statistics and exports of these products as such are probably negligible,
but there are appreciable exports of antiseptics, insecticides, and
disinfectants in which they are incorporated, as well as of products or
parts of products molded of resins made from cresylic acid.
Competitive conditions.
British coal tar is principally of gas-house origin and contains a higher
percentage of tar acids (cresylic acid and phenol) than coke-oven tar,
the principal kind recovered in the United States. The recovery of these
tar acids from either kind of tar is usually not practicable, unless the
distiller can dispose of the major products, creosote oil and pitch.
British distillers have in the past ordinarily had a market for all
their products; exporting large quantities of creosote oil to the United
States, pitch to continental Europe, and tar acids and naphthalene to
the United States, Germany, and other countries. Domestic distillers
have sold cresylic acid, creosote oil, naphthalene, etc., in local
markets in competition with duty-free imports from the United Kingdom,
the Netherlands, Belgium, and Germany, but have found it difficult to
dispose of pitch. The domestic production of coal tar ordinarily exceeded
600 million gallons, approximately one-half of which has been burned as
fuel. Since the profit in distilling depends upon the markets for all
of the joint products of the distillation, the large amount remaining
undistilled can be understood.
The domestic production of cresylic acid may be expected to increase
substantially, for several reasons: (1) The principal foreign producing
countries have decreased exports because of increased demand for some of
the coal-tar distillation products at home; (2) increased world prices;
and (3) the development of topping, which allows the production of tar
acids and naphthalene from coal tar without complete distillation.
Imports of refined cresylic acid are unimportant because the duty on the
refined is high relative to the duty-free condition of the crude. Most of
the imports of refined are either reexported or used in the manufacture
of one proprietary antiseptic. The principal domestic market for cresylic
acid is as a raw material for synthetic resins, and most of the domestic
refined and most of the duty-free imported crude is now consumed by
this industry. It may therefore be said that practically all imports of
cresylic acid are duty-free and that, while they are sometimes refined by
the consumer, they compete directly with domestic production of refined
grades.
Phenol, already discussed, is closely related to cresylic acid—in
chemical composition, in production by distillation from coal tar, and
in use as a raw material for synthetic resins. To a considerable extent
the proportions of phenol and cresylic acid used in the manufacture of
tar-acid resins can be altered to take advantage of the changing price
differential between the two.
All of the separated or mixed cresols are produced in commercial
quantities in this country. Consumption in the United States, especially
of types and grades used in synthetic resins, has increased appreciably
in recent years, and is supplied chiefly by domestic production. A
comparison of the quantity and value of domestic production and of
imports in 1934 is shown in table 83.
TABLE 83.—_The cresols: Comparison of production and imports, 1934_
---------------+------------------------------+--------------------------
| Production | Imports
Product +----------+--------+----------+--------+------+----------
| Quantity | Value |Unit value|Quantity| Value|Unit value
---------------+----------+--------+----------+--------+------+----------
| _Pounds_ | | |_Pounds_| |
Metacresol | ([1]) | ([1]) | | 21,054|$8,400| $0.399
Paracresol | ([2]) | ([2]) | $0.350| 38,935|10,344| .266
Metaparacresol | 2,033,424|$122,005| .060| ([1]) | ([1])|
Orthocresol | 835,016| 66,801| .080| 25,865| 2,711| .105
Orthometapara | | | | | |
cresol | 8,929,836| 625,088| .070| 38,744|12,906| .333
+----------+--------+----------+--------+------+----------
Total |11,798,276| 813,894| | 124,598|34,361|
---------------+----------+--------+----------+--------+------+----------
[1] None, production reported for first time in 1935.
[2] Not publishable.
Sources: Production, Dyes and Other Synthetic Organic Chemicals
in the United States; imports, invoice analyses, U. S. Tariff
Commission.
SYNTHETIC TAR ACIDS OTHER THAN PHENOL
Certain synthetic tar acids other than synthetic phenol are used
commercially in the manufacture of synthetic resins in the United States.
Among these are para tertiary amyl phenol, para tertiary butyl phenol,
ortho phenyl phenol, para phenyl phenol, and resorcinal.
Para tertiary amyl phenol.
Para tertiary amyl phenol is made by reacting amylene with phenol in
the presence of sulphuric acid as a catalyst. At ordinary temperatures
it is a solid, melting at about 88° C. and boiling between 250°-265° C.
Its use is of increasing importance as a component in tar-acid resins,
especially in oil-soluble varnish resins. Owing to its phenol coefficient
of approximately 60, it is also used as a germicide, fumigant, and
insecticide. Commercial production was reported for the first time
in 1933. Since then the output has increased appreciably each year,
accompanied by material reductions in sales prices.
According to United States Patent No. 1,800,295, dated April 14, 1931, a
resin fast to light and soluble in oils is obtained by heating 82 parts
of p-tertiary amyl phenol with 90 parts of formaldehyde, in the presence
of sodium hydroxide. This substituted phenol resin passes slowly into the
infusible state, thus permitting better control of the reaction.
Para tertiary butyl phenol.
Para tertiary butyl phenol is a white solid with an aromatic odor,
melting at approximately 100° C. It is a new commercial product and is
used in resins for paints and varnishes. It is the most important resin
material in this group.
Phenyl phenols.
Both ortho and para phenyl phenol are commercially produced and are used
to some extent in resins to replace phenol. The ortho isomer is a white
solid boiling at 284° C. and melting at about 56° C. It is used chiefly
as a germicide, though small quantities are used in resins.
Para phenyl phenol is a white solid melting at about 165° C. and boiling
at 322° C. Commercial production was reported for the first time in
1933. The output has increased each year since and the selling price has
gradually declined.
Resorcinol.
Resorcinol, usually obtained by fusing meta benzene disulphonic acid with
caustic soda, is a colorless, crystalline substance with a peculiar odor.
It melts at 119° C. and boils at 276° C. It is used in medicine, in the
manufacture of intermediates and dyes, and to some extent in synthetic
resins. Resorcinol condenses with formaldehyde at such a rapid rate
that some means must be applied to slow up the reaction. It is used to
increase the rate of condensation of tar-acid resins and to reduce the
danger of sticking or undercure.
Domestic production of resorcinol has decreased in recent years. Its
relatively high cost is probably an important factor in limiting its use
in synthetic resins.
FORMALDEHYDE
Description and uses.
At ordinary temperature and pressure formaldehyde is a gas. It enters
commerce as formalin, an aqueous solution containing 40 percent
formaldehyde by volume (37 percent by weight) and from 6 to 14 percent
methyl alcohol. It is generally made by the oxidation of methyl alcohol.
Commercial formalin contains polymers which tend to precipitate in water
solution; these are kept in solution by allowing from 6 to 14 percent
methyl alcohol to remain in the solution.
The principal use of formaldehyde is in the manufacture of synthetic
resins. Other uses are (in the order of their importance): In the
manufacture of synthetic indigo; in the manufacture of hydrosulphite; as
a disinfectant, deodorant, and preservative; as a fungicide; in embalming
fluids; in tanning leather; and in the manufacture of coated paper and
wallpaper.
United States production.
The domestic output of formaldehyde has increased with the increased
demand by resin makers. Production and sales in 1937 were more than
double those in 1930. There are three domestic makers, two of which
produce methyl alcohol, the raw material. Their plants are located in New
Jersey and Oklahoma.
Statistics of production and sales are shown in table 84.
TABLE 84.—_Formaldehyde: United States production and sales, in specified
years_
-------+----------+----------------------------
|Production| Sales
Year +----------+--------+----------+--------
| Quantity |Quantity| Value | Value
| | | |per lb.
-------+----------+--------+----------+--------
| _1,000 |_1,000 | |
| pounds_ |pounds_ | |
1914 | ([1]) | 8,426| $655,174| $0.078
1919 | 25,007| 19,664| 3,928,322| .200
1921 | 9,657| 6,056| 651,681| .108
1922 | 23,958| 16,140| 1,676,401| .104
1923 | 24,081| 18,855| 2,474,506| .131
1924 | 26,155| 20,542| 1,971,053| .096
1925 | 31,456| 23,392| 1,895,913| .081
1926 | 31,953| 22,552| 2,050,967| .091
1927 | 29,920| 24,597| 2,256,534| .092
1928 | 38,718| 27,934| 2,491,615| .089
1929 | 51,786| ([2]) | ([2]) |
1930 | 40,763| ([2]) | ([2]) |
1931 | ([1]) | ([1]) | ([1]) |
1932 | ([1]) | ([1]) | ([1]) |
1933 | 52,236| 46,424| 2,122,925| .046
1934-37| ([2]) | ([2]) | ([2]) |
-------+----------+--------+----------+--------
[1] Not available.
[2] Not publishable; figures would disclose operations of
individual firms.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Production in other countries.
Formaldehyde is produced in England, Germany, France, Czechoslovakia,
Italy, Sweden, the Soviet Union, Japan, and Canada. Production data are
not available but Germany and England are probably the leading foreign
producers. Estimated productive capacity in the Soviet Union is given
as 10 million pounds annually; in Japan 6.5 million pounds; in France 4
million pounds; and in Italy 3 million pounds.
United States imports and exports.
Imports of formaldehyde have been negligible since 1920 when 428,444
pounds, valued at $210,191, were imported. There were no imports from
1928 until 1935, when 375 pounds valued at $72 were imported from Canada.
In 1936 imports amounted to 20 pounds, valued at $14, from Switzerland.
The United States exports about 5 percent of its production of
formaldehyde. Canada is the principal destination of exports, and
prior to 1934 Japan was an important market. Table 85 shows exports of
formaldehyde to principal markets, in recent years.
TABLE 85.—_Formaldehyde: United States exports to principal markets, in
specified years, 1929-37_
-------------------+---------+---------+---------+---------
Exported to— | 1929 | 1931 | 1933 | 1934
-------------------+---------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------+---------
Canada | 19,321| 716,132|1,095,847|1,236,103
Japan |1,464,763| 622,407| 729,875| 11,250
Netherlands Indies | 626,689| 650,875| | 344,725
United Kingdom | 303| 345,896| 305|
China | 29,030| 229,760| 215,050| 572,700
All other countries| 448,063| 339,777| 332,101| 433,068
+---------+---------+---------+---------
Total |2,588,169|2,904,847|2,373,178|2,597,846
+---------+---------+---------+---------
| Value
+---------+---------+---------+---------
Canada | $4,405| $36,471| $46,611| $58,348
Japan | 124,411| 33,395| 43,254| 562
Netherlands Indies | 42,807| 38,462| | 15,536
United Kingdom | 510| 18,629| 192|
China | 3,354| 13,019| 11,998| 27,407
All other countries| 49,742| 22,709| 18,966| 23,444
+---------+---------+---------+---------
Total | 225,229| 162,685| 121,021| 125,297
+---------+---------+---------+---------
| Unit value
+---------+---------+---------+---------
Canada | $0.228| $0.051| $0.043| $0.047
Japan | .085| .054| .059| .050
Netherlands Indies | .068| .059| | .045
United Kingdom | 1.683| .054| .630|
China | .116| .057| .056| .048
All other countries| .111| .067| .057| .054
+---------+---------+---------+---------
Average | .087| .056| .051| .048
+---------+---------+---------+---------
| Percent of total quantity
+---------+---------+---------+---------
Canada | 0.8| 24.7| 46.2| 47.6
Japan | 56.6| 21.4| 30.7| .4
Netherlands Indies | 24.2| 22.4| | 13.3
United Kingdom | | 11.9| |
China | 1.1| 7.9| 9.1| 22.0
All other countries| 17.3| 11.7| 14.0| 16.7
+---------+---------+---------+---------
Total | 100.0| 100.0| 100.0| 100.0
-------------------+---------+---------+---------+---------
-------------------+---------+---------+---------
Exported to— | 1935 | 1936 | 1937[1]
-------------------+---------+---------+---------
| Quantity (pounds)
+---------+---------+---------
Canada |1,493,993|1,105,277|1,187,661
Japan | | |
Netherlands Indies | 71,375| 200| 335,275
United Kingdom | | 2|
China | 598,342| 459,490| 938,700
All other countries| 334,100| 279,289| 403,236
+---------+---------+---------
Total |2,497,810|1,844,258|2,864,872
+---------+---------+---------
| Value
+---------+---------+---------
Canada | $83,805| $53,062| $50,780
Japan | | |
Netherlands Indies | 2,866| 13| 13,411
United Kingdom | | 1|
China | 28,239| 19,258| 34,274
All other countries| 18,676| 16,520| 20,498
+---------+---------+---------
Total | 133,586| 88,854| 118,963
+---------+---------+---------
| Unit value
+---------+---------+---------
Canada | $0.056| $0.048| $0.043
Japan | | |
Netherlands Indies | .040| .065| .040
United Kingdom | | .500|
China | .047| .042| .037
All other countries| .056| .059| .051
+---------+---------+---------
Average | .053| .048| .042
+---------+---------+---------
| Percent of total quantity
+---------+---------+---------
Canada | 59.8| 59.9| 41.4
Japan | | |
Netherlands Indies | 2.8| | 11.7
United Kingdom | | |
China | 24.0| 24.9| 32.8
All other countries| 13.4| 15.2| 14.1
+---------+---------+---------
Total | 100.0| 100.0| 100.0
-------------------+---------+---------+---------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
The competitive situation with respect to formaldehyde is determined
largely by the output and price of the raw material, methanol. The United
States produces large quantities of synthetic and natural methanol and
is a net exporter of that product. Both methanol and formaldehyde are
produced in many foreign countries, and foreign production is expanding.
Although methanol is now the main, if not the sole, raw material utilized
in making formaldehyde, plants for making the latter direct from natural
gas, or from petroleum gas hydrocarbons are contemplated or actually
under construction. Should such processes develop to an appreciable
extent, the competitive situation of the United States may change, but
in such case it is unlikely that this country would be so affected as to
change its position as a moderate exporter.
HEXAMETHYLENETETRAMINE
Description and uses.
Hexamethylenetetramine is a white crystalline powder made by the
interaction of formaldehyde and ammonia. It is used in tar-acid resins
to replace formaldehyde, though its higher cost has limited its use to
small proportions as a finishing or hardening agent. Other uses are as
an internal antiseptic in medicine (marketed under trade names such as
Urotropin, Cystogen, Aminoform, Urisol, and Cystamin), as an accelerator
in the vulcanization of rubber (a declining use), and in artificial
cork. During the World War it was used in gas masks as an absorbent for
phosgene.
United States production.
The domestic production of hexamethylenetetramine declined during the
depression, but has been increasing in the last few years. Production in
1937, however, was still below that of 1929. Statistics of production are
shown in table 86.
TABLE 86.—_Hexamethylenetetramine: United States production and sales,
1923, and 1925-37_
-------+----------+-----------------------------
|Production| Sales
Year |(quantity)+---------+--------+----------
| | Quantity| Value |Unit value
-------+----------+---------+--------+----------
| _Pounds_ | _Pounds_| |
1923 | 1,381,073|1,155,083|$974,877| $0.84
1925 | 1,657,993|1,506,286| 994,458| .66
1926 | 1,495,220| ([1]) | ([1]) |
1927 | 1,315,213| ([1]) | ([1]) |
1928 | 1,661,645| ([1]) | ([1]) |
1929 | 2,368,020| ([1]) | ([1]) |
1930 | 1,871,690| ([1]) | ([1]) |
1931 | ([2]) | | ([2]) |
1932 | ([2]) | | ([2]) |
1933-37| ([1]) | | ([1]) |
-------+----------+---------+--------+----------
[1] Not publishable; figures would disclose operations of
individual firms.
[2] Not available.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Hexamethylenetetramine is made by two firms in New Jersey and by one in
West Virginia. The raw materials utilized are formaldehyde and liquid
or anhydrous ammonia. One company makes its own requirements of both,
and another makes its own formaldehyde. Most of the production of
hexamethylenetetramine is sold, marketed in barrels, drums, kegs, and
cans.
Production in other countries.
Hexamethylenetetramine is made in a number of foreign countries, with
Germany probably the leading foreign producer. Exports from Germany
declined from 445,000 pounds in 1931 to 182,000 pounds in 1934, the
decline being due chiefly to the expansion of production in countries
previously large importers, particularly the United Kingdom, Japan,
Czechoslovakia, and France.
United States imports and exports.
Imports of hexamethylenetetramine to the United States are shown in table
87.
TABLE 87.—_Hexamethylenetetramine: United States imports for consumption,
1923-37_
-----------------+--------------+--------+-------+----------+----------
| | | | | Computed
Calendar year | Rate of duty |Quantity| Value |Unit value|ad valorem
| | | | | rate
-----------------+--------------+--------+-------+----------+----------
| |_Pounds_| | | _Percent_
1923 |25 percent | 47,373|$24,722| $0.522|
1924 | do | 3,826| 3,998| 1.045|
1925 | do | 20,771| 10,453| .503|
1926 | do | 23,481| 10,237| .436|
1927 | do | 3,417| 1,715| .502|
1928 | do | 5,898| 1,643| .279|
1929 | do | 5,562| 1,857| .334|
1930: | | | | |
Jan. 1-June 17 | do | | | |
June 18-Dec. 31| 11 cents | | | |
| per pound | | | |
1931 | do | | | |
1932 | do | 1,103| 336| .305| 36.1
1933 | do | 1,103| 293| .266| 41.4
1934 | do | 612| 273| .446| 24.7
1935 | do | | | |
1936 | do | 7,496| 1,510| .201| 54.6
1937[1] | do | 10,895| 8,197| .200| 54.9
-----------------+--------------+--------+-------+----------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Imports of hexamethylenetetramine in 1928 came principally from the
United Kingdom, the remainder from Germany. In 1929 they came wholly from
Germany; in 1932 and 1933 from Belgium; and in 1934 principally from
Canada, with the rest from the United Kingdom. In 1936 Belgium supplied
7,166 pounds valued at $1,368 and Germany 330 pounds valued at $142.
Exports of hexamethylenetetramine are not shown in official statistics.
It is known, however, that some has been exported, and that in 1933, at
least, exports exceeded imports.
Competitive conditions.
Hexamethylenetetramine is made from formaldehyde and ammonia, of
which there are ample supplies in the United States. The market for
hexamethylenetetramine is limited, and imports are small. It is made
in numerous foreign countries, Germany being probably the principal
potential competitor.
FURFURAL
Furfural is an aldehyde found in oat hulls, rice hulls, corn cobs, bran,
and other farm waste products. Commercially it is obtained in the United
States from oat hulls and in the Soviet Union from the husks of sunflower
seeds. It is a colorless liquid, boiling at 158° to 162° C. and freezing
at minus 38° C. Its principal use is in synthetic resins, of which tar
acid-furfural is probably the most important. These resins are used in
molding, for impregnating, and in coatings. Furfural is also used as a
solvent for cellulose ethers and esters, natural gums and resins, and in
the manufacture of derivatives useful as rubber chemicals.
Domestic production is entirely by one firm, located in Iowa. Production
and sales statistics are not publishable, but the maker has stated that
consumption is in “terms of millions of pounds per year.”
18. RAW MATERIALS FOR UREA RESINS
The principal raw materials entering into the manufacture of urea resins
are urea and formaldehyde. Formaldehyde has already been discussed (see
pp. 133-135) and urea and thiourea are discussed below.
UREA
Urea is a white crystalline material, made by condensing carbon dioxide
and ammonia under heat and pressure. It is an excellent fertilizer
because of its high nitrogen content (46.6 percent) but this use is
limited by its relatively high cost. Urea is an important synthetic
resin material, being a constituent of urea-formaldehyde resins, known
commercially under the trade names Beetleware and Plaskon.
Production of urea in the United States was started in 1916, when the
German supply was cut off. In 1920 the domestic output was estimated at
more than 200,000 pounds of fertilizer grade. Production ceased in 1922.
Urea in ammonia solution for use in the manufacture of mixed fertilizer
was first produced in 1933.
Crystal urea production in the United States was begun in 1935 and was
largely made possible by the larger volume of urea in ammonia solution
manufactured for fertilizer use. Prior to that time our requirements of
crystal urea were imported, principally from Germany. Consumers of resin
grade urea report that the domestic product is as good or better than the
imported from Europe. The domestic output of crystal urea in 1936 showed
an appreciable increase over that in 1935.
Statistics of imports of urea are given in table 88, showing imports of
all grades combined. Up to 1931, and again in 1936, the imports were
probably all for fertilizer use. From 1931 through 1935 some portion of
the imports went into the manufacture of resins, but even in this period
most of the imports were probably used in fertilizer.
TABLE 88.—_Urea: United States imports for consumption, 1919-20 and
1923-37_
-------------------+------------+----------+-------+----------
Year |Rate of duty| Quantity | Value |Unit value
-------------------+------------+----------+-------+----------
| | _Pounds_ | |
1919 |25 percent | 14,290| $9,741| $0.682
1920 | do | 23,693| 14,085| .594
1923 |35 percent | 45,711| 5,892| .129
1924 | do | 94,307| 12,891| .137
1925 | do | 146,438| 15,886| .108
1926 | do | 377,729| 30,346| .080
1927 | do | 813,120| 51,799| .064
1928 | do | 1,788,927|101,900| .057
1929 | do | 4,588,313|228,401| .050
1930: | | | |
Jan. 1-June 17 | do | 2,459,140|120,263| .049
June 18-Dec. 31|Free |17,843,840|719,982| .040
1931 | do |11,695,040|445,674| .038
1932 | do | 7,291,200|267,787| .037
1933 | do |12,918,080|483,238| .037
1934 | do |10,850,560|423,675| .039
1935 | do | 8,189,440|379,427| .046
1936 | do | 6,095,040|272,679| .045
1937[1] | do | 5,297,600|266,166| .050
-------------------+------------+----------+-------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 89 shows the sources of imports of urea in recent years. Germany
has supplied from 90 to 100 percent of the total quantity, and Canada
and the Netherlands the greater part of the remainder. There have been
occasional shipments from Belgium, France, and Japan.