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.