Synthetic resins and their raw materials

Chapter VI: Part 6

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There are about 14 molders of synthetic resins in Canada, of which all but 3 are in Ontario. These firms make a general line of molded articles including electrical articles, closures, costume jewelry, and smokers’ accessories. Appreciable quantities of molded articles are imported from the United States and smaller quantities from Germany.

UNION OF SOVIET SOCIALIST REPUBLICS

The synthetic resin industry in the Union of Soviet Socialist Republics is concentrated in two public departments, known as Public Commissariates: (a) Public Department for Heavy Industry and (b) Public Department for Light Industry.

The Department for Heavy Industry, known as Soyuzchemplastmass, controls the following plants:

1. Karbolit-pawod in Ljubatschani, producing tar-acid resin laminated fabric known as Textolite.

2. Karbolit-stroj in Ljubatschani, making cast phenolic resins.

3. Karbolitni-pawer in Dubrowka, making tar-acid resin molding compounds. This plant has at least 350 molding presses producing electrical parts and automotive parts. The number of presses was to have been increased to 1,000 in 1937.

4. Komsomolskaja prawda in Leningrad manufactures articles, including phone sets, from cast phenolic resins.

5. Ochtenski Chimkombinat in Ochta. This plant makes nitrocellulose plastics. No information could be obtained by our Chargé d’Affaires at Moscow concerning its production of synthetic resins, although it is believed to be considerable.

The Department for Light Industry has a resin section known as Mosplastmass producing casein plastics only.

THE NETHERLANDS

There has been no production of synthetic resins in the Netherlands; but a plant is under construction (October 1937) at Groningen for the manufacture of alkyd resins. The manufacture of surface coating and electrical parts from imported resins is carried on, chiefly by N. V. Philips’ Gloeilampenfabrieken, Afdeeling Inkoop, Eindhaven, manufacturers of radios, filament lamps, and electrical appliances. Efforts are being made to employ resins for other purposes, such as the bonding of plywood and the manufacture of closures and novelties, but little has been accomplished thus far. The relatively high cost of the resins is the principal difficulty. Molding compounds and laminated sheets, rods, and tubes are imported from Germany, Great Britain, Austria, and the United States.

The paint, varnish, and lacquer industry in the Netherlands has been experimenting with synthetic resins for several years. Alkyd resins of the glycerol phthalate type are being used by Dutch paint makers, imported principally from Germany and Austria. In spite of high cost, they have been found to have many advantages, especially better and more uniform quality. The prices of gums and resins in the Netherlands during the latter part of 1936 are shown in table 31.

TABLE 31.—_Prices of gums and resins in the Netherlands, 1936_

--------------------------------------+------------
|Florins per
Type | 100 kilos
--------------------------------------+------------
Damar |37.
Congo copal (various qualities) |12 to 45.
Indian copal (various qualities) |20 to 35.
Kauri (various qualities) |25 to 200.
Shellac (various qualities) |37 to 52.
Pine resin (rosin) (various qualities)|13 to 14.
Synthetic resins |80 to 120.
--------------------------------------+------------

The Dutch aviation industry is using tar-acid resins to bond plywood for wing surfacing on Fokker-type wooden planes. The advantages obtained are excellent adhesiveness and resistance to moisture and temperature changes. In this application they have replaced casein.

Germany supplies more than 85 percent of the Netherland imports of synthetic resins, as shown in table 32.

TABLE 32.—_Synthetic resins: Netherland imports by countries, 1931 and 1933-37_

[Pounds]
---------------+---------+---------+---------
Source | 1931 | 1933 | 1934
---------------+---------+---------+---------
Germany |1,203,393|1,257,568|1,207,857
United Kingdom | 8,520| 47,843| 64,458
Austria | 63,758| 7,297| 30,886
UNITED STATES | 3,168| 24,193| 27,434
Belgium | 2,640| 3,923|
France | | 3,120| 4,129
Czechoslovakia | 3,326| 4,948|
Switzerland | 1,789| 4,193|
Other countries| 1,450| 1,027| 2,629
+---------+---------+---------
Total |1,288,044|1,354,112|1,337,393
---------------+---------+---------+---------

[Pounds]
---------------+---------+---------+---------
Source | 1935 | 1936 | 1937[1]
---------------+---------+---------+---------
Germany |1,351,581|1,490,310|2,449,311
United Kingdom | 94,565| 335,099|1,223,553
Austria | 63,642| ([2]) | 132,276
UNITED STATES | 50,888| ([2]) | ([2])
Belgium | 1,514| ([2]) | ([2])
France | 616| ([2]) | ([2])
Czechoslovakia | | ([2]) | ([2])
Switzerland | | ([2]) | ([2])
Other countries| 1,573| 216,051| 207,232
+---------+---------+---------
Total |1,564,379|2,041,460|4,012,372
---------------+---------+---------+---------

[1] Preliminary.

[2] Not separately reported.

Source: Consular reports.

DENMARK

The annual output of synthetic resins in Denmark is about 500,000 pounds, almost entirely of the tar-acid type.

Bakelite is produced by the Nordiske Kabel and Traadfabrikker A. S. Fabrikvej at Copenhagen. Other brands made in Denmark are Nokait, Helomit, and Etronit. There are 14 manufacturers of finished products, making electrical equipment principally.

POLAND

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

16. RAW MATERIALS FOR ALKYD RESINS

The alkyd resins are made chiefly from phthalic anhydride and glycerin. Phthalic anhydride in turn is made from naphthalene. Polybasic acids such as maleic, succinic, etc., may also be used with glycerin to form alkyd resins. Naphthalene, phthalic anhydride, maleic and other polybasic acids, and glycerin are discussed in the order named.

NAPHTHALENE

The discovery of naphthalene in coal tar was made simultaneously by Garden and Brande in 1819, and its composition was determined by Faraday in 1826 and later by Laurent in 1832. Naphthalene is almost invariably a constituent of the products obtained when organic matter is heated to comparatively high temperatures. For example, it is formed in small quantities when acetylene, alcohol, acetic acid, benzene, or toluene are heated to high temperatures. Together with certain aromatic hydrocarbons it is formed in the cracking of petroleum and in the hydrogenation of petroleum fractions. Naphthalene is a constituent of the principal varieties of tar produced from coal in the manufacture of gas and coke under ordinary conditions, but not of low-temperature tar. It is present in coal gas although its presence must be kept as low as possible to avoid blocking service pipes in cold weather. The proportion in gas tar varies with the kinds of coal used and is greater the higher the temperature used during carbonization; it usually amounts to 4 to 6 percent but is sometimes as much as 10 percent. In tars obtained from byproduct coke ovens the proportion of naphthalene and other aromatic hydrocarbons depends on the type of oven used. Byproduct coke-oven tar averages 10 to 11 percent naphthalene; blast-furnace tar contains only very small amounts.

Processes to synthesize naphthalene were described as early as 1873 by Aronheim, in 1876 by Wroden and Znatowicz, and in 1884 by Baeyer and Perkin. English Patent No. 26,061 of 1898 claims that it may be obtained by heating barium carbide with barium hydroxide to a high temperature. None of these processes has become of commercial importance.

Recovery of naphthalene.

Naphthalene is recovered in the distillation of coal tar, in the fraction boiling at 180° to 250° C., in the creosote oil fraction boiling at 240° to 270° C. and most abundantly in the carbolate or middle oil fraction boiling at 200° to 250° C. When these fractions are allowed to cool most of the naphthalene crystallizes out and is separated by draining and hot-pressing. This crude material is partially purified by washing with hot caustic soda solution to remove tar acids and then with mineral acid to remove basic substances. Refined naphthalene is obtained by subliming, or preferably by distilling the crude product.

Description and uses.

The Tariff Act of 1930 defines crude naphthalene as naphthalene solidifying under 79° C. after the removal of all water present; and refined naphthalene as that having a solidifying point at or above 79° C. after the removal of all water present.

Crude grades, melting between 70° and 78.5° C., are found in commerce as yellow, red, or brown crystalline solids. These grades are used in the manufacture of phthalic anhydride and other coal-tar intermediates; in the manufacture of lampblack; to enrich illuminating gas and sometimes motor fuel; in synthetic tanning materials; and in certain insecticides. Probably its most important outlets are as a raw material for phthalic anhydride (see p. 98) and refined naphthalene.

Refined grades, melting above 79° C., are marketed as white, crystalline lumps or flakes. Their principal uses are in the manufacture of intermediates, dyes, medicinals, solvents, and textile assistants; as moth repellants; as a lubricant when mixed with rapeseed oil; to remove the “bloom” from lubricating oils; as a preservative for rubber goods and animal skins; and in explosives (trinitro naphthalene). In 1936 more than 75 coal-tar intermediates made from naphthalene were commercially produced in the United States. Of the 75 million pounds of these intermediates produced in that year, 31 million pounds were phthalic anhydride, an important component of synthetic resins of the alkyd type.

United States production.

Crude naphthalene is produced in the United States by byproduct coke-oven operators, gas works that produce their own coal tar, and also by firms that purchase coal tar and distill it. Statistics of production by groups are shown in table 33.

TABLE 33.—_Crude naphthalene: United States production, 1918-37_

----+-----------------------------+------------------------------
| By producers of tar | By purchasers of tar
----+----------+---------+--------+----------+----------+--------
| Quantity | | Unit | Quantity | | Unit
| | Value | value | | Value | value
----+----------+---------+--------+----------+----------+--------
| _1,000 | | _Per | _1,000 | | _Per
| pounds_ | | pound_ | pounds_ | | pound_
1918| | | | 40,138|$1,281,440| $0.032
1919| | | | 12,612| 327,201| .030
1923| 11,872| $201,824| $0,017| 41,453| 652,148| .016
1925| 9,239| 92,389| .010| 34,135| 519,773| .015
1926| 7,747| 100,709| .013| 45,166| 494,986| .011
1927| 8,303| 91,331| .011| 45,298| 470,806| .010
1928| [1]12,182| 146,186| .012| 35,180| 395,059| .011
1929| [1]19,761| 316,182| .016| 19,502| 366,491| .020
1930| [1]12,640| 151,681| .012| 18,617| 304,574| .020
1931| [1]7,623| 76,229| .010| 13,311| 199,665| .015
1932| [1]4,632| 41,690| .09| 8,961| 125,453| .014
1933| [1]6,618| 66,181| .010| 24,003| 360,040| .015
1934| [1]10,743| 139,665| .013| 27,179| 489,222| .018
1935| [1]12,937| 168,185| .013| 34,716| 624,890| .018
1936| [1]37,552| 600,836| .016| 51,984| 1,195,632| .023
1937| [1]60,797|1,215,942| .020| 55,182| 1,545,100| .028
----+----------+---------+--------+----------+----------+--------

----+------------------------------
| Total production
----+----------+----------+--------
| Quantity | | Unit
| | Value | value
----+----------+----------+--------
| _1,000 | | _Per
| pounds_ | | pound_
1918| 40,138|$1,281,440|$0.032
1919| 12,612| 327,201| .026
1923| 53,325| 853,972| .016
1925| 43,374| 612,162| .014
1926| 52,913| 595,695| .011
1927| 53,601| 562,137| .010
1928| 47,362| 541,245| .011
1929| 39,263| 682,673| .017
1930| 31,257| 456,255| .015
1931| 20,934| 275,894| .013
1932| 13,593| 167,143| .012
1933| 30,621| 426,221| .014
1934| 37,922| 628,887| .016
1935| 47,653| 793,075| .017
1936| 89,536| 1,796,468| .020
1937| 115,979| 2,667,522| .023
----+----------+----------+--------

[1] Crude and refined. Refined naphthalene included here is
probably small so that the figures here and those for total
production are substantially accurate.

Source: Bureau of Mines and U.S. Tariff Commission.

Refined naphthalene is obtained from domestic crude, imported crude, and recently from petroleum cracking and hydrogenation. Table 34 shows the annual production and sales of refined naphthalene since 1916. The difference between the figures for the quantity produced and that sold represents the amount used by refiners in the manufacture of other products.

TABLE 34.—_Refined naphthalene: United States production and sales, 1917-37_

------+-------------------------------+--------------------------------
| Production | Sales
Year +----------+-----------+--------+----------+-----------+---------
| Quantity | Value | Value | Quantity | Value | Value
------+----------+-----------+--------+----------+-----------+---------
| _1,000 | _1,000 | _Per | _1,000 | _1,000 | _Per
| pounds_ | dollars_ | pound_ | pounds_ | dollars_ | pound_
1917 | 35,343 | 2,334 | $0.07 | | |
1918 | 28,112 | 2,163 | .08 | | |
1919 | 17,625 | 1,161 | .07 | | |
1920 | 30,231 | 2,309 | .08 | | |
1921 | 13,554 | | | 13,183 | 741 | $0.056
1922 | 17,420 | | | 14,060 | 794 | .057
1923 | 28,184 | | | 21,871 | 1,271 | .058
1924 | 15,324 | | | 11,961 | 603 | .050
1925 | 17,581 | | | 12,508 | 610 | .049
1926 | 18,072 | | | 12,456 | 576 | .046
1927 | 21,233 | | | ([1]) | |
1928 | 24,992 | | | ([1]) | |
1929 | 31,144 | | | 21,120 | 1,027 | .049
1930 | 31,956 | | | 20,171 | 949 | .047
1931 | 34,959 | | | 21,260 | 829 | .039
1932 | 25,825 | | | 18,877 | 783 | .041
1933 | 42,708 | | | 28,658 | 1,065 | .037
1934 | 38,730 | | | 21,257 | 1,100 | .052
1935 | 46,564 | | | 28,761 | 1,212 | .042
1936 | 52,694 | | | 30,499 | 1,841 | .060
1937 | 52,194 | | | 29,657 | 1,893 | .060
------+----------+-----------+--------+----------+-----------+---------

[1] Not publishable.

Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.

_Organization of the industry._—There are 10 domestic producers of crude naphthalene, operating 52 tar-distilling plants in the following States: Ohio (7), Pennsylvania (6), Illinois and New York (5 each), Alabama, Minnesota, and New Jersey (3 each), Missouri, Rhode Island, Wisconsin, Utah, West Virginia (2 each), and Michigan, Massachusetts, Maryland, Kentucky, Oregon, Connecticut, Tennessee, Indiana, Virginia, and Washington (1 each). Although these plants do not all recover naphthalene as such, they are equipped to recover a crude mixture of naphthalene and tar acids for shipment to a central extracting and refining plant. The principal producing plants are located in Pennsylvania (2), New Jersey (2), Illinois (1), Indiana (1), and West Virginia (1).

The purchasers of tar produced 77 percent of the total output of crude naphthalene in 1935 and 58 percent in 1936.

There are 8 producers of refined naphthalene located in the following States: New Jersey (3), Pennsylvania (2), California, Indiana, and Ohio (1 each).

_Trend of production._—Although the United States is the largest producer of coal tar, the limited demand for the main products of tar distillation (creosote oil and pitch) has tended to restrict the amount distilled, thereby reducing the output of naphthalene and the tar acids to a point where the domestic output was not sufficient to meet our requirements. As a result, large quantities of these products have been imported. In 1936 we produced 560 million gallons of coal tar, containing from 400 million to 500 million pounds of naphthalene.[17] In the same year we distilled about 300 million gallons of tar, containing 230 million to 270 million pounds of naphthalene,[17] and our actual recovery of crude naphthalene was 89,536,000 pounds.

Early in 1935 the price of crude naphthalene was about 1.5 cents per pound or 15 cents per gallon, at which level there was little incentive to isolate it from the various fractions of tar distillation. Late in 1935 and in 1936 a serious shortage in naphthalene prevailed, largely because of increased demand by synthetic resin makers but also because of restrictions on exports from certain European countries. The price of the crude then advanced in domestic markets to from 2.5 to 3 cents per pound, with the demand greatly exceeding the supply. Between 1930 and 1936 the apparent consumption of crude naphthalene (production plus imports) increased from 59 million to 129 million pounds, or more than 100 percent. During the same period production increased from 31 million to 89 million pounds; and imports increased from 27 million pounds in 1930 to 48 million pounds in 1935 but declined to 40 million pounds in 1936.

Domestic producers of naphthalene are increasing their output, and they state that continued prices of 2.5 to 3 cents per pound for naphthalene solidifying at about 75° C. or slightly higher will stimulate production sufficiently to meet all present and near-future requirements. Estimates obtained in the summer of 1936 from the large tar distillers and a petroleum refiner indicate that production was appreciably greater in 1937 than in 1935. These estimates included the potential output of two new tar distillation plants under construction, the topping of large quantities of tar (hitherto used as fuel without removing any of the products), the recovery of appreciable quantities of naphthalene by several petroleum refiners, and increased output by other producers.

Imports of crude naphthalene in 1937 amounted to 52,664,277 pounds valued at $1,133,157, or 2.2 cents per pound.

World production.

The output of naphthalene in the principal producing countries, in 1933 and 1935, is shown in table 35. Most of these statistics were estimated from the output of tar or of other distillation products given in official reports of the countries or in consular reports.

The figures in table 35 indicate that the output in 1935 was an increase of about 100 million pounds over 1933 or 41 percent. Notwithstanding this sharp increase in world production, consumers had difficulty in obtaining their requirements. It is believed that the world output in 1937 substantially exceeded that in 1935.

TABLE 35.—_Naphthalene (all grades): World production, by countries, 1933 and 1935_

[In thousands of pounds]
--------------+---------+---------
Country | 1933 | 1935
--------------+---------+---------
Germany | 109,148| 145,530
Great Britain | 45,750|[1]55,000
UNITED STATES | 30,620| 47,653
France | 30,000|[1]33,000
Netherlands |[1]15,000|[1]15,000
Belgium | 11,025|[1]25,000
Czechoslovakia| 6,835| 10,805
U. S. S. R. |[1]10,000|[1]15,000
Poland | [1]5,000| [1]8,000
Spain | [1]1,250| [1]2,000
Italy | [1]2,500| [1]3,000
Canada | [1]2,000| [1]3,000
Total | 269,128| 362,988
--------------+---------+---------

[1] Estimated.

Source: Official statistics of the several countries and consular
reports.

_Germany._—Germany is the largest producer of naphthalene and the third largest producer of coal tar. With increased production of coal tar and intensive efforts to recover the maximum of naphthalene there has been a larger output of naphthalene in recent years, but increased consumption has created a scarcity in Germany as in all other important producing countries. As a result, greatly reduced quantities are available for export, a situation that is in marked contrast to earlier periods when superabundant production created a marketing problem. The manufacture of phthalic anhydride for alkyd resins is requiring increased quantities of naphthalene.

The demand for alkyd resins has been given a marked impetus by the development of a new standardized linseed oil varnish substitute known as El Varnish, the use of which is required by the Control Board for Industrial Fats in Germany for certain interior and exterior painting (see p. 77). Increased requirements for other important purposes such as intermediates, dyes, black pigments, and explosives have also contributed to the scarcity of naphthalene. In order to conserve domestic supplies, the Reich Government, from December 1935 until late in 1937 prohibited its export without special permit. The prospect of continued strong domestic demand apparently will curtail for an indefinite period the quantities available for export.

The international scarcity of naphthalene resulted in a sharp increase in its price in Germany as elsewhere. The export embargo augmented the domestic German supply, although a shortage still existed and large consumers found it difficult to secure adequate amounts. The shortage of foreign exchange greatly curtailed imports of naphthalene from nearby countries.

The German Government issued a decree requiring that beginning July 1, 1936, the entire national output of coal tar should be delivered to plants equipped for the recovery of tar products distilling up to 240° C. (naphthalene boils at 218° C.). This measure assured maximum recovery of benzol, toluol, xylol, solvent naphtha, phenol, cresol, xylenol, other tar acids, and naphthalene. The decree contemplated an official list of distillation units, and all tar producers were required to report to the official trade control board for mineral oil their monthly output, quantities distilled, and quantities delivered to other distillation plants.

German production, imports, exports, and apparent consumption of naphthalene are shown in table 36. Production increased from 108 million pounds in 1928 to 146 million pounds in 1935; imports decreased from 9 to 4 million pounds; exports decreased from 48 to 22 million pounds; and apparent consumption increased from 69 to 128 million pounds in the same years.

TABLE 36.—_Naphthalene: German production, imports, exports, and apparent consumption, 1928-37_

[In thousands of pounds]
----+----------+-------+-------+---------------
Year|Production|Imports|Exports| Apparent
| | | | consumption[1]
----+----------+-------+-------+---------------
1928| 108,173| 9,471| 48,332| 69,312
1929| 124,362| 8,032| 39,739| 92,655
1930| 103,194| 3,892| 34,614| 72,472
1931| 92,169| 2,403| 39,077| 55,495
1932| 90,626| 952| 29,720| 61,852
1933| 109,148| 7,483| 31,842| 84,783
1934| 132,300| 8,641| 35,044| 105,891
1935| 145,530| 4,246| 22,169| 127,603
1936| ([2]) | 493| 8,153| ([2])
1937| ([2]) | 33| 24,966| ([2])
----+----------+-------+-------+---------------

[1] Production plus imports, minus exports.

[2] Not available.

Sources: Consular reports (production); Der auswartige Handel
(imports and exports).

Imports of naphthalene into Germany in past years have been supplied by nearby countries, notably the Saar (which became an integral part of Germany in February 1935), Belgium, Czechoslovakia, Poland, the Soviet Union, and others. The United States has been the most important foreign market for German naphthalene, taking from 50 to 75 percent of the total quantity exported. Other important buyers were Belgium, Italy, Japan, and France. Table 92 (see p. 144) shows the quantity and value of imports and exports by countries in recent years.

_Great Britain._—The recovery and distillation of coal tar in Great Britain is highly developed. The annual output of tar, principally gas-works tar, is somewhat smaller than in the United States, although the quantities distilled for the recovery of separate components exceed the quantities distilled in the United States. In 1935 the tar distilled in England and Wales totaled 330 million gallons and in Scotland, 31 million gallons, or a combined total of 361 million gallons as compared with about 280 million distilled in this country.

Production of naphthalene in Great Britain is shown in table 37.

TABLE 37.—_Naphthalene: Production in Great Britain, in specified years_

-------+--------------
Year | Production
-------+--------------
|_1,000 pounds_
1924 | 13,730
1930 | 41,400
1933 | 45,750
1935[1]| 55,000
1936[1]| 70,000
-------+------------

[1] Estimated.

Source: Consular reports.

Table 38 shows exports of naphthalene from Great Britain in recent years. The United States has been the best customer, in most recent years taking 50 percent or more of the total exported. Our imports from Great Britain have been entirely crude naphthalene, duty-free.

Imports of naphthalene into Great Britain are not shown separately in official statistics. It is known that the Netherlands exported small quantities to Great Britain in 1929 and 1933.

TABLE 38.—_Naphthalene: Exports from the United Kingdom_

----+-------------------+---------------------------------------
| Quantity | Value
+---------+---------+-------------------+-------------------
Year| | | To all countries | To United States
| To all |To United+--------+----------+--------+----------
|countries| States | Pounds |Dollars[1]| Pounds |Dollars[1]
| | |sterling| |sterling|
----+---------+---------+--------+----------+--------+----------
| _1,000 | _1,000 | | | |
| pounds_| pounds_| | | |
1928| 5,132| ([2]) | 20,607| 100,278| ([2]) | ([2])
1929| 9,185| 4,312| 32,348| 157,110| 12,558| 60,993
1932| 11,132| 7,514| 26,869| 94,205| 14,274| 50,046
1933| 14,718| 10,480| 38,172| 161,728| 19,604| 83,059
1934| 11,955| 6,492| 35,226| 177,514| 13,025| 65,637
1935| 14,490| 7,999| 49,939| 244,789| 18,413| 90,256
1936| 26,332| 13,412| 120,372| 598,357| 46,158| 229,447
----+---------+---------+--------+----------+--------+----------

[1] Conversion to dollars at annual average quotations of the
Federal Reserve Board.

[2] Not available.

Source: The Trade of the United Kingdom, 1929 and 1936.

_Belgium._—The distillation of coal tar is one of the oldest and most important branches of the Belgian chemical industry. Approximately 90 batteries of byproduct-coke ovens, with a total of 3,000 ovens are in operation. Practically all of the coal tar produced in these operations is distilled for the recovery of the several products. The output of naphthalene is shown in table 39.

TABLE 39.—_Naphthalene: Belgian production, 1928-35_

-------+--------------
Year | Quantity
-------+--------------
|_1,000 pounds_
1928 | 26,000
1929 | 26,500
1930 | 24,200
1931 | 22,000
1933 | 12,000
1935[1]| 25,000
-------+------------

[1] Estimated.

Source: Consular reports.

Belgian imports and exports of naphthalene, by countries, are shown in tables 93 and 94 (see pp. 146, 147). Belgium is a net importer of crude naphthalene and a net exporter of refined naphthalene. In 1937, it imported 9 million pounds and exported 6.7 million of crude; it imported only 19 thousand pounds and exported 14 million pounds of refined.

_Czechoslovakia._—The annual output of naphthalene in Czechoslovakia is shown in table 40.

TABLE 40.—_Naphthalene: Czechoslovak production, in specified years, 1928-35_

----+--------------
Year| Quantity
----+--------------
|_1,000 pounds_
1928| 5,733
1930| 6,174
1931| 2,205
1932| 1,543
1933| 6,835
1934| 9,040
1935| 10,805
----+-------------

Source: Consular reports.

_France._—Naphthalene is produced in France by a number of manufacturers, most of whom consume their production in their own factories. The French output is said to be insufficient to meet domestic requirements. Estimated production is given as approximately 30 million pounds annually. Appreciable quantities are imported from nearby countries. Imports from Belgium in recent years average between 1 million and 3 million pounds.

_Poland._—Production of crude naphthalene in Poland is shown in table 41.

TABLE 41.—_Crude naphthalene: Polish production, 1928-36_

----+--------------
Year| Quantity
----+--------------
|_1,000 pounds_
1928| 4,708
1929| 5,257
1930| 3,925
1931| 3,486
1932| 3,704
1933| 4,795
1934| 7,705
1935| 5,021
1936| 2,836
----+--------------

Source: Consular reports.

_The Netherlands._—Statistics of production are not available. Exports in recent years, however, have averaged about 10 million pounds annually. It is believed that the production of crude naphthalene exceeds 15 million pounds a year.

Table 95 (see p. 148) shows Netherland imports and exports of naphthalene by countries in recent years. Imports in 1937 amounted to 2 million pounds and exports to 15 million pounds.

_Canada._—Statistics of production are not available. The annual output of crude naphthalene is estimated at 2 to 3 million pounds.

Imports of refined naphthalene are usually about 1 million pounds (see table 96, p. 150). Exports are probably small, although in 1929 and 1934 those to the United States alone were over 1 million pounds.

_The Soviet Union._—Statistics of production of naphthalene in the Soviet Union are not available. The annual output has been estimated at 10 million pounds in 1933 and 15 million pounds in 1935. Exports have increased substantially in recent years, those to the United States from 1 million pounds in 1934 to 6 million pounds in 1935. Exports to Germany were 361 thousand pounds in 1933; 1 million pounds in 1934; and 531 thousand pounds in 1935.

_Japan._—Japanese production of naphthalene has been small compared with the output of other tar products. The output of crude naphthalene in 1934 was reported to have been 381 thousand pounds. Expansion of the byproduct coking industry in Japan and Manchuria has increased the production of coal tar, byproduct ammonia, and benzol. Japan has imported large quantities of naphthalene in recent years, principally from Germany and Belgium. The increased consumption in Europe may so reduce supplies from these sources as to cause Japan to increase the recovery at home.

Japanese imports of naphthalene from principal sources, are shown in table 97 (see p. 150). In 1936, 12.6 million pounds were imported.

United States imports.

_Rates of duty._—Prior to September 8, 1916, all grades of naphthalene were imported free of duty. Since that time crude naphthalene has remained free but refined naphthalene has been subject to the tariff treatment shown in table 42.

TABLE 42.—_Naphthalene: Rates of duty upon imports into the United States, 1916-38_

[1] Ad valorem based on American selling price or United States
value.

[2] Generalized to all countries which do not discriminate
against United States products.

Under the Tariff Act of 1930, crude naphthalene is on the free list[18] and refined naphthalene is dutiable at 7 cents per pound and 40 percent ad valorem on the basis of American selling price, since it is competitive with refined naphthalene produced in this country.[19] Under the trade agreement with Belgium, effective May 1, 1935, the duty on refined naphthalene was reduced to 20 percent[20] ad valorem and 3½ cents per pound on imports from that country. Under the Trade Agreements Act this reduction applies also to imports from all other countries which do not discriminate against commerce of the United States. In July 1938 Germany was the only one not receiving the reduced rate, exports from that country being subject to the rates specified under the Tariff Act of 1930.

_Import statistics._—Table 43 shows imports of crude naphthalene (solidifying at less than 79° C.) and table 44 of refined naphthalene (solidifying at or above 79° C.) The unit invoice values of imports of refined naphthalene in 1924, 1926, 1927, 1928, and 1935 indicate that the imported product was probably not naphthalene as recorded but one of its derivatives provided for elsewhere in paragraph 27.

TABLE 43.—_Crude naphthalene (solidifying at less than 79° C.): United States imports for consumption, in specified years, 1919-37_

--------------+--------------+--------------+----------+-----------
Calendar year | Rate of duty | Quantity | Value | Value per
| | | | pound
--------------+--------------+--------------+----------+-----------
| |_1,000 pounds_| |
1919 | Free | 3,239 | $92,265 | $0.028
1920 | do. | 15,012 | 530,219 | .035
1923 | do. | 20,992 | 575,702 | .027
1924 | do. | 5,267 | 96,491 | .018
1925 | do. | 1,980 | 26,593 | .013
1926 | do. | 6,963 | 126,088 | .018
1927 | do. | 6,576 | 131,436 | .020
1928 | do. | 19,926 | 357,679 | .018
1929 | do. | 35,007 | 598,718 | .017
1930 | do. | 27,667 | 397,292 | .014
1931 | do. | 30,971 | 318,578 | .013
1932 | do. | 27,002 | 234,557 | .009
1933 | do. | 42,786 | 451,019 | .010
1934 | do. | 47,995 | 669,383 | .014
1935 | do. | 48,455 | 643,249 | .013
1936 | do. | 39,806 | 785,396 | .020
1937[1] | do. | 52,664 |1,133,157 | .022
--------------+--------------+--------------+----------+-----------

[1] Preliminary.

Source: Foreign Commerce and Navigation of the United States.

TABLE 44.—_Refined naphthalene (solidifying at or above 79° C): United States imports for consumption, in specified years, 1919-37_

---------------+---------------------+---------+-------+------+---------
| | | | |Computed
Calendar year | Rate of duty |Quantity | Value |Unit | ad
| | | |value |valorem
| | | | | rate
---------------+---------------------+---------+-------+------+---------
| | _Pounds_| | |_Percent_
1919 |15 percent + 2½ cents| 7,650| $384|$0.050| 64.8
| per pound | | | |
1920 | do. |3,697,562|416,172| .112| 37.2
1923 |55 percent + 7 cents | 9,605| 194| .020| 401.6
| per pound | | | |
1924 | do. | 4,549| 1,147| .252| 82.8
1925 | do. | | | |
1926 |40 percent + 7 cents | 424| 125| .295| 63.7
| per pound | | | |
1927 | do. | 18,668| 3,077| .165| 82.5
1928 | do. | 27| 6| .222| 71.5
1929 | do. | ⎫ | | |
1930 | do. | ⎪ | | |
Jan. 1-June 17 | do. | ⎪ | | |
June 18-Dec. 31| | ⎬ None | | |
1931 | do. | ⎪ | | |
1932 | do. | ⎪ | | |
1933 | do. | ⎭ | | |
1934 | do. | 66| 6| .091| 116.7
1935 | do.[1] | 99| 31| .313| 62.4
1936 |20 percent + 3½ cents| 30| 20| .667| 50.5
| per pound[2] | | | |
1937[3] | do.[2] | 5,055| 1,085| .215| 36.3
---------------+---------------------+---------+-------+------+---------

[1] From Germany. No imports under trade agreement rate.

[2] Belgo-Luxemburg trade agreement rate.

[3] Preliminary.

Source: Foreign Commerce and Navigation of the United States.

Table 45 shows the principal sources of our imports of crude naphthalene in recent years. Germany was the principal source until 1936; the United Kingdom, previously the next most important source, was first in 1936 and 1937. In the last three years appreciable quantities have been received from Poland, Czechoslovakia, and the Soviet Union, hitherto unimportant sources.

TABLE 45.—_Crude naphthalene (solidifying under 79° C.): United States imports for consumption from principal sources, in specified years_

-------------------+---------+---------+---------+---------
Source | 1929 | 1931 | 1933 | 1934
-------------------+---------+---------+---------+---------
| Quantity in thousands of pounds
-------------------+---------+---------+---------+---------
Germany | 21,931 | 17,444 | 20,797 | 22,219
Belgium | 2,531 | 253 | 4,970 | 7,314
United Kingdom | 8,096 | 11,339 | 15,704 | 6,968
Poland and Danzig | | | | 5,766
Canada | 1,488 | 331 | 223 | 1,073
Netherlands | 44 | 937 | 1,092 | 621
Czechoslovakia | | | | 2,984
U. S. S. R. | | | | 1,050
All other countries| 918 | 667 | |
+---------+---------+---------+---------
Total | 35,007 | 30,971 | 42,786 | 47,995
+---------+---------+---------+---------
| Value
+---------+---------+---------+---------
Germany |$382,078 |$170,463 |$242,501 |$326,607
Belgium | 48,508 | 2,506 | 57,243 | 90,424
United Kingdom | 124,427 | 123,890 | 135,853 | 78,968
Poland and Danzig | | | | 89,002
Canada | 23,344 | 3,808 | 2,729 | 18,703
Netherlands | 614 | 11,837 | 12,693 | 8,739
Czechoslovakia | | | | 44,371
U. S. S. R. | | | | 12,569
All other countries| 19,747 | 6,074 | |
+---------+---------+---------+---------
Total | 598,718 | 318,578 | 451,019 | 669,383
+---------+---------+---------+---------
| Value per pound
+---------+---------+---------+---------
Germany | $0.017 | $0.010 | $0.012 | $0.015
Belgium | .019 | .010 | .012 | .012
United Kingdom | .015 | .011 | .009 | .011
Poland and Danzig | | | | .015
Canada | .016 | .011 | .012 | .017
Netherlands | .014 | .013 | .012 | .014
Czechoslovakia | | | | .015
U. S. S. R. | | | | .012
All other countries| .022 | .009 | |
+---------+---------+---------+---------
Average | .017 | .010 | .011 | .014
+---------+---------+---------+---------
| Percent of total quantity
+---------+---------+---------+---------
Germany | 62.7 | 56.3 | 48.6 | 46.3
Belgium | 7.2 | .8 | 11.6 | 15.3
United Kingdom | 23.1 | 36.6 | 36.7 | 14.5
Poland and Danzig | | | | 12.0
Canada | 4.3 | 1.1 | .5 | 2.2
Netherlands | .1 | 3.0 | 2.6 | 1.3
Czechoslovakia | | | | 6.2
U. S. S. R. | | | | 2.2
All other countries| 2.6 | 2.2 | |
+---------+---------+---------+---------
Total | 100.0 | 100.0 | 100.0 | 100.0
-------------------+---------+---------+---------+---------

-------------------+---------+---------+----------
Source | 1935 | 1936 | 1937[1]
-------------------+---------+---------+----------
| Quantity in thousands of pounds
-------------------+---------+---------+----------
Germany | 15,742 | 2,712 | 12,129
Belgium | 2,388 | 2,025 | 1,995
United Kingdom | 10,689 | 16,301 | 17,594
Poland and Danzig | 5,075 | 1,969 | 2,312
Canada | 76 | 255 | 734
Netherlands | 1,344 | 3,794 | 3,359
Czechoslovakia | 6,960 | 6,595 | 6,414
U. S. S. R. | 6,158 | 5,145 | 7,091
All other countries| 22 | 1,010 | 1,038
+---------+---------+----------
Total | 48,455 | 39,806 | 52,664
+---------+---------+----------
| Value
+---------+---------+----------
Germany |$230,820 | $75,314 | $287,901
Belgium | 31,375 | 55,503 | 51,227
United Kingdom | 123,545 | 273,964 | 340,760
Poland and Danzig | 63,992 | 35,439 | 55,184
Canada | 1,169 | 4,093 | 7,941
Netherlands | 19,724 | 105,404 | 93,045
Czechoslovakia | 98,099 | 120,529 | 128,197
U. S. S. R. | 74,354 | 97,815 | 146,331
All other countries| 171 | 17,335 | 22,571
+---------+---------+----------
Total | 643,249 | 785,396 |1,133,157
+---------+---------+----------
| Value per pound
+---------+---------+----------
Germany | $0.015 | $0.028 | $0.024
Belgium | .013 | .027 | .026
United Kingdom | .012 | .017 | .019
Poland and Danzig | .013 | .018 | .024
Canada | .015 | .016 | .011
Netherlands | .015 | .028 | .028
Czechoslovakia | .014 | .018 | .020
U. S. S. R. | .012 | .019 | .021
All other countries| .008 | .017 | .022
+---------+---------+----------
Average | .013 | .020 | .022
+---------+---------+----------
| Percent of total quantity
+---------+---------+----------
Germany | 32.5 | 6.8 | 23.0
Belgium | 14.9 | 5.1 | 3.8
United Kingdom | 22.0 | 41.0 | 33.4
Poland and Danzig | 10.5 | 5.0 | 4.4
Canada | .2 | .6 | 1.4
Netherlands | 2.8 | 9.5 | 6.4
Czechoslovakia | 14.4 | 16.6 | 12.2
U. S. S. R. | 12.7 | 12.9 | 13.4
All other countries| | 2.5 | 2.0
+---------+---------+----------
Total | 100.0 | 100.0 | 100.0
-------------------+---------+---------+----------

[1] Preliminary.

Source: Compiled from official statistics of the United States
Department of Commerce.

United States exports.

Exports are not shown separately; it is doubtful if any naphthalene is exported. Demand in the United States has exceeded domestic production.

Competitive conditions.

The commercial development and widespread application of surface coatings and finishes made from alkyd resins, in which phthalic anhydride and glycerin are the principal components, has resulted in a world-wide shortage of naphthalene, which is a raw material used in making phthalic anhydride. In recent years about one-half of domestic requirements of crude naphthalene have been imported (see table 46) from Europe, principally Germany and the United Kingdom. Increased demand for the same purposes, in these countries, has so reduced the quantities available for export as to create a serious shortage in the United States. Germany placed an embargo on exports late in 1935 and continued it until late in 1937.

TABLE 46.—_Crude naphthalene: United States production, imports, and apparent consumption in specified years_

--------+--------------+--------------+--------------+----------------
| | | Apparent |Percent supplied
Year | Production[1]| Imports[2] |consumption[3]| by
| | | | imports
--------+--------------+--------------+--------------+----------------
|_1,000 pounds_|_1,000 pounds_|_1,000 pounds_|
1923 | 53,325 | 20,992 | 74,317 | 28
1927 | 53,601 | 6,577 | 60,178 | 11
1929 | 39,263 | 35,007 | 74,270 | 47
1931 | 20,934 | 30,971 | 51,905 | 60
1932 | 13,593 | 27,002 | 40,595 | 66
1933 | 30,621 | 42,786 | 73,407 | 58
1934 | 37,922 | 47,995 | 85,917 | 56
1935 | 47,653 | 48,455 | 96,108 | 50
1936 | 89,536 | 39,806 | 129,342 | 31
1937[4] | 115,979 | 52,664 | 168,643 | 31
--------+--------------+--------------+--------------+----------------

[1] From table 33.

[2] From table 43.

[3] Production plus imports.

[4] Preliminary.

Vast quantities of naphthalene potentially available in this country were not recovered because of the low prices prevailing until 1936. Since then an increase in the price of crude naphthalene from 1.55 cents to 2.5 cents and 3 cents per pound has stimulated production and has led to additional recovery.

PHTHALIC ANHYDRIDE

Description and uses.

Phthalic anhydride is an aromatic polybasic organic acid anhydride made from naphthalene by vapor phase catalytic oxidation. It is marketed as white needle-shaped crystals or flakes having a melting point of 130° to 131° C. and boiling at 284° to 285° C. It is the cheapest and most widely used aromatic organic acid. Its most important use is in the manufacture of synthetic resins of the alkyd type. Other important uses are in dye intermediates; in phenolphthalein; in benzoic acid; in dyes such as indigo, phloxines, rhodamines, erythrosines; and in esters such as dibutyl phthalate (widely used as a plasticizer in nitrocellulose lacquers and films and of interest as a greaseless lubricant), diethyl phthalate (used as a perfume fixative and denaturant of alcohol), dimethyl phthalate (used as a plasticizer in cellulose acetate films), and diamyl phthalate (used as a plasticizer). Important new processes using phthalic anhydride as a raw material include the syntheses of anthraquinone, substituted anthraquinones, and benzoyl benzoic acid.

Before the World War phthalic anhydride was made by heating naphthalene with sulphuric acid in the presence of mercury; the sulphuric acid acted as an oxidizer, and sulphur dioxide and carbon dioxide were liberated. This process was used in Europe and in the United States to produce the small quantities of phthalic anhydride needed for the manufacture of certain dyes and intermediates. It proved highly unsatisfactory as to operation; the yield varying widely from batch to batch. The sales price of the phthalic anhydride produced at that time was as high as $4.25 per pound, whereas it is 12 to 14 cents per pound today.

In September 1916, Gibbs and Conover, working in the Color Laboratory of the Bureau of Chemistry and Soils, United States Department of Agriculture, developed a process for the synthesis of phthalic anhydride by the direct vapor phase catalytic oxidation of naphthalene. This work was done under the United States Government’s wartime investigation of the manufacture of intermediates and dyes. Gibbs and Conover were granted United States Patent No. 1,285,117 covering the basic process, and the invention was assigned to the people of the United States. This process revolutionized the manufacture of phthalic anhydride, causing the market price to drop to $2.85 per pound in 1918, to 46 cents per pound in 1920, and to 13 cents in 1930. With each decline in price new outlets were found, and domestic production increased practically every year, rising from 227,000 pounds in 1918 to 23,500,000 pounds in 1935.

By a remarkable coincidence the same basic process was developed in Germany, by Alfred Wohl, in the laboratories of the Interessen Gemeinschaft Industrie A. G. (German I. G.), at almost the same time that Gibbs and Conover made their discovery. In 1920 Wohl applied for a United States patent covering this process, claiming invention in the summer of 1916. There was some doubt whether his discovery had been made 2 months earlier or 3 days later than that of Gibbs and Conover, but in July 1934 the United States Court of Customs and Patent Appeals rendered a decision in favor of the German inventor, allowing Wohl’s claim filed with the German patent office on June 28, 1916. Therefore, Wohl’s claim covering the air oxidization process was upheld and he was granted United States Patent No. 1,971,888, issued August 28, 1934 and assigned to the German I. G.

Several domestic firms began commercial production of phthalic anhydride about 1918 under the patent of Gibbs and Conover and have since operated the process continuously. Such manufacturers are presumably protected from possible patent litigation and the payment of royalties under the Wohl patent by section 3 of the so-called Nolan Act of 1921, which states: “No patent granted or validated ... shall affect the right of any citizen of the United States or his successor in business to continue the manufacture, use, or sale commenced before the passage of this Act, nor shall the continued manufacture, use, or sale by such citizen ... constitute an infringement.”

United States production.

Table 47 shows the production and sales of phthalic anhydride from 1917 through 1937.

TABLE 47.—_Phthalic anhydride: United States production and sales, 1917-37_

------+------------+------------------------+-----------
| | Sales |
Year | Production +------------+-----------+ Unit value
| | Quantity | Value |
------+------------+------------+-----------+-----------
| _Pounds_ | _Pounds_ | |
1917 | 138,857 | 138,857 | $587,240 | $4.23
1918 | 227,414 | 227,414 | 648,650 | 2.85
1919 | 290,677 | 290,677 | 290,037 | .99
1920 | 796,210 | 796,210 | 362,431 | .46
1921 | 202,471 | 202,471 | 79,162 | .39
1922 | 1,629,182 | 1,317,625 | 461,944 | .35
1923 | 2,343,802 | 2,091,100 | 596,508 | .29
1924 | 2,787,308 | 2,277,073 | 556,265 | .24
1925 | 3,900,332 | 3,560,429 | 701,840 | .20
1926 | 4,379,108 | 3,446,175 | 604,949 | .18
1927 | 4,549,820 | 4,064,476 | 686,946 | .17
1928 | 6,030,854 | 5,445,432 | 888,156 | .16
1929 | 9,168,946 | 7,450,037 | 1,147,953 | .15
1930 | 6,693,001 | 5,614,012 | 724,909 | .13
1931 | ([1]) | | |
1932 | 6,259,000 | 5,695,000 | 663,000 | .12
1933 | 14,075,844 | 11,593,716 | 1,271,887 | .11
1934 | 20,680,379 | 13,511,253 | 1,575,787 | .12
1935 | 23,421,558 | 17,931,662 | 2,105,134 | .12
1936 | 31,244,378 | 22,905,873 | 2,824,471 | .12
1937 | 45,210,784 | 17,565,905 | 2,492,473 | .14
------+------------+------------+-----------+-----------

[1] Not available.

Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.

There are six domestic makers of phthalic anhydride, with producing units at Bridgeville, Pa., Buffalo, N. Y., Philadelphia, Pa., Deepwater Point, N. J., Saint Louis, Mo., and Detroit, Mich. Five of these firms have been producing in commercial quantities continuously for a number of years and it is therefore believed that these companies may continue to produce without the payment of royalties. New producers using this process, however, might be at a disadvantage unless licensed to operate without the payment of royalties by the owner of the patent.

The production of phthalic anhydride has increased remarkably since the discovery of the vapor phase catalytic process of manufacture. Until 1922 the only large outlet was the coal-tar dye industry. The development of new uses for phthalic esters, principally dibutyl phthalate, increased the demand during the period 1922-28. With the drop in price of phthalic anhydride, resins made from it and glycerin became of commercial interest and about 1929 their production began to increase sharply. Most of the increased output since that year is accounted for by its use in alkyd resins. As previously stated, surface coatings made from these resins are now applied to practically all “indoor” surfaces, both wood and metal, and to “outdoor” use on metal. Largely as a result of the growing popularity of surface coatings of the alkyd type the domestic production of phthalic anhydride exceeded 45 million pounds in 1937 and may reach 50 million pounds in 1938. This estimate is based on the present trend of consumption of alkyd resins and current use therein of phthalic anhydride. Should other polybasic acids be used in greater proportion the estimate would have to be revised. Considerable research work is being done on certain polybasic acids, with very promising results in some instances. Maleic anhydride is being used commercially, as are adipic acid, malic acid, and succinic acid. Other possibilities include such acids as citric, tartaric, sebacic, fumaric, and oxalic.

Production in other countries.

Phthalic anhydride is manufactured in Germany, England, France, Italy, and Japan, but no statistics of foreign production or of international trade are available. The output in Germany is known to be increasing rapidly and is believed to be the principal reason for the German embargo on exports of naphthalene.

In England there are two makers: Imperial Chemical Industries, Ltd., and Monsanto Chemicals, Ltd. The latter is a branch of the American firm of the same name.

In Italy, production was started in 1928 by the A. C. N. A. at Cengio. Capacity is given as 600,000 pounds annually, and the process is essentially the same as in this country.

Japanese production is estimated at 6 million pounds a year. Nihon Seuryo’s plant is the principal one, and the Nishijima mill, at Osaka, the next in importance.

United States foreign trade.

Imports of phthalic anhydride are dutiable under paragraph 27 at 7 cents per pound and 40 percent ad valorem based on American selling price. There were practically no imports since the World War until 1937, when 223,431 pounds were imported from England to relieve a temporary shortage.

Exports, if any, are not shown separately in official statistics.

Competitive conditions.

Phthalic anhydride is the cheapest polybasic organic acid and therefore the most widely used in the production of alkyd resins. The rapid rise in consumption of surface coatings and finishes made from these resins presages greater demand for phthalic anhydride (and glycerin) in the future, particularly if this type of outdoor finish for wood is successful.

The world-wide shortage of naphthalene, with attendant sharp increases in price, raises the question of whether there may not be partial or complete replacement of phthalic anhydride by other polybasic acids in certain types of alkyd resins. The probability of such replacement seems remote unless the use of other polybasic acids, at present much higher priced, so improves the properties of the resins as to give a superior product. Approximately 100 pounds of naphthalene are required to produce 109 pounds of phthalic anhydride. Naphthalene at 3 cents per pound gives phthalic anhydride a raw material cost of 2.75 cents per pound as compared with 1.45 cents per pound when naphthalene was 1.55 cents per pound. In other words, the increase of 1.5 cents per pound in naphthalene, meant an increase of only about 1⅓ cents per pound in the raw material cost of phthalic anhydride, and only approximately ¼ cent per pound in the raw material cost of an alkyd resin surface coating containing about 20-percent phthalic anhydride.

POLYBASIC ACIDS OTHER THAN PHTHALIC ANHYDRIDE

Maleic acid and anhydride.

Maleic anhydride is obtained as a byproduct in the manufacture of phthalic anhydride and as a major product by the vapor phase catalytic oxidation of benzene. Domestic production, still small compared with phthalic anhydride, has increased many fold during the past two or three years. In 1937 there were three producers of maleic anhydride, with an output totaling 2,114,176 pounds. The uses of maleic acid derivatives other than in making resins are minor.

Malic acid and malomalic acid.

Malic acid is widely distributed in the vegetable kingdom, occurring especially in unripe apples. Commercially it is obtained by synthesis. Domestic production was reported for the first time in 1935. Malomalic acid is formed by heating malic acid. United States Patent No. 1,091,627 covers a resin made from malic acid and glycerin which will increase the toughness of phthalate resins. United States Patent No. 1,667,198 suggests the use of malomalic acid to form resins of glass-like appearance.

Adipic acid.

Adipic acid is made by oxidation of cyclohexanol. When condensed with glycerin it yields an alkyd resin which is soft and rubbery and which does not harden when heated. Numerous patents have been granted on the preparation of adipic acid and its resins. Commercial production of adipic acid was first reported in 1935, and the output increased in 1936 and in 1937.

Succinic acid and anhydride.

Succinic acid is a white crystalline powder melting at 185° C. and boiling at 234° C., with decomposition to succinic anhydride. It may be obtained by the reduction of maleic acid. Condensation with glycerin gives a resin tougher and more flexible than is obtained with phthalic anhydride.

In 1937 there were two commercial producers of succinic acid. It is believed that small quantities are used in combination with phthalic anhydride in alkyd resins.

Fumaric acid.

Fumaric acid is a white crystalline powder obtained by the prolonged heating of or by the action of mineral acids on maleic acid. Fumaric acid and maleic acid are structurally identical and the former decomposes at about 280° C., forming the latter. In 1937 there was one domestic maker of fumaric acid.

GLYCERIN

Description and uses.

Glycerin (glycerol) is a clear, colorless or almost colorless, odorless, syrupy, hygroscopic liquid. It is obtained as a byproduct of the soap and fatty acid (oleic acid or red oil and stearic acid) industries. Other sources are insignificant; glycerin can be produced by the fermentation of carbohydrates such as molasses, but when glycerin prices are low this process is not profitable. The chief commercial grades of crude glycerin are “soap lye” glycerin, a byproduct of the soap industry, containing about 80 percent glycerin, and “saponification” grade, a byproduct of the fatty acid industry, containing about 88 percent glycerin. Chemically pure grades contain about 95 percent and dynamite grades about 98.5 percent glycerin. Other grades include “30° yellow distilled” containing about 96 percent glycerin.

The uses of glycerin are extremely varied, the most important being in the manufacture of alkyd resins and ester gums; in the manufacture of nitroglycerin and dynamite; as a moistening, antiseptic, and sweetening agent in tobacco; in pharmaceutical and medicinal preparations; and in certain soft drinks, soaps, and inks.

United States production.

The output of both the crude and the refined has increased in recent years, reaching new highs in 1937. Chemically pure glycerin constitutes about 60 percent of the total refined output and dynamite and other grades about 40 percent. In the production statistics shown in table 48, grades such as yellow distilled are included with the dynamite grade. Since large soap makers refine their own crude glycerin, the sale of crude is only a small part of the total output.

Table 48 shows domestic production of glycerin by grades and table 49 production for sale.

TABLE 48.—_Glycerin: United States production by grades, in specified years, 1919-37_

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Synthetic resins and their raw materialsChapter VI: Part 6

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