound | | | |
1931 | do | | | |
1932 | do | 1,103| 336| .305| 36.1
1933 | do | 1,103| 293| .266| 41.4
1934 | do | 612| 273| .446| 24.7
1935 | do | | | |
1936 | do | 7,496| 1,510| .201| 54.6
1937[1] | do | 10,895| 8,197| .200| 54.9
-----------------+--------------+--------+-------+----------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Imports of hexamethylenetetramine in 1928 came principally from the
United Kingdom, the remainder from Germany. In 1929 they came wholly from
Germany; in 1932 and 1933 from Belgium; and in 1934 principally from
Canada, with the rest from the United Kingdom. In 1936 Belgium supplied
7,166 pounds valued at $1,368 and Germany 330 pounds valued at $142.
Exports of hexamethylenetetramine are not shown in official statistics.
It is known, however, that some has been exported, and that in 1933, at
least, exports exceeded imports.
Competitive conditions.
Hexamethylenetetramine is made from formaldehyde and ammonia, of
which there are ample supplies in the United States. The market for
hexamethylenetetramine is limited, and imports are small. It is made
in numerous foreign countries, Germany being probably the principal
potential competitor.
FURFURAL
Furfural is an aldehyde found in oat hulls, rice hulls, corn cobs, bran,
and other farm waste products. Commercially it is obtained in the United
States from oat hulls and in the Soviet Union from the husks of sunflower
seeds. It is a colorless liquid, boiling at 158° to 162° C. and freezing
at minus 38° C. Its principal use is in synthetic resins, of which tar
acid-furfural is probably the most important. These resins are used in
molding, for impregnating, and in coatings. Furfural is also used as a
solvent for cellulose ethers and esters, natural gums and resins, and in
the manufacture of derivatives useful as rubber chemicals.
Domestic production is entirely by one firm, located in Iowa. Production
and sales statistics are not publishable, but the maker has stated that
consumption is in “terms of millions of pounds per year.”
18. RAW MATERIALS FOR UREA RESINS
The principal raw materials entering into the manufacture of urea resins
are urea and formaldehyde. Formaldehyde has already been discussed (see
pp. 133-135) and urea and thiourea are discussed below.
UREA
Urea is a white crystalline material, made by condensing carbon dioxide
and ammonia under heat and pressure. It is an excellent fertilizer
because of its high nitrogen content (46.6 percent) but this use is
limited by its relatively high cost. Urea is an important synthetic
resin material, being a constituent of urea-formaldehyde resins, known
commercially under the trade names Beetleware and Plaskon.
Production of urea in the United States was started in 1916, when the
German supply was cut off. In 1920 the domestic output was estimated at
more than 200,000 pounds of fertilizer grade. Production ceased in 1922.
Urea in ammonia solution for use in the manufacture of mixed fertilizer
was first produced in 1933.
Crystal urea production in the United States was begun in 1935 and was
largely made possible by the larger volume of urea in ammonia solution
manufactured for fertilizer use. Prior to that time our requirements of
crystal urea were imported, principally from Germany. Consumers of resin
grade urea report that the domestic product is as good or better than the
imported from Europe. The domestic output of crystal urea in 1936 showed
an appreciable increase over that in 1935.
Statistics of imports of urea are given in table 88, showing imports of
all grades combined. Up to 1931, and again in 1936, the imports were
probably all for fertilizer use. From 1931 through 1935 some portion of
the imports went into the manufacture of resins, but even in this period
most of the imports were probably used in fertilizer.
TABLE 88.—_Urea: United States imports for consumption, 1919-20 and
1923-37_
-------------------+------------+----------+-------+----------
Year |Rate of duty| Quantity | Value |Unit value
-------------------+------------+----------+-------+----------
| | _Pounds_ | |
1919 |25 percent | 14,290| $9,741| $0.682
1920 | do | 23,693| 14,085| .594
1923 |35 percent | 45,711| 5,892| .129
1924 | do | 94,307| 12,891| .137
1925 | do | 146,438| 15,886| .108
1926 | do | 377,729| 30,346| .080
1927 | do | 813,120| 51,799| .064
1928 | do | 1,788,927|101,900| .057
1929 | do | 4,588,313|228,401| .050
1930: | | | |
Jan. 1-June 17 | do | 2,459,140|120,263| .049
June 18-Dec. 31|Free |17,843,840|719,982| .040
1931 | do |11,695,040|445,674| .038
1932 | do | 7,291,200|267,787| .037
1933 | do |12,918,080|483,238| .037
1934 | do |10,850,560|423,675| .039
1935 | do | 8,189,440|379,427| .046
1936 | do | 6,095,040|272,679| .045
1937[1] | do | 5,297,600|266,166| .050
-------------------+------------+----------+-------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 89 shows the sources of imports of urea in recent years. Germany
has supplied from 90 to 100 percent of the total quantity, and Canada
and the Netherlands the greater part of the remainder. There have been
occasional shipments from Belgium, France, and Japan.
TABLE 89.—_Urea: United States imports for consumption by countries, 1931
and 1933-37_
-------------------+----------+----------+----------
Imported from— | 1931 | 1933 | 1934
-------------------+----------+----------+----------
| Quantity (pounds)
+----------+----------+----------
Germany |10,496,640|12,649,280|10,660,160
Netherlands | 922,880| 147,840| 20,160
Canada | 185,920| 120,960| 168,000
All other countries| 89,600| | 2,240
+----------+----------+----------
Total |11,695,040|12,918,080|10,850,560
+----------+----------+----------
| Value
+----------+----------+----------
Germany | $401,976| $473,703| $415,777
Netherlands | 31,523| 5,034| 666
Canada | 9,107| 4,501| 7,032
All other countries| 3,068| | 200
+----------+----------+----------
Total | 445,674| 483,238| 423,675
+----------+----------+----------
| Unit value
+----------+----------+----------
Germany | $0.038| $0.037| $0.039
Netherlands | .034| .034| .033
Canada | .049| .037| .042
All other countries| .034| | .089
+----------+----------+----------
Average | .038| .037| .039
-------------------+----------+----------+----------
-------------------+---------+---------+---------
Imported from— | 1935 | 1936 | 1937[1]
-------------------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------
Germany |7,869,120|6,095,040|5,297,600
Netherlands | | |
Canada | 320,320| |
All other countries| | |
+---------+---------+---------
Total |8,189,440|6,095,040|5,297,600
+---------+---------+---------
| Value
+---------+---------+---------
Germany | $366,371| $272,679| $266,166
Netherlands | | |
Canada | 13,056| |
All other countries| | |
+---------+---------+---------
Total | 379,427| 272,679| 266,166
+---------+---------+---------
| Unit value
+---------+---------+---------
Germany | $0.047| $0.045| $0.050
Netherlands | | |
Canada | .041| |
All other countries| | |
+---------+---------+---------
Average | .046| .045| .050
+---------+---------+---------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Imports of urea enter the United States free of duty under paragraph 1793
of the Tariff Act of 1930. In spite of that fact a substantial production
in the United States has been achieved. This is due, at least to a
considerable extent, to the production of crude urea in ammonia solution,
which is used in ammoniating superphosphates for fertilizer use. It is
shipped by tank car but would be difficult to transport by ship. The
volume market for this form of the product has aided in the production of
crystal urea for both resin and fertilizer use.
THIOUREA
Thiourea (thiocarbamide) is a white crystalline solid, melting at 180°
C. It is made commercially by treating a solution of calcium cyanamide
with sulphur and ammonium sulphide or with hydrogen sulphide and
ammonia. The principal uses of thiourea are in making intermediates and
pharmaceuticals, as a photographic developer, as an insecticide, and in
medicine. Because of the water resistance it imparts it was for some
time widely used in urea resins. During the past few years, however, its
use in resins has declined sharply owing to its deleterious action on
ordinary molds and its slow rate of cure. In molding compounds, thiourea
requires about 10 minutes curing time as compared with 3 minutes or
less for urea resins and tar-acid resins. Since ways have been found
to fabricate water-resistant urea resins without using thiourea, the
consumption of thiourea in this use has declined.
There is no known commercial domestic production of thiourea.
Imports through the New York Customs District, according to invoice
analyses made by the Tariff Commission, are shown in table 90. Thiourea
is dutiable at 25 percent under paragraph 5 of the act of 1930.
TABLE 90.—_Thiourea: United States imports through the New York Customs
District, 1931-37_
----+--------+-------+----------+------------------------
Year|Quantity| Value |Unit value| Source
|(pounds)| | |
----+--------+-------+----------+------------------------
1931| 81,560|$24,254| $0.297|Germany and Switzerland.
1932| 19,347| 4,760| .246|Germany.
1933| | | |
1934| 15,738| 5,982| .380| Do.
1935| 29,480| 10,500| .356| Do.
1936| 81,031| 19,782| .244| Do.
1937| ([1]) | | |
----+--------+-------+----------+------------------------
[1] Not available.
Source: Invoice analyses of paragraph 5, of Tariff Act of 1930.
Compiled by U. S. Tariff Commission.
19. RAW MATERIALS FOR VINYL RESINS
Vinyl resins are made chiefly from vinyl acetate and vinyl chloride.
Description and uses.
Vinyl acetate is an unsaturated ester of the hypothetical vinyl alcohol.
It is made from acetylene and acetic acid, and is a colorless liquid with
a pleasant sweetish odor, boiling at 73° C. On account of its tendency
to polymerize to polyvinyl acetate, a trace of copper salt is added for
shipment. To render the vinyl acetate chemically active again, the copper
salt is removed by distillation. At present the sole use of vinyl acetate
is for the manufacture of synthetic resins. (See pp. 43-50.)
Vinyl chloride, a salt of vinyl alcohol, is obtained commercially from
acetylene. It is a gas (boiling at about minus 14° C.) used in the
manufacture of synthetic resins. Vinyl chloride mixed with vinyl acetate
is polymerized to a synthetic resin.
United States production.
Until 1938 the one domestic maker of vinyl acetate produced only
experimental lots, the bulk of our requirements being imported from
Canada. In that year large units to manufacture vinyl acetate were built
at Niagara Falls, N. Y., and at Belle, W. Va. The remarkable properties
of safety glass made from vinyl resin sheets, together with several other
new and important applications of these resins, indicate a demand for
vinyl acetate sufficient to warrant these large manufacturing units. The
United States patents covering the processes of manufacture of vinyl
acetate are owned by the Canadian producer, who has licensed the domestic
makers.
Domestic production of vinyl chloride has increased from experimental
quantities in 1927 to large-scale commercial output, increasing
substantially each year since 1933.
United States imports.
There has been no import of vinyl chloride. Imports of vinyl acetate
(unpolymerized), entirely from Canada, are shown in table 91.
TABLE 91.—_Vinyl acetate, unpolymerized: United States imports for
consumption, 1931-37_
-------+--------+--------+------
Year |Quantity| Value | Unit
|(pounds)| | value
-------+--------+--------+------
1931 | 77,269| $11,489|$0.149
1932 | 104,129| 14,053| .135
1933 | 159,757| 21,134| .132
1934 | 217,182| 39,462| .182
1935 | 776,426| 149,876| 0.193
1936[1]| 449,905| 58,499| .130
1937[2]| 297,496| 39,074| .131
-------+--------+--------+------
[1] Duty reduced from 30 percent ad valorem and 6 cents per pound
to 15 percent ad valorem and 3 cents per pound under Canadian
trade agreement, effective Jan. 1, 1936.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
Domestic consumption of vinyl acetate and vinyl chloride has increased
in recent years from experimental to commercial quantities. Many years
of intensive research looking toward large outlets for the resins made
from these compounds has apparently been successful. The largest single
application indicated at this time is for safety glass sheets.
The large increase in domestic consumption expected in the immediate
future will probably be supplied chiefly from expanding domestic
production and imports from Canada will probably decline even under
the reduced trade-agreement duty except to fill possible temporary
shortages.
APPENDIXES
A. Statistical tables on foreign trade in raw materials for synthetic
resins.
B. Trade names for synthetic resins made in the United States.
C. Trade names for synthetic resins made in Great Britain.
D. Trade names for synthetic resins made in Germany.
E. List of United States manufacturers of raw materials for synthetic
resins.
F. Glossary.
APPENDIX A
STATISTICAL TABLES ON FOREIGN TRADE IN RAW MATERIALS FOR SYNTHETIC RESINS
TABLE 92.—_Naphthalene: German imports and exports, by countries, 1929
and 1932-37_
------------------------+----------+----------+----------------------
| 1929 | 1932 | 1933
------------------------+----------+----------+----------------------
IMPORTS | Quantity (pounds)
+----------+----------+----------------------
Total from all countries| 8,032,019| 952,167| 7,482,633
+----------+----------+----------------------
Czechoslovakia | 1,688,283| ([1]) | 2,839,304
Saar Basin | 1,531,977| ([1]) | 1,833,125
Netherlands | 1,457,020| ([1]) | 1,164,029
Poland | 2,524,487| ([1]) | 832,457
U. S. S. R | 284,834| 246,033| 361,334
+----------+----------+----------------------
| Value
+----------+----------+------------+---------
| | | _1,000 |
| _Dollars_| _Dollars_|reichsmarks_|_Dollars_
Total from all countries| 110,948| 12,112| 271| 82,704
+----------+----------+------------+---------
Czechoslovakia | 26,666| ([1]) | 114| 34,790
Saar Basin | 17,380| ([1]) | 56| 17,090
Netherlands | 14,999| ([1]) | 27| 8,240
Poland | 38,332| ([1]) | 31| 9,461
U. S. S. R | 4,762| 4,750| 22| 6,714
------------------------+----------+----------+------------+---------
|
------------------------+----------+----------+----------------------
EXPORTS | Quantity (pounds)
+----------+----------+----------------------
Total to all countries |39,738,576|29,720,213| 31,842,140
+----------+----------+----------------------
UNITED STATES |17,070,218|13,820,858| 21,824,879
Belgium-Luxemburg | 8,835,596| 7,399,960| 3,958,800
Japan | ([1]) | ([1]) | 801,152
Italy | 4,500,691| 2,068,797| 1,163,589
Netherlands | 734,573| 295,857| 275,134
+----------+----------+----------------------
| Value
+----------+----------+------------+---------
| | | _1,000 |
| _Dollars_| _Dollars_|reichsmarks_|_Dollars_
Total to all countries | 774,256| 288,790| 1,392| 424,809
+----------+----------+------------+---------
UNITED STATES | 329,273| 132,758| 921| 281,070
Belgium-Luxemburg | 98,330| 42,749| 95| 28,992
Japan | ([1]) | ([1]) | 50| 15,259
Italy | 78,330| 23,324| 50| 15,259
Netherlands | 19,761| 4,987| 21| 6,409
------------------------+----------+----------+------------+---------
------------------------+----------------------+----------------------
| 1934 | 1935
------------------------+----------------------+----------------------
IMPORTS | Quantity (pounds)
+----------------------+----------------------
Total from all countries| 8,640,930 | 4,245,839
+----------------------+----------------------
Czechoslovakia | 1,602,744 |
Saar Basin | 3,641,338 | 1,129,858
Netherlands | 26,014 | 18,078
Poland | 1,060,633 | 33,730
U. S. S. R | 1,024,037 | 531,088
+----------------------+----------------------
| Value
+------------+---------+------------+---------
| _1,000 | | _1,000 |
|reichsmarks_|_Dollars_|reichsmarks_|_Dollars_
Total from all countries| 273| 107,494| 165| 66,426
+------------+---------+------------+---------
Czechoslovakia | 51| 20,081| |
Saar Basin | 78| 30,712| 25| 10,064
Netherlands | 2| 788| 1| 403
Poland | 29| 11,419| 2| 805
U. S. S. R | 48| 18,900| 27| 10,870
------------------------+------------+---------+------------+---------
|
------------------------+----------------------+----------------------
EXPORTS | Quantity (pounds)
+----------------------+----------------------
Total to all countries | 35,043,660 | 22,169,458
+----------------------+----------------------
UNITED STATES | 21,631,535 | 12,052,769
Belgium-Luxemburg | 5,685,663 | 2,010,816
Japan | 3,434,767 | 1,880,965
Italy | 695,992 | 492,728
Netherlands | 427,913 | 413,142
+----------------------+----------------------
| Value
+------------+---------+------------+---------
| _1,000 | | _1,000 |
|reichsmarks_|_Dollars_|reichsmarks_|_Dollars_
Total to all countries | 1,504| 592,200 | 1,067| 429,553
+------------+---------+------------+---------
UNITED STATES | 879| 346,106| 468| 188,407
Belgium-Luxemburg | 130| 51,188| 50| 20,129
Japan | 203| 79,931| 131| 52,738
Italy | 30| 11,812| 23| 9,259
Netherlands | 29| 11,419| 19| 7,649
------------------------+------------+---------+------------+----------
------------------------+----------------------+-----------------------
| 1936 | 1937
------------------------+----------------------+-----------------------
IMPORTS | Quantity (pounds)
+----------------------+-----------------------
Total from all countries| 493,169 | 33,069
+----------------------+-----------------------
Czechoslovakia | ([1]) | ([1])
Saar Basin | |
Netherlands | 28,660 | ([1])
Poland | ([1]) | ([1])
U. S. S. R | ([1]) | ([1])
+----------------------+-----------------------
| Value
+------------+---------+------------+----------
| _1,000 | | _1,000 |
|reichsmarks_|_Dollars_|reichsmarks_|_Dollars_
Total from all countries| 22| 8,865| 1| 402
+------------+---------+------------+----------
Czechoslovakia | ([1]) | ([1]) | ([1]) | ([1])
Saar Basin | | | |
Netherlands | 3| 1,209| ([1]) | ([1])
Poland | ([1]) | ([1]) | ([1]) | ([1])
U. S. S. R | ([1]) | ([1]) | ([1]) | ([1])
------------------------+------------+---------+------------+----------
|
------------------------+----------------------+-----------------------
EXPORTS | Quantity (pounds)
+----------------------+-----------------------
Total to all countries | 8,152,390 | 24,966,434
+----------------------+-----------------------
UNITED STATES | 3,420,437 | 14,167,201
Belgium-Luxemburg | 457,675 | 1,184,311
Japan | 253,529 | 2,031,980
Italy | 134,481 | 615,083
Netherlands | 198,414 | 66,138
+----------------------+-----------------------
| Value
+------------+---------+------------+----------
| _1,000 | | _1,000 |
|reichsmarks_|_Dollars_|reichsmarks_|_Dollars_
Total to all countries | 703| 283,288| 1,949| 783,576
+------------+---------+------------+----------
UNITED STATES | 168| 67,699| 789| 317,210
Belgium-Luxemburg | 21| 8,462| 60| 24,122
Japan | 29| 11,686| 177| 71,161
Italy | 18| 7,253| 47| 18,896
Netherlands | 14| 5,642| 7| 2,814
------------------------+------------+---------+------------+----------
[1] Not separately shown.
Source: Der Auswärtige Handel Deutschlands, 1929. Monatliche
Nachweise über den auswärtigen Handel, Deutschlands, 1932-37.
TABLE 93.—_Crude naphthalene: Belgian imports and exports, 1932-37_
---------------+----------+-----------------+-----------------
| 1932 | 1933 | 1934
+----------+-----------------+-----------------
IMPORTS | Quantity (pounds)
+----------+-----------------+-----------------
Total from all | | |
countries |14,114,070| 10,935,698 | 15,328,363
+----------+-----------------+-----------------
Netherlands | 8,187,443| 7,583,163 | 9,363,598
Germany | 5,800,744| 3,122,816 | 5,290,599
+----------+-----------------+-----------------
| Value
+----------+-------+---------+-------+---------
| |_1,000 | |_1,000 |
| _Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total from all | | | | |
countries | 74,299| 2,059| 73,711| 3,015| 140,419
+----------+-------+---------+-------+---------
Netherlands | 41,352| 1,327| 47,506| 1,881| 87,605
Germany | 31,611| 661| 23,663| 970| 45,176
+----------+-------+---------+-------+---------
EXPORTS | Quantity (pounds)
+----------+-----------------+-----------------
Total to all | | |
countries | 1,102,300| 5,955,727 | 3,395,745
+----------+-----------------+-----------------
UNITED STATES | | 3,991,428 | 2,499,355
France | 871,699| 1,262,354 | 352,075
+----------+-----------------+-----------------
| Value
+----------+-------+---------+-------+---------
| |_1,000 | |_1,000 |
| _Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total to all | | | | |
countries | 10,964| 2,503| 89,605| 1,181| 55,003
+----------+-------+---------+-------+---------
UNITED STATES | | 1,562| 55,918| 707| 32,927
France | 8,404| 446| 15,966| 243| 11,317
---------------+----------+-------+---------+-------+---------
---------------+-----------------+-----------------+-----------------
| 1935 | 1936 | 1937
+-----------------+-----------------+-----------------
IMPORTS | Quantity (pounds)
+-----------------+-----------------+-----------------
Total from all | | |
countries | 12,114,718 | 17,102,405 | 9,178,411
+-----------------+-----------------+-----------------
Netherlands | 8,786,874 | 10,315,764 | 5,983,064
Germany | 1,297,628 | 178,573 | ([1])
+-----------------+-----------------+-----------------
| Value
+-------+---------+-------+---------+-------+---------
|_1,000 | |_1,000 | |_1,000 |
|francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total from all | | | | | |
countries | 3,299| 121,562| 7,017| 237,385| 4,277|144,357
+-------+---------+-------+---------+-------+---------
Netherlands | 2,139| 78,818| 3,916| 132,478| 2,808| 94,776
Germany | 341| 12,565| 77| 2,605| ([1]) | ([1])
+-------+---------+-------+---------+-------+---------
EXPORTS | Quantity (pounds)
+-----------------+-----------------+-----------------
Total to all | | |
countries | 6,796,782 | 11,538,215 | 6,700,220
+-----------------+-----------------+-----------------
UNITED STATES | 1,709,888 | 2,119,062 | 1,009,927
France | 2,930,134 | 5,163,835 | 4,382,745
+-----------------+-----------------+-----------------
| Value
+-------+---------+-------+---------+-------+---------
|_1,000 | |_1,000 | |_1,000 |
|francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total to all | | | | | |
countries | 3,059| 112,719| 7,020| 237,487| 3,918|132,240
+-------+---------+-------+---------+-------+---------
UNITED STATES | 543| 20,009| 1,461| 49,426| 492| 16,606
France | 1,460| 53,798| 3,227| 109,169| 2,769| 93,459
---------------+-------+---------+-------+---------+-------+---------
[1] Not separately reported.
Source: Bulletin Mensuel du Commerce.
TABLE 94.—_Refined naphthalene: Belgian imports and exports, 1932-37_
---------------+----------+-----------------+-----------------
| 1932 | 1933 | 1934
+----------+-----------------+-----------------
IMPORTS | Quantity (pounds)
+----------+-----------------+-----------------
Total from all | | |
countries | 7,055| 1,323 | 7,275
+----------+-------+---------+-------+---------
| Value
+----------+-------+---------+-------+---------
| |_1,000 | |_1,000 |
| _Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total from all | | | | |
countries | 150| 8| 286| 15| 699
+----------+-------+---------+-------+---------
EXPORTS | Quantity (pounds)
+----------+-----------------+-----------------
Total to all | | |
countries |15,362,314| 15,298,822 | 14,792,425
+----------+-----------------+-----------------
Japan | 6,566,401| 4,582,922 | 2,867,523
United Kingdom | 695,772| 1,297,407 | 2,168,004
Argentina | 1,078,490| 1,130,519 | 988,102
British India | 792,995| 996,920 | 1,153,226
Canada | 841,496| 942,026 | 421,740
Netherlands | 449,518| 472,225 | 510,365
+----------+-----------------+-----------------
| Value
+----------+-------+---------+-------+---------
| |_1,000 | |_1,000 |
| _Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total to all | | | | |
countries | 326,026| 11,310| 404,889| 10,032| 467,224
+----------+-------+---------+-------+---------
Japan | 130,650| 3,498| 125,226| 1,966| 91,563
United Kingdom | 14,053| 893| 31,969| 1,524| 70,978
Argentina | 24,154| 811| 29,033| 719| 33,486
British India | 18,867| 752| 26,921| 764| 35,582
Canada | 17,670| 696| 24,916| 301| 14,019
Netherlands | 9,934| 375| 13,425| 306| 14,251
+----------+-------+---------+-------+---------
---------------+-----------------+-----------------+-----------------
| 1935 | 1936 | 1937
+-----------------+-----------------+-----------------
IMPORTS | Quantity (pounds)
+-----------------+-----------------+-----------------
Total from all | | |
countries | 112,214 | 2,866 | 19,180
+-------+---------+-------+---------+-------+---------
| Value
+-------+---------+-------+---------+-------+---------
|_1,000 | |_1,000 | |_1,000 |
|francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total from all | | | | | |
countries | 78| 2,874| 8| 271| 42| 1,418
+-------+---------+-------+---------+-------+---------
EXPORTS | Quantity (pounds)
+-----------------+-----------------+-----------------
Total to all | | |
countries | 16,148,695 | 11,419,167 | 14,071,300
+-----------------+-----------------+-----------------
Japan | 4,202,849 | 3,447,113 | 2,514,126
United Kingdom | 315,919 | 455,029 | 1,316,808
Argentina | 1,376,773 | 970,685 | 1,173,729
British India | 705,252 | 243,477 | 715,172
Canada | 90,168 | ([1]) | ([1])
Netherlands | 971,788 | 477,516 | 571,432
+-----------------+-----------------+-----------------
| Value
+-------+---------+-------+---------+-------+---------
|_1,000 | |_1,000 | |_1,000 |
|francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_
Total to all | | | | | |
countries | 11,219| 413,400| 9,391| 317,698| 11,602| 391,591
+-------+---------+-------+---------+-------+---------
Japan | 2,949| 108,665| 2,454| 83,019| 1,643| 55,455
United Kingdom | 212| 7,812| 445| 15,054| 896| 30,242
Argentina | 976| 35,964| 615| 20,805| 991| 33,448
British India | 498| 18,350| 321| 10,859| 640| 21,601
Canada | 66| 2,432| ([1])| ([1])| ([1])| ([1])
Netherlands | 695| 25,609| 568| 19,215| 697| 23,525
+-------+---------+-------+---------+-------+---------
[1] Not separately reported.
Source: Bulletin Mensuel du Commerce.
TABLE 95.—_Crude and refined naphthalene: Netherland imports and exports
by countries, 1929 and 1932-37_
---------------------+---------+---------+-------------------
| 1929 | 1932 | 1933
---------------------+---------+---------+-------------------
IMPORTS | Quantity (pounds)
+---------+---------+-------------------
Total from all | | |
countries | 896,908| 775,759| 908,597
+---------+---------+-------------------
Belgium-Luxemburg| 191,044| 477,508| 569,514
Germany | 705,820| 270,262| 330,921
Italy | ([1])| ([1])| 2,315
United Kingdom | | ([1])| 97
+---------+---------+-------------------
| Value
+---------+---------+---------+---------
| | | _1,000 |
Total from all |_Dollars_|_Dollars_|guilders_|_Dollars_
countries | 25,874| 13,733| 38| 19,885
+---------+---------+---------+---------
Belgium-Luxemburg | 5,708| 8,309| 24| 12,265
Germany | 20,153| 4,960| 13| 6,775
Italy | ([1])| ([1])| ([1])| 681
United Kingdom | | ([1])| ([1])| 23
+---------+---------+---------+---------
EXPORTS | Quantity (pounds)
+---------+---------+-------------------
Total to all | | |
countries |4,816,436|6,807,060| 10,770,410
+---------+---------+-------------------
Belgium-Luxemburg|2,820,043|6,768,631| 8,757,006
Germany |1,511,897| | 1,174,745
UNITED STATES | 44,092| | 661,380
United Kingdom | 333,902| ([1])| 100,001
+---------+---------+-------------------
| Value
+---------+---------+---------+---------
| | | _1,000 |
Total to all |_Dollars_|_Dollars_|guilders_|_Dollars_
countries | 49,058| 40,784| 158| 81,490
+---------+---------+---------+---------
Belgium-Luxemburg| 25,503| 39,886| 124| 63,928
Germany | 13,877| | 17| 8,756
UNITED STATES | 482| | 12| 6,103
United Kingdom | 5,556| ([1])| 2| 938
---------------------+---------+---------+---------+---------
---------------------+-------------------+-------------------
| 1934 | 1935
---------------------+-------------------+-------------------
IMPORTS | Quantity (pounds)
+-------------------+-------------------
Total from all | |
countries | 1,186,361 | 1,177,256
+-------------------+-------------------
Belgium-Luxemburg| 568,328 | 524,962
Germany | 522,993 | 418,409
Italy | ([1]) | ([1])
United Kingdom | ([1]) | ([1])
+-------------------+-------------------
| Value
+---------+---------+---------+---------
| _1,000 | | _1,000 |
Total from all |guilders_|_Dollars_|guilders_|_Dollars_
countries | 45| 30,220| 39| 26,747
+---------+---------+---------+---------
Belgium-Luxemburg | 22| 14,903| 21| 13,947
Germany | 19| 13,132| 12| 7,817
Italy | ([1])| ([1])| ([1])| ([1])
United Kingdom | ([1])| ([1])| ([1])| ([1])
+---------+---------+---------+---------
EXPORTS | Quantity (pounds)
+-------------------+-------------------
Total to all | |
countries | 9,764,389 | 10,851,416
+-------------------+-------------------
Belgium-Luxemburg| 9,307,821 | 9,178,854
Germany | ([1]) | 17,846
UNITED STATES | 410,225 | 681,332
United Kingdom | ([1]) | ([1])
+-------------------+-------------------
| Value
+---------+---------+---------+---------
| _1,000 | | _1,000 |
Total to all |guilders_|_Dollars_|guilders_|_Dollars_
countries | 132| 89,135| 170| 115,204
+---------+---------+---------+---------
Belgium-Luxemburg| 122| 82,146| 129| 87,380
Germany | ([1])| ([1])| ([2])| 257
UNITED STATES | 8| 5,183| 17| 11,782
United Kingdom | ([1])| ([1])| ([1])| ([1])
---------------------+---------+---------+---------+---------
---------------------+-------------------+-------------------
| 1936 | 1937
---------------------+-------------------+-------------------
IMPORTS | Quantity (pounds)
+-------------------+-------------------
Total from all | |
countries | 1,666,678 | 2,361,127
+-------------------+-------------------
Belgium-Luxemburg| 703,267 | 835,543
Germany | ([1]) | ([1])
Italy | ([1]) | ([1])
United Kingdom | 604,060 | 1,053,799
+-------------------+-------------------
| Value
+---------+---------+---------+---------
| _1,000 | | _1,000 |
Total from all |guilders_|_Dollars_|guilders_|_Dollars_
countries | 83| 53,519| 115| 63,302
+---------+---------+---------+---------
Belgium-Luxemburg | 42| 27,082| 60| 33,027
Germany | ([1])| ([1])| ([1])| ([1])
Italy | ([1])| ([1])| ([1])| ([1])
United Kingdom | 21| 13,541| 36| 19,816
+---------+---------+---------+---------
EXPORTS | Quantity (pounds)
+-------------------+-------------------
Total to all | |
countries | 14,422,493 | 15,330,788
+-------------------+-------------------
Belgium-Luxemburg| 10,568,852 | 9,261,525
Germany | ([1]) | ([1])
UNITED STATES | 3,207,693 | 2,546,313
United Kingdom | ([1]) | ([1])
+-------------------+-------------------
| Value
+---------+---------+---------+---------
| _1,000 | | _1,000 |
Total to all |guilders_|_Dollars_|guilders_|_Dollars_
countries | 435| 280,492| 553| 304,399
+---------+---------+---------+---------
Belgium-Luxemburg| 255| 164,426| 294| 161,832
Germany | ([1])| ([1])| ([1])| ([1])
UNITED STATES | 143| 92,208| 100| 55,045
United Kingdom | ([1])| ([1])| ([1])| ([1])
---------------------+---------+---------+---------+---------
[1] Not separately reported.
[2] Less than 500.
Source: Nederland-Jaarstatistiek (1929 and 1932-35) and
Maandstatistiek (1936-37).
TABLE 96.—_Refined naphthalene: Canadian imports by countries, 1928-29
and 1932-37_
------------------------+-------+---------+---------+---------
| 1928 | 1929 | 1932 | 1933
------------------------+-------+---------+---------+---------
| Quantity (pounds)
+-------+---------+---------+---------
Total from all countries|565,866|1,075,415|1,223,372|1,053,114
+-------+---------+---------+---------
UNITED STATES | 32,274| 4,049| 17,560| 9,553
United Kingdom | 26,000| 8,600| 32,400| 148,144
Belgium | ([2]) | 841,876|1,102,203| 895,042
+-------+---------+---------+---------
| Value (United States dollars)
+-------+---------+---------+---------
Total from all countries| 18,162| 32,411| 21,787| 22,014
+-------+---------+---------+---------
UNITED STATES | 1,428| 245 577| 545| 188 696
United Kingdom | 1,014| 363 670| 3,779| 13,603
Belgium | ([2]) | 25,906| 19,401| 17,657
------------------------+-------+---------+---------+---------
------------------------+-------+---------+-------+---------
| 1934 | 1935 | 1936 | 1937[1]
------------------------+-------+---------+-------+---------
| Quantity (pounds)
------------------------+-------+---------+-------+---------
Total from all countries|844,929|1,342,530|884,059|1,256,289
------------------------+-------+---------+-------+---------
UNITED STATES | 3,145| 3,620| 2,091| 2,018
United Kingdom |484,868|1,321,310|879,548|1,254,271
Belgium 895,042|347,956| 17,600| ([2]) |
------------------------+-------+---------+-------+---------
| Value (United States dollars)
------------------------+-------+---------+-------+---------
Total from all countries| 25,482| 40,060| 46,670| 57,455
------------------------+-------+---------+-------+---------
UNITED STATES |243 185| 696| 243| 185
United Kingdom | 38,865| 38,865| 46,229| 57,270
Belgium | 11,431| 499| ([2]) |
------------------------+-------+---------+-------+---------
[1] Preliminary.
[2] Not shown separately.
Source: Trade of Canada.
TABLE 97.—_Naphthalene: Japanese imports by countries, 1928-29 and
1932-36_
------------------------+---------+---------+---------+----------------
| 1928 | 1929 | 1932 | 1933
------------------------+---------+---------+---------+----------------
| Quantity (pounds)
+---------+---------+---------+----------------
Total from all countries|2,773,320|2,902,686|6,765,572| 7,876,566
+---------+---------+---------+----------------
Belgium | 379,900| 403,180|2,857,448| 3,950,056
Germany | 491,541| 403,180|1,935,213| 2,525,036
Kwangtung Province |1,790,766| 864,298|1,272,372| 169,976
+---------+---------+---------+----------------
| Value
+---------+---------+---------+------+---------
| | | |_1,000|_Dollars_
|_Dollars_|_Dollars_|_Dollars_| yen_ |
Total from all countries| 62,653| 94,504| 97,265| 625| 160,286
+---------+---------+---------+------+---------
Belgium | 12,531| 14,291| 42,448| 309| 79,245
Germany | 16,707| 14,291| 28,111| 200| 51,291
Kwangtung Province | 29,238| 21,667| 13,774| 13| 3,334
+---------+---------+---------+------+---------
----------------------+----------------+----------------+---------------
| 1934 | 1935 | 1936
----------------------+----------------+----------------+---------------
| Quantity (pounds)
+----------------+----------------+----------------
Total from all | 7,364,557| 8,979,696| 12,641,977
countries | | |
+----------------+----------------+----------------
Belgium | 1,590,138| 2,926,430| 3,163,801
Germany | 4,679,670| 3,486,239| 2,727,816
Kwangtung Province| 241,146| 1,103,322|
+----------------+----------------+----------------
| Value
+------+---------+------+---------+------+---------
|_1,000|_Dollars_|_1,000|_Dollars_|_1,000|_Dollars_
| yen_ | | yen_ | | yen_ |
Total from all | 560| 166,404| 697| 200,088| 1,613| 467,680
countries | | | | | |
+------+---------+------+---------+------+---------
Belgium | 122| 36,252| 234| 67,174| 410| 118,997
Germany | 357| 106,083| 283| 81,240| 394| 114,335
Kwangtung Province| | | 12| 3,445| 93| 27,020
+------+---------+------+---------+------+---------
Source: Annual Return of the Foreign Trade of Japan.
TABLE 98.—_Crude glycerin: United States imports for consumption,[1] by
countries, 1929 and 1931-37_
-------------------------+----------+----------+---------+---------
Imported from— | 1929[2] | 1931 | 1932 | 1933
-------------------------+----------+----------+---------+---------
| Quantity (pounds)
+----------+----------+---------+---------
France | 4,931,691| 2,550,457|1,653,825|2,455,264
Cuba | 1,074,271| 1,170,667|1,232,219|1,216,395
United Kingdom | 3,847,345| 1,631,103| 582,194| 252,238
Belgium | 759,448| 739,892| 310,855| 440,862
Germany | 1,072,173| 674,109| 260,005| 242,901
Philippine Islands (free)| 250,165| 180,490| 197,841| 268,449
Argentina | 494,638| 458,068| 154,525| 288,832
Netherlands | 262,299| 425,796| 125,733| 226,994
Canada | 1,304,220| 1,161,085| 80,440|
Denmark | 54,988| 175,273| | 124,278
Union of Soviet Socialist| | | |
Republics | 132,334| | 64,969| 889,618
All other countries | 668,329| 966,023| 317,866| 67,254
+----------+----------+---------+---------
Total |14,851,901|10,132,963|4,980,472|6,473,085
+----------+----------+---------+---------
| Value
+----------+----------+---------+---------
France | $280,062| $114,575| $53,391| $80,068
Cuba | 69,668| 67,709| 50,147| 56,737
United Kingdom | 216,307| 8 2,262| 19,802| 7,722
Belgium | 49,568| 46,275| 12,362| 17,627
Germany | 65,446| 40,596| 12,240| 10,745
Philippine Islands (free)| 16,796| 10,993| 9,150| 14,078
Argentina | 29,758| 23,532| 6,516| 7,947
Netherlands | 18,963| 23,301| 5,349| 10,664
Canada | 67,821| 59,495| 4,246|
Denmark | 2,966| 9,358| | 5,171
Union of Soviet Socialist| | | |
Republics | 9,113| | 2,738| 34,060
All other countries | 37,084| 47,343| 12,614| 2,076
+----------+----------+---------+---------
Total | 863,552| 525,599| 188,555| 246,895
+----------+----------+---------+---------
| Percent of total imports by quantity
+----------+----------+---------+---------
France | 33.2| 25.2| 33.2| 37.9
Cuba | 7.2| 11.6| 24.7| 18.8
United Kingdom | 25.9| 16.1| 11.7| 3.9
Belgium | 5.1| 7.3| 6.3| 6.8
Germany | 7.2| 6.7| 5.2| 3.8
Philippine Islands (free)| 1.7| 1.8| 4.0| 4.1
Argentina | 3.3| 4.5| 3.1| 4.5
Netherlands | 1.8| 4.2| 2.5| 3.5
Canada | 8.8| 11.4| 1.6|
Denmark | .4| 1.7| | 1.9
Union of Soviet Socialist| | | |
Republics | .9| | 1.3| 13.7
All other countries | 4.5| 9.5| 6.4| 1.1
+----------+----------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------------+----------+----------+---------+---------
-------------------------+----------+---------+----------+----------
Imported from— | 1934 | 1935 | 1936 | 1937[3]
-------------------------+----------+---------+----------+----------
| Quantity (pounds)
+----------+---------+----------+----------
France | 4,880,013| 578,617| 1,058,692| 2,102,785
Cuba | 1,178,238|2,550,617| 2,159,741| 2,476,790
United Kingdom | 1,494,445| 578,231| 1,403,880| 1,640,691
Belgium | 2,358,479| 257,290| 404,371| 818,514
Germany | 1,539,919| 198,767| 77,723| 518,231
Philippine Islands (free)| 180,549|1,578,523| 303,551| 793,225
Argentina | 680,443| 100,902| 1,154,888| 2,131,068
Netherlands | 1,393,072| 267,366| 1,037,118| 325,275
Canada | 629,880|1,946,450| 671,465| 333,855
Denmark | 58,449| | 442,768| 133,671
Union of Soviet Socialist| | | |
Republics | 146,695| 14,883| 2,017,992| 1,634,874
All other countries | 541,045| 149,288| 416,796| 532,451
+----------+---------+----------+----------
Total |15,081,227|8,220,934|11,148,985|13,441,430
+----------+---------+----------+----------
| Value
+----------+---------+----------+----------
France | $324,840| $45,245| $121,612| $370,622
Cuba | 92,692| 228,011| 230,340| 381,683
United Kingdom | 97,972| 50,549| 134,475| 284,779
Belgium | 160,301| 19,217| 46,417| 146,014
Germany | 103,401| 22,699| 8,874| 92,446
Philippine Islands (free)| 14,984| 74,798| 32,708| 145,348
Argentina | 45,251| 7,972| 115,198| 349,675
Netherlands | 92,754| 23,208| 127,050| 47,898
Canada | 51,716| 172,426| 70,672| 53,014
Denmark | 4,062| | 47,256| 26,220
Union of Soviet Socialist| | | |
Republics | 10,137| 1,463| 222,347| 254,745
All other countries | 41,955| 11,146| 42,411| 90,938
+----------+---------+----------+----------
Total | 1,040,065| 656,734| 1,199,360| 2,243,382
+----------+---------+----------+----------
| Percent of total imports by quantity
+----------+---------+----------+----------
France | 32.4| 7.1| 9.5| 15.6
Cuba | 7.8| 31.0| 19.4| 18.4
United Kingdom | 9.9| 7.0| 12.6| 12.2
Belgium | 15.6| 3.1| 3.6| 6.1
Germany | 10.2| 2.4| .7| 3.9
Philippine Islands (free)| 1.2| 19.2| 2.7| 5.9
Argentina | 4.5| 1.2| 10.4| 15.8
Netherlands | 9.2| 3.3| 9.3| 2.4
Canada | 4.2| 23.7| 6.0| 2.5
Denmark | .4| | 4.0| 1.0
Union of Soviet Socialist| | | |
Republics | 1.0| .2| 18.1| 12.2
All other countries | 3.6| 1.8| 3.7| 4.0
+----------+---------+----------+----------
Total | 100.0| 100.0| 100.0| 100.0
-------------------------+----------+---------+----------+----------
[1] Includes imports from Cuba and shipments from Philippine Islands.
[2] General imports.
[3] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 99.—_Refined glycerin: United States imports for consumption, by
countries, 1929 and 1931-37_
-------------------+---------+---------+---------+---------
Imported from— | 1929[1] | 1931 | 1932 | 1933
-------------------+---------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------+---------
Netherlands |3,114,642|1,054,810|1,705,855|2,153,490
Germany |1,824,672| 197,890| 384,131| 406,716
United Kingdom | 165,770| 38,561| 153,289| 50,421
France | | 592,979| 44,905| 125,889
Canada | 105| 81,295| 14,520|
Czechoslovakia | | | |
All other countries| 388,282| | 44,808| 39,171
+---------+---------+---------+---------
Total |5,493,471|1,965,535|2,347,508|2,775,687
+---------+---------+---------+---------
| Value
+---------+---------+---------+---------
Netherlands | $294,595| $75,462| $100,451| $132,172
Germany | 154,432| 17,152| 26,582| 22,826
United Kingdom | 18,301| 2,850| 9,666| 3,111
France | | 40,005| 2,278| 7,210
Canada | 19| 5,506| 1,358|
Czechoslovakia | | | |
All other countries| 33,383| | 2,024| 1,672
+---------+---------+---------+---------
Total | 500,730| 140,975| 142,359| 166,991
+---------+---------+---------+---------
| Percent of total imports by quantity
+---------+---------+---------+---------
Netherlands | 56.7| 53.7| 72.7| 77.6
Germany | 33.2| 10.1| 16.4| 14.7
United Kingdom | 3.0| 1.9| 6.5| 1.8
France | | 30.2| 1.9| 4.5
Canada | | 4.1| .6|
Czechoslovakia | | | |
All other countries| 7.1| | 1.9| 1.4
+---------+---------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------+---------+---------+---------+---------
-------------------+---------+------+---------+---------
Imported from— | 1934 | 1935 | 1936 | 1937[2]
-------------------+---------+------+---------+---------
| Quantity (pounds)
+---------+------+---------+---------
Netherlands | 775,074|16,913|1,542,924|2,776,046
Germany | 276,908| 600| 319| 352,680
United Kingdom | 951,196|28,176| 572,919| 373,416
France | | 584| 413,977|2,967,528
Canada | | | 765,676| 19,782
Czechoslovakia | | | 112,562| 506,598
All other countries| 210,764|22,293| 39,110| 539,070
+---------+------+---------+---------
Total |2,213,942|68,566|3,447,487|7,535,120
+---------+------+---------+---------
| Value
+---------+------+---------+---------
Netherlands | $66,445|$2,718| $273,432| $636,644
Germany | 27,159| 252| 129| 96,542
United Kingdom | 93,938| 2,760| 99,204| 76,001
France | | 97| 79,242| 751,816
Canada | | | 114,523| 4,922
Czechoslovakia | | | 21,650| 148,612
All other countries| 21,447| 2,450| 5,856| 112,652
+---------+------+---------+---------
Total | 208,989| 8,277| 594,036|1,827,189
+---------+------+---------+---------
| Percent of total imports by quantity
+---------+------+---------+---------
Netherlands | 35.0| 24.7| 44.7| 36.8
Germany | 12.5| .9| | 4.7
United Kingdom | 43.0| 41.1| 16.6| 5.0
France | | .8| 12.0| 39.4
Canada | | | 22.2| .3
Czechoslovakia | | | 3.3| 6.7
All other countries| 9.5| 32.5| 1.2| 7.1
+---------+------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------+---------+------+---------+---------
[1] General imports.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
APPENDIX B
TRADE NAMES FOR SYNTHETIC RESINS MADE IN THE UNITED STATES
_Trade name_ _Maker_
Tar-acid resins:
Amberol Resinous Products & Chemical Co., Inc., Phila.,
Pa.
Artifex Artifex Products Co., Camden, N. J.
Bakelite Bakelite Corp., New York, N. Y.
Beckacite Beck, Koller & Co., Inc., Detroit, Mich.
Beckasol Beck, Koller & Co., Inc., Detroit, Mich.
Beckopol Beck, Koller & Co., Inc., Detroit, Mich.
Catalin Catalin Corp., New York, N. Y.
Celeron Continental-Diamond Fibre Co., Newark, Del.
Coltrock Colt’s Patent Fire Arms Mfg. Co., Hartford, Conn.
Colasta Colasta Co., Inc., Hoosick Falls, N. Y.
Dilecto Continental-Diamond Fibre Co., Newark, Del.
Dura Paramet Chemical Corp., Long Island City, N. Y.
Durez General Plastics, Inc., N. Tonawanda, N. Y.
Durite Durite Plastics, Phila., Pa.
Fabroil General Electric Co., Schenectady, N. Y.
Fiberlon Fiberloid Corp., Indian Orchard, Mass.
Fibroc Fibroc Insulation Co., Valparaiso, Ind.
Gemstone A. Knoedler Co., Lancaster, Pa.
Haveg Haveg Corp., Newark, Del.
Herculite Colasta Co., Inc., Hoosick Falls, N. Y.
Indur Reilly Tar & Chemical Corp., Indianapolis, Ind.
Insurok Richardson Co., Melrose Park, Ill.
Joanite Joanite Corp., Long Island City, N. Y.
Kellite Kellogg Switchboard & Supply Co., Chicago, Ill.
Lewisol John D. Lewis, Mansfield, Mass.
Makalot Makalot Corp., Boston, Mass.
Marblette Marblette Corp., Long Island City, N. Y.
Micarta Westinghouse Electric & Mfg. Co., Trafford, Pa.
Moldarta Westinghouse Electric & Mfg. Co., Trafford, Pa.
Pandura Paramet Chemical Corp., Long Island City, N. Y.
Panelyte Panelyte Corp., Trenton, N. J.
Paranol Paramet Chemical Corp., Long Island City, N. Y.
Phenac American Cyanamid Co., New York, N. Y.
Phenalin E. I. du Pont de Nemours & Co., Wilmington, Del.
Prystal Catalin Corp., New York, N. Y.
Resinox Resinox Corp., New York, N. Y.
Spauldite Spaulding Fibre Co., Tonawanda, N. Y.
Syntex Jones-Dabney Co., Inc., Louisville, Ky.
Synthane Synthane Corp., Oaks, Pa.
Taylor Taylor Fibre Co., Norristown, Pa.
Textolite General Electric Co., Schenectady, N. Y.
Waterlite Watertown Mfg. Co., Watertown, Conn.
Other makers of tar acid resins in the United States include:[27]
Aluminum Industries, Cincinnati, Ohio; California Flaxseed
Products Co., Los Angeles, Calif.; Cook Paint & Varnish Co.,
Chicago, Ill.; Ford Motor Co., Detroit, Mich.; Heresite &
Chemical Co., Manitowoc, Wis.; Millergum Co., Chicago, Ill.;
Nubian Paint & Varnish Co., Chicago, Ill.; Varcum Chemical Co.,
Niagara Falls, N. Y.; Vita Var Corp., Newark, N. J.
Alkyd resins:
Amberlac Resinous Products & Chemical Co., Inc., Phila.,
Pa.
Aquaplex Resinous Products & Chemical Co., Inc., Phila.,
Pa.
Beckol Beck, Koller & Co., Inc., Detroit, Mich.
Beckosol Beck, Koller & Co., Inc., Detroit, Mich.
Dulux E. I. du Pont de Nemours & Co., Wilmington, Del.
Duraplex Resinous Products & Chemical Co., Inc., Phila.,
Pa.
Esterol Paramet Chemical Corp., Long Island City, N. Y.
Glyptal General Electric Co., Schenectady, N. Y.
Lewisol John D. Lewis, Mansfield, Mass.
Makalot Makalot Corp., Boston, Mass.
Paraplex Resinous Products & Chemical Co., Inc., Phila.,
Pa.
Rauzene Robert Rauh, Inc., Newark, N. J.
Rezyl American Cyanamid Co., New York, N. Y.
Syntex Jones-Dabney Co., Inc., Louisville, Ky.
Teglac American Cyanamid Co., New York, N. Y.
Other makers of alkyd resins in the United States include:[27]
Atlas Powder Co., Wilmington, Del.; Bakelite Corp., New York,
N. Y.; Andrew Brown Co., Los Angeles, Calif.; California
Flaxseed Products, Los Angeles, Calif.; Carboygen Chemical Co.,
Garwood, N. J.; General Paint Co., Tulsa, Okla.; Hercules Powder
Co., Wilmington, Del.; Nubian Paint & Varnish, Chicago, Ill.;
Pittsburgh Plate Glass Co., Milwaukee, Wis.; Valentine & Co.,
Inc., New York, N. Y.
Urea resins:
Beetle American Cyanamid Co., New York, N. Y.
Beckamine Beck, Koller & Co., Detroit, Mich.
Plaskon Plaskon Co., Inc., Toledo, Ohio.
RHoplex Rohm & Haas, Philadelphia, Pa.
Syntex Jones-Dabney Co., Inc., Louisville, Ky.
Uformite Resinous Products & Chemical Co., Phila., Pa.
Other makers of urea resins in the United States include: E. I.
du Pont de Nemours & Co., Wilmington, Del.; Bakelite Corp., New
York, N. Y.
Acrylate resins:
Acryloid Resinous Products & Chemical Co., Phila., Pa.
Acrysol Resinous Products & Chemical Co., Phila., Pa.
Crystalite Resinous Products & Chemical Co., Phila., Pa.
Lucite E. I. du Pont de Nemours & Co., Wilmington, Del.
Plexiglas Resinous Products & Chemical Co., Phila., Pa.
Plexigum Resinous Products & Chemical Co., Phila., Pa.
Primal Resinous Products & Chemical Co., Phila., Pa.
Coumarone-indene resins:
Cumar Barrett Co., New York.
Neville Neville Co., Pittsburgh, Pa.
Nevindene Neville Co., Pittsburgh, Pa.
Petroleum resins:
Santo-Resin Monsanto Chemical Co., St. Louis, Mo.
Petropol Pure Oil Co., Chicago, Ill.
Polystyrene resins:
Bakelite polystyrene Bakelite Corp., New York, N. Y.
Carbide & Carbon Chemicals Corp., New York, N. Y.
Styron Dow Chemical Co., Midland, Mich.
Vinyl resins:
Butvar Shawinigan Products, Inc., Indian Orchard, Mass.
Vinyloid Carbide & Carbon Chemicals Corp., New York.
Vinylite Carbide & Carbon Chemicals Corp., New York.
Vinal Carbide & Carbon Chemicals Corp., New York.
Vinylseal Carbide & Carbon Chemicals Corp., New York.
Flamenol General Electric Co., Schenectady, N. Y.
Koroseal B. F. Goodrich Co., Akron, Ohio.
E. I. du Pont de Nemours & Co., Wilmington, Del.
APPENDIX C
TRADE NAMES FOR SYNTHETIC RESINS MADE IN GREAT BRITAIN
_Trade name_ _Maker_
Tar-acid resins for moulding and laminating:
Bakelite Bakelite, Ltd., London.
Britsulite British Insulite Ltd., Manchester.
Elo Birkby’s Ltd., Liversedge, Yorkshire.
Fabrolite British Thompson Houston Co., Ltd., Rugby.
Holite E. S. Hole, London.
Indurite Indurite Moulding Powders Ltd., Radcliffe,
Lancashire.
Lorival Lorival Mfg. Co., Ltd., Southall, Middlesex.
Mouldrite Imperial Chemical Industries, Ltd., London.
Nestorite James Ferguson & Sons, Ltd., London.
Permaplastic Permastic Ltd., Weybridge, Surrey.
Rockite F. A. Hughes & Co., Ltd., London.
Oil soluble tar-acid resins:
Bakelaque Attwater & Sons, Ltd., Preston, Lancashire.
Damard Bakelite, Ltd., London.
Damarda Bakelite, Ltd., London.
Epok British Resin Products, Ltd., Kingston-on-Thames.
Erinite Erinoid Ltd., Stroud, Gloucester.
Formapex Ioco Rubber & Waterproofing Co., Ltd.,
Anniesland, Glasgow.
Keebush Bushings, Ltd., Hebburn-on-Tyne.
Cast phenolic resin:
Catalin Catalin Ltd., Waltham Abbey, Essex.
Urea resins:
Beetle Beetle Products Co., Ltd., Oldbury,
Worcestershire.
Mouldrite Imperial Chemical Industries, Ltd., London.
Pollopas Beetle Products Co., Ltd., Oldbury,
Worcestershire.
Scarat Beetle Products Co., Ltd., Oldbury,
Worcestershire.
Alkyd resins:
Albertalates Albert Products, Ltd., Erith, Kent.
Dulux Nobel Chemical Finishes Ltd., London.
Glyptal British Thompson Houston Co., Ltd., Rugby.
Micanite Micanite and Insulators Co., Ltd., Walthamstow,
London.
Paralac Imperial Chemical Industries, Ltd., London.
Acrylate resins:
Diakon and Perspex Mouldrite Ltd., Division of Imperial Chemical
Industries, Ltd., London.
Aniline resins:
Panilax Micanite and Insulators Co., Ltd., London.
APPENDIX D
TRADE NAMES FOR SYNTHETIC RESINS MADE IN GERMANY
_Trade name_ _Maker_
Tar-acid resins:
Alberid Dr. Kurt Albert G. m. b. H., Chemische Fabrik,
Wiesbaden-Biebrich.
Albertol Dr. Kurt Albert G. m. b. H., Chemische Fabrik,
Wiesbaden-Biebrich.
Ambresit Chemische Fabrik Ambra, Zittau i. Sachsen (in
liquidation).
Ammoplaste I. G. Farbenindustrie A. G., Frankfort-on-Main.
Backdura Bakelite G. m. b. H., Berlin.
Bakelit Bakelite G. m. b. H., Berlin.
Bakelit A (Resol) Bakelite G. m. b. H., Berlin.
Bakelit C Bakelite G. m. b. H., Berlin.
Bezet Harz Louis Blumen, Zwickau i. Sachsen.
Boschbakelite Robert Bosch A. G., Stuttgart.
Celloresen Louis Blumer, Zwickau i. Sachsen.
Dekorit Dr. F. Raschig G. m. b. H., Ludwigshafen a.
Rhein.
Durax
Durophen Dr. Kurt Albert G. m. b. H., Wiesbaden-Biebrich.
Elastolith Herold A. G., Hamburg 33.
Ethyl cellulose I. G. Farbenindustrie A. G., Frankfort-on-Main.
Faturan Dr. Heinr. Traun & Sohne, Hamburg.
Ferrozell Deutsche Ferrozell G. m. b. H., Augsburg.
Greif Faturan Dr. H. Traun & Sohne, Hamburg.
Havegit Saureschutz G. m. b. H., Berlin.
Herolith Herold A. G., Hamburg.
Hornolith Hornolith G. m b. H., Berlin S 59.
Ivorax Herold A. G., Hamburg.
Koraton Wedig & Reu.
Kunstharz 26 Z I. G. Farbenindustrie A. G., Frankfort-on-Main.
Laccain Louis Blumer, Zwickau i. Sachsen.
Leukorit Dr. F. Raschig G. m. b. H., Ludwigshafen a.
Rhein.
Lithocorn A. Elhardt Sohne, Kempten, Bayern.
Marbolith Herold A. G., Hamburg 33.
Metakalin I. G. Farbenindustrie A. G., Frankfort-on-Main.
Neoresit August Nowak A. G., Bautzen.
Novolack Bakelite G. m. b. H., Berlin.
Novotext Allgemeine Elektrizitats-Gesellschaft, Berlin.
Ornalith Herold A. G., Hamburg
Phenolplaste I. G. Farbenindustrie A. G., Frankfort-on-Main.
Redmanol (Bakelit A) Bakelite G. m. b. H., Berlin.
Resenoplast Louis Blumer, Zwickau i. Sachsen.
Resinit Bakelite G. m. b. H., Berlin.
Resinole Dr. F. Raschig G. m. b. H., Ludwigshafen a.
Rhein.
Resit Bakelite G. m. b. H., Berlin.
Resol Bakelite G. m. b. H., Berlin.
Schellackersatz I. G. Farbenindustrie A. G., Frankfort-on-Main.
Dr. A. Wacker Gesellschaft für Elektrochemische
Industrie G. m. b. H., München.
Dr. Kurt Albert, Wiesbaden-Biebrich.
Sipilite Bakelite G. m. b. H., Berlin.
Supraresen Louis Blumer, Zwickau i. Sachsen.
Syntellac Dr. A. Wacker G. m. b. H., München.
Tenazit Allgemeine Elektrizitats-Gesellschaft, Berlin.
Toplast Louis Blumer, Zwickau i. Sachsen.
Trolon Rheinisch-Westfalische Sprengstoff Fabriken,
Troisdorf.
Turbax Jaroslaw’s Erste Glimmerwarenfabrik, Berlin
SO 36.
Vigorith Dr. F. Raschig, Ludwigshafen a. Rhein.
Vinnapas Dr. A. Wacker G. m. b. H., München.
Wackerschellack Dr. A. Wacker G. m. b. H., München.
Wenjazit Kunst-Rohstoff A. G., Hamburg-Einbeck.
Alkyd resins:
Alftalate Dr. Kurt Albert G. m. b. H., Chemische Fabrik,
Wiesbaden-Biebrich.
Alkydal I. G. Farbenindustrie A. G., Frankfort-on-Main.
Beckacite Beckacite Kunstharzfabrik, G. m. b. H.,
Hamburg-Wandsbeck.
Beckosol Beckacite Kunstharzfabrik, G. m. b. H.,
Hamburg-Wandsbeck.
Duxol Louis Blumer, Zwickau i. Sachsen.
Duxalid Louis Blumer, Zwickau i. Sachsen.
Geaphthal Allgemeine Elektrizitats-Gesellschaft, Berlin.
Glyptal Dr. Kurt Albert G. m. b. H., Wiesbaden-Biebrich.
Urea resins:
Hares L H. Rommler A. G., Berlin W 62.
Locron I. G. Farbenindustrie, A. G., Frankfort-on-Main.
Pluviusin Kunstharzfabrik Dr. F. Pollack, Vienna, German
branch Berlin.
Pollopas Rheinisch-Westfalische Sprengstoff Fabriken,
Troisdorf, Bez. Koln.
Vinyl resins:
Acronal I. G. Farbenindustrie, A. G., Frankfort-on-Main.
Mowilith I. G. Farbenindustrie, A. G., Frankfort-on-Main.
Polystyrene resins:
Metastyrol I. G. Farbenindustrie, A. G., Frankfort-on-Main.
Mollit I. G. Farbenindustrie, A. G., Frankfort-on-Main.
Trolitul Rheinisch-Westfalische Sprengstoff Fabriken,
Troisdorf.
Acrylate resins:
Plexigum Rohm & Haas, Darmstadt.
Other resins:
Coumarone resins Kokawerke & Chemische Fabriken A. G., Berlin
N. W. 40.
Harz No. 30 Ciba A. G., Berlin-Wilmersdorf.
Harz No. 238 Ciba A. G., Berlin-Wilmersdorf.
Ultrasit Chemische Fabrik Ambra, Zittau, Sachsen, (in
liquidation).
Utilith Deutsche Rohstoffindustrie, Augsburg.
APPENDIX E
LIST OF UNITED STATES MANUFACTURERS OF RAW MATERIALS FOR SYNTHETIC
RESINS[28]
Phenol:
Barrett Co., New York, N. Y.
Calco Chemical Co., Inc., Bound Brook, N. J.
Dow Chemical Co., Midland, Mich.
Koppers Co., Pittsburgh, Pa.
Monsanto Chemical Co., St. Louis, Mo.
Reilly Tar & Chemical Corp., Indianapolis, Ind.
Cresols:
Barrett Co., New York, N. Y.
Calco Chemical Co., Inc., Bound Brook, N. J.
Givaudan-Delawanna, Inc., Delawanna, N. J.
Koppers Co., Pittsburgh, Pa.
Reilly Tar & Chemical Corp., Indianapolis, Ind.
Swann & Co., Birmingham, Ala.
Xylenols:
Barrett Co., New York, N. Y.
Calco Chemical Co., Inc., Bound Brook, N. J.
Reilly Tar & Chemical Corp., Indianapolis, Ind.
Butyl phenol (p-tertiary), Dow Chemical Co., Midland, Mich.
Phenyl phenols, Dow Chemical Co., Midland, Mich.
Resorcinol, tech.:
E. I. du Pont de Nemours & Co., Wilmington, Del.
Pennsylvania Coal Products Co., Petrolia, Pa.
Naphthalene:
Barrett Co., New York, N. Y.
Calco Chemical Co., Inc., Bound Brook, N. J.
Coopers Creek Chemical Co., West Conshohocken, Pa.
E. I. du Pont de Nemours & Co., Wilmington, Del.
Reilly Tar & Chemical Corp., Indianapolis, Ind.
Shell Chemical Co., San Francisco, Calif.
Standard Naphthalene Products Corp., South Kearney, N. J.
White Tar Co. of N. J., Inc., Pittsburgh, Pa.
Phthalic acid and anhydride:
American Cyanamid Co., New York, N. Y.
Barrett Co., New York, N. Y.
E. I. du Pont de Nemours & Co., Wilmington, Del.
Monsanto Chemical Co., St. Louis, Mo.
National Aniline & Chemical Co., Inc., New York, N. Y.
Maleic acid and anhydride:
National Aniline & Chemical Co., Inc., New York, N. Y.
American Cyanamid Co., New York, N. Y.
Monsanto Chemical Co., St. Louis, Mo.
Malic acid, National Aniline & Chemical Co., Inc., New York, N. Y.
Adipic acid, E. I. du Pont de Nemours & Co., Wilmington, Del.
Succinic acid and anhydride:
American Cyanamid Co., New York, N. Y.
National Aniline & Chemical Co., Inc., New York, N. Y.
Urea, E. I. du Pont de Nemours & Co., Wilmington, Del.
Formaldehyde:
E. I. du Pont de Nemours & Co., Wilmington, Del.
Empire Oil & Refining Co., Bartlesville, Okla.
Heyden Chemical Corp., New York, N. Y.
Hexamethylenetetramine, tech.:
E. I. du Pont de Nemours & Co., Wilmington, Del.
Heyden Chemical Corp., New York, N. Y.
Monsanto Chemical Co., St. Louis, Mo.
Furfural, Quaker Oats Co., Chicago, Ill.
Vinyl acetate:
Carbide & Carbon Chemicals Corp., New York, N. Y.
E. I. du Pont de Nemours & Co., Wilmington, Del.
Niacet Chemicals Corp., Niagara Falls, N. Y.
Vinyl chloride, Carbide & Carbon Chemicals Corp., New York, N. Y.
APPENDIX F
GLOSSARY[29]
_Alkyd resin._—Any condensation product involving a polybasic acid and
a polyhydric alcohol. Typical examples are phthalic glyceride and its
modifications containing combined fatty acids or rosin. Representative
examples are Rezyls and Glyptal.
_Aminoplast._—General terms for synthetic resins from amino or amido
compounds. A typical example is urea-formaldehyde.
_Amorphous._—Devoid of crystalline structure. This condition is rare.
Many substances which are apparently amorphous show microcrystallinity,
particularly under X-ray examination.
_A-stage resins._—Thermosetting resins reacted only to the initial stage
where they are soluble and fusible. The normal stage of a resin used for
impregnation.
_Bonding strength._—The amount of adhesion between a binder and filler.
More specifically, the measure of the extent to which the composite
layers of a laminated product are bonded together.
_Brittleness._—Liability to break, generally to a conchoidal fracture.
_B-stage resins._—Thermosetting resins reacted to a stage where they
soften when heated and swell in contact with liquids but do not entirely
fuse or dissolve. This is the preferred stage for the resin in molding
compositions.
_Casting._—Forming a material into a shape by pouring it when liquid into
a mold. The product from the mold is used as such or mechanically worked
in various ways to the final articles, as by sewing, cutting, blanking,
turning, drilling, forming, swaging, grinding, polishing, sanding, or
routing.
_Compressive strength._—Resistance to deformation under applied pressure.
_Condensation._—A chemical reaction in which two or more molecules
combine with a separation of water or some other simple substance.
Applied to synthetic resins it means the formation of a resin by
combination of a number of molecules with elimination of water,
ammonia, hydrogen chloride, or other simple substance. Examples of
condensation resins are alkyd, phenol-aldehyde, and urea-formaldehyde
resins. The final products are also called condensation-polymers. (See
Polymerization.)
_Copolymerization._—The term applied when two or more substances
polymerize at the same time to yield a product which is not a mixture of
separate polymers but a complex having properties different from either
polymer alone. For example, vinylite is produced by polymerization of a
mixture of vinyl acetate and vinyl chloride.
_C-stage resins._—Thermosetting resins in the final stage in which they
are infusible and insoluble. The state of the resin in the final molded
article.
_Curing._—The change of a binder from the soluble-fusible condition
to the substantially insoluble-infusible form by chemical action. The
heat-setting of a resinoid. Action is analogous to vulcanization of
rubber.
_Dielectric strength._—Voltage gradient at which a continuous electrical
discharge will take place between two electrodes when the material in
question is placed between the electrodes and a potential difference is
applied to them.
_Elastic._—A substance which exhibits rubberlike properties or “high
elasticity” over a wide range of applied forces.
_Elastic deformation._—When a substance reverts to its original
dimensions on release of an applied stress.
_Elastic limit._—The point at which a body begins to yield under a
stress; that is, when the stress is equal to or greater than the internal
friction.
_Elasticity._—The property by virtue of which a body reverts to its
normal bulk or shape after deformation by an applied force.
_Extrusion molding._—A molding procedure for extended shapes of uniform
cross section, whereby a heat-softened substance is forced through an
orifice of form coinciding with the cross section of the article.
_Flexibility._—Capability of bending without breaking.
_Gums._—Viscous vegetable secretions which harden but, unlike resins, are
water soluble. The name is often applied, particularly in the varnish
industry, to natural resins such as copals.
_Hardness._—Property of substances determined by their ability to
abrade or indent one another. Often measured by the extent or depth of
indentation produced by a standard substance under a predetermined load.
_Impact strength._—The measure of toughness of a material. Generally
determined by the energy required to break a specimen in one blow.
_Injection molding._—A molding procedure whereby a heat-softened plastic
material is forced from a receptacle into a cavity which gives the
article of desired shape. Used particularly for thermoplastics since
the scrap can be reused. As soon as the composition in the mold cools
sufficiently to be rigid, the mold is opened and the molded article
removed. An analogy of injection molding in another field is shown by the
linotype machine.
_Inserts._—Parts of a finished molded article which are of different
material from the molding composition but are set in place or positioned
by the molding operation.
_Laminated products._—Sheets of material united by a binder. For example,
sheets of paper or wood coated and/or impregnated with a resinous
composition and subjected to pressure, generally with heat.
_Monomer._—The simplest repeating structural unit of a polymer. For
addition polymers this represents the originally unpolymerized compound.
_Phenoplast._—A general term for phenol-aldehyde resins. Synonymous with
popular term “phenolics.”
_Plastics._—All substances that can be molded. In general a plastic is a
substance which behaves as a solid at stresses less than a certain amount
known as the yield value and as a viscous liquid at stresses greater
than this. The name is also applied to substances which originally but
not ultimately fulfill this condition. For example, it is applied to
thermoset compositions or resinoids in the final stages.
_Plasticity._—Susceptibility to and the retention of deformation.
Capacity of taking and retaining the form of a mold. The property of
solids by virtue of which they hold their shape permanently under the
action of small shearing stresses but are readily deformed, worked, or
molded under larger stresses.
_Polymerization._—A chemical change resulting in the formation of
a new compound whose molecular weight is a multiple of that of the
original substances. The products of the reaction are called polymers.
To distinguish from those resulting from condensation (q. v.), they
are often designated addition polymers, since the reaction is that of
successive addition of a large number of relatively small molecules
(monomers) to form the final polymer.
_Power factor._—In an insulating material, the ratio of total power
loss (watts) in the material to the product of voltage and current in a
capacitor in which that material is a dielectric.
_Preforms._—Molding powders converted by pressure and without heat
into a denser coherent form which approximates the shape of the final
hot-pressed article. Molding material converted to preforms has about
half the bulk factor of the original powder. Other forms of densified
composition which do not necessarily approximate the shape of the final
molding are tablets, briquettes, pellets, pills, and balls.
_Resin._—A term generally referring to a physical condition at room
temperature approximating the physical properties of natural resins.
However, the temperature of reference should not be limited to room
temperature and the term is here intended to embrace all substances which
within a certain temperature range show these, properties. For example,
many oil-modified alkyd resins are viscous liquids at room temperature
but not at lower temperatures; polystyrene is a resin at room temperature
but rubberlike when warmed.
_Resinoids._—The class name applied to thermosetting resins. Temporary
thermoplastics. The name is also often applied to the final cured resins.
_Softening point._—Resins have no sharp melting point. Application of
heat causes gradual change from a brittle or exceedingly thick and slow
flowing material to a softer and less viscous liquid. The softening point
is the temperature at which the material flows at a definite rate or to a
definite distance.
_Synthetic resin._—A complex, substantially amorphous, organic semisolid
or solid material (usually a mixture of substances) built up by chemical
reaction of comparatively simple compounds and, depending upon the
temperature at which the examination is made, approximating the natural
resins in various physical properties: namely, luster, fracture,
comparative brittleness, insolubility in water, fusibility or plasticity
when heated or exposed to heat and pressure, and, at a certain more
or less narrow temperature range before fusion, showing a degree of
rubberlike extensibility; but commonly deviating widely from natural
resins in chemical constitution and behavior with reagents.
_Synthetic rubber._—Caoutchouc synthesized in the laboratory. The term is
a misnomer and most probably represents an impossibility.
_Tensile strength._—The greatest internal force per unit of cross section
which a material develops before failure under tension.[30]
_Thermoplastic._—The property of softening under heat. All molding
materials are thermoplastic at the initial application of heat. One class
(the so-called thermoplastics) remains soft permanently under heat; the
other (thermosetting), after first softening, sets or cures more or less
quickly to a more solid form. A practical distinction is that with the
first class the mold must be cooled before the molded article is removed,
but not with the second. A thermoplastic substance is adequately rigid
at normal temperatures and under ordinary conditions of stress but is
capable of deformation under heat and pressure.
_Thermosetting._—The property of undergoing a chemical change when
heated whereby a hardened product is obtained. Property most pronounced
in phenol and urea formaldehyde resins and less so with alkyds. A
thermosetting substance possesses initially the properties of a
thermoplastic but under the influence of heat undergoes chemical change
so that it is no longer thermoplastic but becomes permanently infusible.
_Viscosity._—Internal friction or resistance to change of form of a
liquid. The constant ratio of shearing stress to rate of shear.
_Water-absorption._—Amount of water taken up when exposed to humid
conditions or when immersed. Both rate of absorption and total absorption
are important, also change in dimensions. A certain amount of absorbed
water may improve mechanical properties but usually weakens electrical
characteristics.
FOOTNOTES
[1] A glossary of technical terms is included in appendix F. p. 160 of
this report. There are, however, certain fundamental terms which it would
be advisable to have clearly in mind at this point.
[2] Shellac is a substance secreted by lac insects feeding on certain
types of hardwood trees.
[3] Journal of the Society of Chemical industry, 1901. Vol. 20, p. 1075.
[4] Current sales prices in the United States average between 7 and 10
cents per pound and any imports would be dutiable under the provisions
of par. 28 of the Tariff Act of 1930 at 45 percent ad valorem based on
American selling price plus 7 cents per pound. Based on an American
selling price of 7 cents per pound, the import duty would be slightly
more than 10 cents per pound, while on an American selling price of 10
cents per pound the duty would be 11.5 cents per pound.
[5] Zelov, Victor I. Automatic Molding, Pt. 2, Advantages and
limitations. Modern Plastics, v. 15, No. 2, p. 206; October 1937.
[6] For texts and interpretation of exclusion orders see Treasury
Decisions 41512; 41895; 44411; 44491; 44776; and 44977.
[7] American selling price is defined in section 402, (g) as: “The
American selling price of any article manufactured or produced in the
United States shall be the price, including the cost of all containers
and coverings of whatever nature and all other costs, charges, and
expenses incident to placing the merchandise in condition packed ready
for delivery, at which such article is freely offered for sale to all
purchasers in the principal market of the United States, in the ordinary
course of trade and in the usual wholesale quantities in such market, or
the price that the manufacturer, producer, or owner would have received
or was willing to receive for such merchandise when sold in the ordinary
course of trade and in the usual wholesale quantities, at the time of
exportation of the imported article.”
[8] United States value is defined in section 402, (e) as: “The United
States value of imported merchandise shall be the price at which such
or similar imported merchandise is freely offered for sale, packed
ready for delivery, in the principal market of the United States to all
purchasers, at the time of exportation of the imported merchandise, in
the usual wholesale quantities and in the ordinary course of trade, with
allowance made for duty, cost of transportation and insurance, and other
necessary expenses from the place of shipment to the place of delivery, a
commission not exceeding 6 per centum, if any has been paid or contracted
to be paid on goods secured otherwise than by purchase, or profits not to
exceed 8 per centum and a reasonable allowance for general expenses, not
to exceed 8 per centum on purchased goods.”
[9] The reclassifications read:
PAR. 2. “Vinyl acetate, polymerized or unpolymerized, and synthetic
resins made in chief value therefrom, not specially provided for.”
PAR. 11. “Synthetic resins made in chief value from vinyl acetate, not
specially provided for.”
[10] See sections on import under each resin.
[11] Reduced May 23, 1934, from 25 cents per pound and 30 percent by
Presidential proclamation under Section 336 of the Tariff Act of 1930.
[12] Based on the total sales in 1937 reported to the Tariff Commission;
sales in dollars dived by quantity (net resin content).
[13] The new consumption-restriction regulations are—
_Exterior use on plaster, brick, stone, and cement_:
1. Surfaces already painted with oil paint may be repainted with
oil paints, without restrictions;
2. Surfaces calcimined may be painted with paints containing not
more than 15 percent oil;
3. Unpainted surfaces may be painted only with paints free of oil.
_Exterior use on wood_:
Linseed oil paint may be used for the first coat, and succeeding
coats may contain up to 70 percent oil.
_Exterior and interior use on metal_:
Oil paints may be used without restriction.
_Interior use on plaster, brick, stone, and cement_:
1. Surfaces already painted with oil paint may only be repainted
with paint containing not more than 15 percent oil.
2. Unpainted surfaces must be painted with paint free of oil.
_Interior use on wood, to be cleaned with soap and soda_:
El Varnish and oil varnish may be used for the first coat
followed by paint containing up to 70 percent oil.
_Interior use on wood, not cleaned with soap and soda_:
As above, except that succeeding coats may contain not more than
40 percent oil.
[14] Acknowledgment: Most of the information about the industry in Great
Britain was submitted by Norman Inwood of the staff of the American
consulate general at London, England.
[15] Acknowledgment: Information obtained on the synthetic resin industry
in France was furnished by Addison E. Southard, American consul general
at Paris.
[16] Acknowledgment: Much of the information on the Japanese synthetic
resin industry included herein was furnished by Carl H. Boehringer,
Assistant Trade Commissioner at Tokyo at the request of the U.S. Tariff
Commission.
[17] These figures are based on an average naphthalene content of coal
tar of slightly less than 10 percent. The total amount contained would,
of course, not be recovered even under ideal market conditions as to
price and demand.
[18] Par. 1651. Coal-tar products: ... naphthalene which after the
removal of all the water present has a solidifying point less than 79° C.
... (Free).
[19] Par. 27. Coal-tar products:
(_a_) (1), (5) ... naphthalene which after the removal of all water
present has a solidifying point of 79° C. or above; all the foregoing
products in this paragraph whether obtained, derived, or manufactured
from coal tar or other sources; ... 40 percent ad valorem and 7 cents per
pound.
(_c_) The ad valorem rates provided in this paragraph shall be based upon
the American selling price (as defined in subdivision (g) of section
402, title IV), of any similar competitive article manufactured or
produced in the United States. If there is no similar competitive article
manufactured or produced in the United States then the ad valorem rate
shall be based upon the United States value, as defined in subdivision
(e) of section 402, title IV.
(_d_) For the purposes of this paragraph any coal-tar product provided
for in this act shall be considered similar to or competitive with any
imported coal-tar product which accomplishes results substantially equal
to those accomplished by the domestic product when used in substantially
the same manner.
[20] Upon American selling price or United States value.
[21] The relevant provisions of this act are as follows:
Par. 27 (b) ... phenol, carbolic acid which on being subjected to
distillation yields in the portion distilling below one hundred and
ninety degrees centigrade a quantity of tar acids equal to or more than
5 per centum of the original distillate, ..., and any mixture of any of
the foregoing products with any of the products provided for in paragraph
1651, 20 per centum ad valorem and 3½ cents per pound.
(c) The ad valorem rates provided in this paragraph shall be based upon
the American selling price (as defined in subdivision (g) of section
402, title IV), of any similar competitive article manufactured or
produced in the United States. If there is no similar competitive article
manufactured or produced in the United States then the ad valorem rate
shall be based upon the United States value, as defined in subdivision
(e) of section 402, title IV.
(d) For the purposes of this paragraph any coal-tar product provided
for in this Act shall be considered similar to or competitive with any
imported coal-tar product which accomplishes results substantially equal
to those accomplished by the domestic product when used in substantially
the same manner.
[22] In 1923 the unit value of domestic sales was 27 cents per pound and
the duty on imports (computed specific rate per pound) was 16 cents; in
1925 the corresponding figures were 21 and 16 cents, respectively.
[23] Par. 1651. Coal-tar products: ..., all mixtures of any of these
distillates and any of the foregoing pitches, and all other materials or
products found naturally in coal tar, whether produced or obtained from
coal tar or other source, and not specially provided for in pars. 27 or
28....
[24] Par. 27 (a) (2). Coal-tar products: All distillates (except
those provided for in sub-paragraph (b)) of coal tar, blast-furnace
tar, oil-gas tar, and water-gas tar, ..., which on being subjected to
distillation yield in the portion distilling below two hundred and
fifteen degrees centigrade a quantity of tar acids equal to or more than
75 per centum of the original distillate.
[25] Par. 27 (b). Metacresol having a purity of 90 per centum or more,
orthocresol having a purity of 90 per centum or more, paracresol having
a purity of 90 per centum or more, ... and any mixture of any of the
foregoing products with any of the products provided for in paragraph
1651, ...
Par. 27 (c). The ad valorem rates provided in this paragraph shall be
based upon the American selling price (as defined in subdivision (g) of
section 402, title IV), of any similar competitive article manufactured
or produced in the United States. If there is no similar competitive
article manufactured or produced in the United States then the ad
valorem rate shall be based upon the United States value, as defined in
subdivision (e) of section 402, title IV.
Par. 27 (d). For the purposes of this paragraph any coal-tar product
provided for in this Act shall be considered similar to or competitive
with any imported coal-tar product which accomplishes results
substantially equal to those accomplished by the domestic product when
used in substantially the same manner.
[26] Par. 27 (b). ... cresylic acid which upon being subjected to
distillation yields in the portion distilling below two hundred and
fifteen degrees centigrade a quantity of tar acids equal to or more than
75 per centum of the original distillate....
[27] Some of the makers of these products do not care to be identified
with their manufacture.
[28] Some of the makers of these products are not listed because they do
not care to be so identified.
[29] Based on pp. 321-4, Modern Plastics, October 1937.
[30] Source: Peele’s Mining Engineers’ Handbook, Ed. 1, p. 2209.
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