Chapter I: Part 1

UNITED STATES TARIFF COMMISSION

SYNTHETIC RESINS
AND THEIR RAW MATERIALS

REPORT No. 131

SECOND SERIES

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

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.

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).