Synthetic Resins And Their Raw Materials - free ebook by United States Tariff Commission

SYNTHETIC RESINS AND THEIR RAW MATERIALS

REPORT No. 131 SECOND SERIES...

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RECENT REPORTS OF THE UNITED STATES TARIFF COMMISSION

For sale by the Superintendent of Documents, Government Printing Office, Washington, D. C., at the prices indicated...

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ERRATA

December 1938 Address All Communications UNITED STATES TARIFF COMMISSION WASHINGTON, D. C....

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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. 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 c

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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

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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 ori

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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, phth

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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

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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

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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 com

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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 u

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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 po

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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 t

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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 p

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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 way

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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 alkal

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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

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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-t

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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 Jap

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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 a

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CAST PHENOLIC RESINS

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 pum

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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

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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

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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 che

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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,

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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

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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 phtha

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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: 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 al

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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 solv

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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 an

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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. 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 obtain

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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

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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

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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. A new development of widespread importance in the sy

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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 acry

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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 &amp; 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

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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. Coumarone and indene are present in appreciable quantities in certain coal-tar fractions, especially in the solvent naphtha fractions distilling betw

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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: 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 limi

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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....

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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. 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 tendenc

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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: Miscible in all proportions with petroleum solvents. Petropol No. 1158 is used by cor

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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....

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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. 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

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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 thickne

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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

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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. Molded Polystyrene Resins. Sou

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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 p

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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

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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 para

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Exports from the United States.

Exports of vinyl resins are not separately shown in official statistics. 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 res

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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

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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....

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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....

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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. The

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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

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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 t

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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 adhe

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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

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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

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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 resin

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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 afte

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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 entr

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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, semiso

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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

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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 ma

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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

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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 advant

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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: 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

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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

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GERMANY

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, con

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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

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FRANCE[15]

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 t

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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: Resin products are widely used by the electrical industries for wall plates, plugs, switches, fuse boxes, etc. Other articles made of synthetic resins are: handl

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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

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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 Corpor

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CANADA

The producers of synthetic resins in Canada are: 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, viny

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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. Karboli

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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

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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....

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POLAND

Production of synthetic resins in Poland in 1936 totaled 660,000 pounds, entirely of the tar-acid type. 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....

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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

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PHTHALIC ANHYDRIDE

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 a

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POLYBASIC ACIDS OTHER THAN PHTHALIC 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 is widely distributed in the v

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GLYCERIN

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, contai

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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

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PHENOL

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

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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, applie

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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 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 increas

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FORMALDEHYDE

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

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HEXAMETHYLENETETRAMINE

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. Duri

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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

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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

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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

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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 .)

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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 Unite

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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 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....

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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 imp

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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 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 1 Not separately reported. Source: Bulletin Mensuel du Commerce. Table 94. — Refined naphthalene: Belgian imports and exports, 1932-37 Table 95. — Crude and refined naphthalene: Netherland imports and

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APPENDIX B TRADE NAMES FOR SYNTHETIC RESINS MADE IN THE UNITED STATES

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 &amp; Varnish Co., Chicago, Ill.; Ford Motor Co., Detroit, Mich.; Heresite &amp; Chemical Co., Manitowoc, Wis.; Millergum Co., Chicago, Ill.; Nubian Paint &amp; Varnish Co., Chicago, Ill.; Varcum Chemical Co., Niagara Falls, N. Y.; Vita Var Corp., Newark, N. J. Other makers of alkyd resins in the United States incl

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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 microcrystallini

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