-------+---------+-----------+----------_Synthetic resins and their raw materials A survey of the types and uses of synthetic resins, the organization of the industry, and the trade in resins and raw materials, with particular references to factors essential to tariff consideration. Under the general provisions of section 332, title III, part II, Tariff act of 1930.

Year | Quantity| Value |Unit value

-------+---------+-----------+----------

| | |_Cents per_

|_Pounds_ | | _pound_

1919 |3,963,392| $1,190,984| 30.0

1920 |1,742,708| 429,116| 24.6

1923 |1,767,407| 318,765| 18.0

1924 |1,415,882| 237,639| 16.8

1925 |1,367,191| 282,078| 20.6

1926 | 767,698| 192,220| 25.0

1927 | 693,144| 143,700| 20.7

1928 |2,051,937| 259,100| 12.6

1929 |1,373,605| 197,986| 14.4

1930 | 607,690| 102,892| 16.9

1931 | 328,143| 48,095| 14.7

1932 | 260,339| 28,609| 11.0

1933 | ([1]) | ([1]) |

1934 | ([1]) | ([1]) |

1935 |3,353,625| 450,248| 13.4

1936 |1,146,026| 182,592| 15.9

1937[2]|1,375,036| 338,148| 24.6

-------+---------+-----------+----------

[1] Not reported separately.

[2] Preliminary.

Source: Foreign Commerce and Navigation of the United States.

Competitive conditions.

Glycerin occurs in chemical combination in animal and vegetable oils

and fats. Since it is obtained as a byproduct, the output is dependent

primarily upon the output of the major products, soaps and fatty acids,

and its production is largely independent of demand. At low prices,

however, less glycerin is recovered.

The United States usually consumes more glycerin than it produces (see

table 55), whereas leading European producing nations produce more than

they consume. In recent years the domestic production has apparently been

approaching domestic requirements. A factor tending to decrease demand

is the increasing resort to substitutes in various uses, particularly

ethylene glycol, ethyl alcohol, and methyl alcohol. On the other hand,

the demand in the resin industry is expanding rapidly.

TABLE 55.—_Refined glycerin: United States production, imports, exports,

and apparent consumption, in specified years_

-------+-------------+----------+----------+--------------

Year |Production[1]|Imports[2]|Exports[3]| Apparent

| | | |consumption[4]

-------+-------------+----------+----------+--------------

| _Pounds_ | _Pounds_ | _Pounds_ | _Pounds_

1927 | 108,392| 8,289| 693| 115,987

1929 | 125,772| 5,358| 1,374| 129,757

1931 | 113,894| 1,966| 328| 115,531

1932 | 105,163| 2,348| 260| 107,250

1933 | 104,120| 2,776| ([5]) | 106,895

1934 | 128,912| 2,214| ([5]) | 131,126

1935 | 123,390| 69| 3,354| 120,105

1936 | 132,922| 3,447| 1,146| 135,223

1937[6]| ([5]) | 7,535| 1,375| ([5])

-------+-------------+----------+----------+--------------

[1] From table 48 (refined basis).

[2] From table 51 (refined).

[3] From table 54 (grade not specified, but chiefly refined).

[4] Production plus imports minus exports.

[5] Not available.

[6] Preliminary.

Up to 1924 (except 1920) imports consisted principally of crude glycerin,

much of which was refined in the United States and included in United

States production; thereafter imports of refined glycerin became

important relative to the crude. Exports are insignificant compared to

either production or imports.

17. RAW MATERIALS FOR TAR-ACID RESINS

The first tar-acid resins were made from phenol and formaldehyde. As a

result this group of resins is frequently spoken of as phenolic resins.

This is true despite the fact that coal-tar acids other than phenol,

particularly the cresols and xylenols, are used in large volume today.

THE TAR ACIDS

The term coal-tar acids is applied to certain organic compounds either

obtained from or known to be present in coal tar. Probably the best known

is phenol or carbolic acid, produced in large quantities in the United

States and abroad. Others of commercial importance are ortho, meta,

and para cresol and the xylenols. All of these are definite chemical

compounds available as such or in mixture with other tar acids. Cresylic

acid is a term widely used in commerce for almost any mixture of tar

acids. Formerly it was used to designate a mixture of ortho, meta, and

para cresols in the proportions in which they are found in coal tar. The

higher boiling tar acids (listed in table 56 below the xylenols) have

little or no commercial importance at this time.

Table 56 lists the tar acids by commercial name, chemical name, boiling

point of the pure compound, and average percentage present in coal

tar. Boiling point is shown because the several tariff classifications

covering tar acids under the acts of 1922 and 1930 (pars. 27 and 1651)

depend upon distillation range (boiling points) for classification and

assessment of duty (see pp. 119 and 124).

TABLE 56.—_Tar acids: Commercial and chemical names, boiling points and

average percentage present in coal tar_

--------------------+-----------------------+---------+----------

| | | Average

Commercial name | Chemical name | Boiling |percent in

| |point ° C| coal tar

--------------------+-----------------------+---------+----------

Phenol |Phenol | 181.5| 0.7

Orthocresol |2-methyl phenol | 190.8| .4

Metacresol |3-methyl phenol | 202.8| .4

Paracresol |4-methyl phenol | 201.8| .3

2-3 Xylenol |2-3-dimethyl phenol | 218.0| ⎫

2-4 Xylenol |2-4-dimethyl phenol | 211.5| ⎪

2-5 Xylenol |2-5-dimethyl phenol | 211.5| ⎬ .2

2-6 Xylenol |2-6-dimethyl phenol | 212.0| ⎪

3-4 Xylenol |3-4-dimethyl phenol | 225.0| ⎪

3-5 Xylenol |3-5-dimethyl phenol | 220.0| ⎭

Ortho ethylphenol |2-ethyl phenol | 206.5| ⎫

Meta ethylphenol |3-ethyl phenol | 217.0| ⎪

Para ethylphenol |4-ethyl phenol | 218.5| ⎪

s-methyl ethylphenol|3-methyl-5-ethyl phenol| 232.5| ⎬ .5

Iso pseudocumenol |2-3-5-trimethyl phenol | 233.0| ⎪

Mesitol |2-4-6-trimethyl phenol | 219.5| ⎪

Pseudocumenol |2-4-5-trimethyl phenol | 234.0| ⎭

--------------------+-----------------------+---------+----------

Source: Ellis, Chemistry of Synthetic Resins.

Since the quantities of tar acids present in coal tar are small (see

table 56), it is usually uneconomical to distill coal tar completely

unless the creosote oil and pitch can be marketed profitably. Beginning

in 1936, production of tar acids in the United States was increased by

the practice of topping. Topping is the recovery in tar distillation of

the light fractions only, leaving a residual thin enough to flow through

the pipe lines to supply fuel to open hearth and other type furnaces.

These light fractions contain the naphthalene and tar acids. The practice

permits recovery of these products from tar to be used as fuel, thus

providing a new alternative intermediate between the two older practices

of either complete distillation or using the undistilled tar as fuel.

In the United States, consumption of most of the tar acids greatly

exceeds the quantities extracted from tar, necessitating large production

of synthetic phenol and importation of large quantities of the cresols

and xylenols. The calculated amount of these tar acids present in the tar

produced in this country vastly exceeds present day requirements. Table

57 shows the approximate amounts of the several tar acids contained in

the coal tar produced and distilled in 1936. These estimates are based on

a 1936 production of coal tar of 560,385,578 gallons and a distillation

of 292,140,249 gallons. The calculation is made by using the percentage

of tar acids in tar shown in table 56 and converting the gallons to

pounds in accordance with the specific weights of the pure tar acids.

Actual production of all tar acids in the United States in 1936 was about

29 million pounds.

TABLE 57.—_Tar acids available in coal tar produced and distilled in 1936_

-----------+--------------+--------------

| Available in | Available in

Tar acid | tar produced | tar distilled

| in 1936[1] | in 1936[2]

-----------+--------------+--------------

|_1,000 pounds_|_1,000 pounds_

Phenol | 34,912 | 18,200

Orthocresol| 19,277 | 10,050

Metacresol | 19,277 | 10,050

Paracresol | 14,290 | 7,450

Xylenols | 10,200 | 5,316

Others | 25,200 | 13,290

-----------+--------------+--------------

[1] 560,385,578 gallons.

[2] 292,140,249 gallons.

The several tar acids are discussed in detail under the following heads:

(_a_) Phenol.

(_b_) The cresols, xylenols, and cresylic acid.

(_c_) Synthetic tar acids other than phenol.

PHENOL

Description and uses.

Phenol (commonly called carbolic acid) is a tar acid obtained from two

sources: (_a_) From one of the fractions recovered in the distillation

of coal tar, a byproduct resulting from the manufacture of coke in

byproduct ovens, and from the manufacture of coal gas; (_b_) from

benzol, by synthesis. The second source has been the more important

since 1923. Phenol, when pure, is a colorless substance of interlaced

or separate needle-shaped crystals with a characteristic aromatic odor.

It is corrosive to the skin and to mucous membrane. When pure it is

water white, melts at about 42° C., and boils at about 181.5° C. It was

discovered in 1834 by Runge.

Phenol is used today chiefly as a component of tar-acid resins. It is

also widely used as an antiseptic and disinfectant, in the manufacture of

explosives (picric acid and ammonium picrate), and as an intermediate for

certain dyes and medicinals. Salicylic acid and its derivatives—aspirin,

salol, and methyl salicylate (artificial oil of wintergreen)—are

important medicinals made from phenol. Another use is in the extraction

of lubricating oils. The relative importance of these various uses in

recent years is indicated by table 58, which gives the estimated domestic

consumption of phenol by uses in 1936-37.

TABLE 58.—_Phenol: Estimated consumption by industries, 1936-37_

------------------------------+-----------------

Use |Percent of

|total consumption

------------------------------+-----------------

Synthetic resins | 60-65

Extraction of lubricating oil | 5

Insecticides and disinfectants| 10

Dyes and intermediates | 5

Other | 15-20

------------------------------+-----------------

United States production.

Prior to 1914 United States production of phenol averaged about a

million pounds a year and was entirely the natural product obtained from

distillates of coal tar. Increased demand during the World War was met

by several synthetic phenol processes, which utilized in part the vast

quantities of benzol available. Our output of phenol reached 64 million

pounds in 1917 and 107 million pounds in 1918. When the armistice was

signed stocks on hand in the United States totaled between 35 million and

40 million pounds, estimated at three times the annual consumption at

that time for nonmilitary purposes. As a result the price dropped from

about 45 cents to 6 cents a pound, and the synthetic plants were closed.

The limited quantities of phenol available to synthetic resin makers

prior to and during the World War caused much concern to that industry

and led to research work for substitutes, work resulting in the

development of many new and modified types of resins in which tar acids

other than phenol were used. But notwithstanding the use of these

other tar acids the increased demand for synthetic resins used up the

accumulated stocks of phenol sooner than was expected.

Of the phenol produced in the United States from 1919 through 1923 a

large part was natural phenol but the rapid increase in demand and the

improvement of processes for synthetic phenol had by 1923 resulted

in four companies beginning production of the synthetic article. The

rapid increase in output, from about 3 million pounds in 1923 to about

15 million pounds in 1925, was almost entirely in synthetic phenol.

Since then a large part of the domestic production has continued to be

synthetic, although the production of natural phenol since 1935 has been

about four times that of 1929.

Adequate quantities of coal tar are usually available to produce

sufficient natural phenol to meet a substantial part of our requirements,

if it were all recovered, but the quantity actually produced is

determined in part by the demand for other coal-tar products, and in part

by the value of the tar as fuel. More than 50 percent of the tar produced

has been burned as fuel, principally at the coke ovens or nearby steel

mills.

The domestic production and sales of phenol, natural and synthetic

combined, are shown in table 59.

TABLE 59.—_Phenol: United States production and sales, in specified

years, 1918-37_

-----------+----------+--------------------------------+---------------

|Production| Sales |

| | | Ratio of sales

Census year+----------+----------+----------+----------+ to total

-----------+----------+----------+----------+----------+---------------

| _1,000 | _1,000 | _1,000 | | _Percent_

1918 | 106,794 | 106,794 | 37,270 | $0.35 |

1919 | 1,544 | 1,544 | 156 | .10 |

1923 | 3,311 | 2,180 | 590 | .27 | 66

1925 | 14,734 | 8,524 | 1,771 | .21 | 58

1926 | 8,691 | 5,480 | 988 | .18 | 63

1927 | 8,041 | 4,595 | 684 | .15 | 57

1928 | 10,227 | 7,746 | 912 | .12 | 76

1929 | 24,178 | 19,939 | 2,248 | .11 | 83

1930 | 21,147 | 17,715 | 1,976 | .11 | 84

1931 | 17,981 | 14,002 | 1,446 | .10 | 78

1932 | 13,965 | 12,181 | 1,269 | .10 | 87

1933 | 33,220 | 27,923 | 2,881 | .10 | 84

1934 | 44,935 | 36,241 | 3,887 | .11 | 81

1935 | 43,419 | 34,575 | 3,431 | .10 | 80

1936 | 48,724 | 40,942 | 4,235 | .10 | 84

1937 | 65,690 | 57,176 | 6,153 | .11 | 87

-----------+----------+----------+----------+----------+---------------

Source: Compiled from annual reports of the Tariff Commission on

dyes and other synthetic organic chemicals in the United States.

_Grades produced for resins._—Increased production of phenol in recent

years is largely due to the demand from makers of synthetic resins. A

number of grades are regularly produced for this purpose, though it is

believed that the technical grade is the principal one used in resins.

The several grades are as follows:

(1) USP.—Either natural or synthetic. This grade contains not less than

98 percent phenol.

(2) Technical.—Various grades containing from 80 to 95 percent phenol, of

which the two most important are 82-84 percent and 90-92 percent.

(3) Mixtures.—Containing from 30 percent to 80 percent phenol and the

remainder of the isomeric cresols.

_Producers._—Natural phenol is obtained in the distillation of coal tar

and to a smaller extent in the purification of ammonia liquors in coke

and gas plants. In 1937 there were four producers of natural phenol with

plants located at Philadelphia, Pa., Follansbee, W. Va., Indianapolis,

Ind., and Pittsburgh, Pa. All these are tar distillers recovering

creosote oil, pitch, cresylic acid, naphthalene, and other crudes from

coal tar.

Synthetic phenol is made from benzene, either by sulfonation followed

by alkaline fusion, or by chlorination and subsequent heating under

pressure with caustic soda. It is produced in large quantities by two

firms, one at Midland, Mich., and the other at St. Louis, Mo. A third

producer is building a plant at North Tonawanda, N. Y., using a process

recently developed in Germany. Operation of this unit will probably start

late in 1938.

World production.

Natural phenol is recovered in practically all European countries and

in Japan. Germany and the United Kingdom are the principal producers

and have also been the leading exporters. Synthetic phenol was made in

Germany as early as 1900, and during the World War. Plants for synthetic

phenol recently installed are now in operation in Germany, Great Britain,

Belgium, and Italy.

Table 60 shows the average annual world production of phenol in recent

years by countries. Half of the total was produced in the United States.

TABLE 60.—_Phenol: Estimated average annual production, by countries,

1933-35_

--------------+-----------------

| Estimated

Produced in— |annual production

--------------+-----------------

| _1,000 pounds_

UNITED STATES | 41,000

United Kingdom| 18,000

Germany | 10,000

Poland | 3,000

Japan | 3,000

Czechoslovakia| 1,000

Belgium | 2,000

France | 2,000

Italy | 1,500

Spain | 700

+-----------------

Total | 82,200

--------------+-----------------

Source: Consular reports.

In the United Kingdom, where tar distillation is a well developed and

highly organized industry, large quantities of gas-works tar, rich in

phenol and other tar acids, are available. Prior to the World War the

United Kingdom was the principal source of phenol, and of the other

products of tar distillation. During the war several synthetic processes

of commercial importance were developed, but they were discontinued after

its close. A new synthetic unit has recently been installed in England

and is now in operation. Increasing consumption of phenol in synthetic

resins during the last decade, particularly in the last several years,

has changed the United Kingdom from an exporter to an importer of phenol.

Estimated consumption of phenol in the United Kingdom is given as 20

million pounds annually—principally in synthetic resins, and in lesser

quantities in dyes, intermediates, antiseptics, and disinfectants.

In Germany the phenol recovered in 1936 amounted to about 20 million

pounds, and recently three commercial units have been installed for the

production of synthetic phenol, one with a reported daily output of

11,000 pounds.

Natural phenol is also recovered in Belgium, France, the Netherlands,

Czechoslovakia, Poland, Italy, and Spain. Synthetic phenol has recently

been produced for the first time in Belgium and Italy. The quantities

normally produced in these countries are small and are supplemented by

imports from Great Britain and Germany.

The production of phenol in Japan has increased rapidly and has been

sufficient since 1930 to meet domestic requirements. The estimated output

increased from 300,000 pounds in 1927 to more than 3 million pounds

annually in recent years. The Miike Dyestuffs Works is reported to be

producing synthetic phenol.

United States imports.

_Rates of duty._—Prior to September 6, 1916, phenol was imported free of

duty. Since that date it has been dutiable at the various rates shown in

table 61. Under the act of 1930 the rate of duty is 3½ cents per pound

and 20 percent ad valorem on the American selling price (the wholesale

price of a similar competitive article manufactured in the United

States).[21]

TABLE 61.—_Phenol: Rates of duty upon imports into the United States,

1916-37_

------------------+------------------------+----------------------------

Period | Rate of duty | Authority

------------------+------------------------+----------------------------

To Sept. 8, 1916 |Free |Free under Tariff Act of

| | 1913 and previous acts.

| |

Sept. 9, 1916, to |2½ cents per pound plus |Under Revenue Act of 1916.

Sept. 21, 1922. | 15 percent ad valorem |

| on foreign value. |

| |

Sept. 22, 1922, to|7 cents per pound plus |Under par. 27 of Tariff Act

Sept. 21, 1924. | 55 percent ad valorem | of 1922; special provision

| on American selling | for first 2 years.

| price[1] or United |

| States value.[2] |

| |

Sept. 22, 1924, to|7 cents per pound plus |Under par. 27 of Tariff Act

Nov. 29, 1927. | 40 percent ad valorem | of 1922, rate provided

| on American selling | for period after the

| price[1] or United | first 2 years.

| States value.[2] |

| |

Nov. 30, 1927, to |3½ cents per pound plus |By Presidential proclamation

June 17, 1930. | 20 percent ad valorem | following a cost of

| on American selling | production investigation

| price[1] or United | under sec. 315 of Tariff

| States value.[2] | Act of 1922.

| |

June 18, 1930 |3½ cents per pound plus |Under par. 27 (b) of Tariff

| 20 percent ad valorem | Act of 1930.

| on American selling |

| price[3] or United |

| States value.[4] |

------------------+------------------------+----------------------------

[1] As defined in subdivision (f) of section 402, title IV, act

of 1922.

[2] As defined in subdivision (d) of section 402, title IV, act

of 1922.

[3] As defined in subsection (g) of section 402, title IV, act of

1930.

[4] As defined in subsection (e) of section 402, title IV, act of

1930.

_Import statistics._—Imports for consumption are shown in tables 62

and 63. Table 62 shows imports of phenol or carbolic acid and table 63

imports of “all distillates of tars yielding below 190° C. an amount of

tar acids equal to or more than 5 percent.” Imports under the latter

classification prior to 1928 were probably chiefly phenol. Phenol imports

consist entirely of the natural product.

TABLE 62.—_Phenol: United States imports for consumption, 1910-37_

-------+----------------------+---------+--------+----------+----------

-------+----------------------+---------+--------+----------+----------

1910[1]|Free |4,507,693|$275,600| $0.061|

1911[1]| do |4,371,014| 265,780| .061|

1912[1]| do |5,686,704| 521,457| .092|

1913[1]| do |8,345,631| 688,771| .083|

1914[1]| do |8,393,216| 531,535| .063|

1915[1]| do |3,106,445| 179,685| .058|

1916[1]|([2]) |2,246,256| 154,841| .069|

1917[1]|15 percent + 2½ cents | 265,519| 17,168| .065| 53.7

1918 | do | 283,337| 62,497| .221| 26.3

1919 | do | 2,061| 264| .128| 34.5

1920 | do | 1,040| 244| .235| 25.8

1921 | do | 250| 142| .568| 19.4

1922 |([3]) |} 280,224| 30,414| .109| 38.0

| |} 69,310| 16,102| .230| 85.1

1923 |55 percent + 7 cents | 126,618| 21,389| .169| 96.4

1924 |([5]) | 176,081| 46,786| .266| 81.4

1925 |40 percent + 7 cents | 256,126| 58,958| .230| 70.4

1926 | do | 218,437| 47,351| .217| 72.3

1927 |([6]) | 500| 100| .200| 75.0

1928 |20 percent + 3½ cents | 1,653| 298| .180| 39.4

1929 | do | 433,385| 44,226| .102| 54.3

1930 | do | 500| 115| .230| 39.4

1931 | do | 2,365| 639| .270| 33.0

1932 | do | None| | |

1933 | do | 3,440| 641| .186| 38.8

1934 | do | None| | |

1935 | do | 2,605| 211| .081| 63.0

1936 | do | 71,429| 8,302| .116| 50.1

1937[7]| do | 32,238| 3,767| .117| 50.0

-------+----------------------+---------+--------+----------+---------

[1] Fiscal year.

[2] 15 percent ad valorem and 2½ cents per pound effective Sept.

9, 1916.

[3] 55 percent ad valorem and 7 cents per pound, effective Sept.

22, 1922.

[4] Ad valorem based on American selling price or United States

value under acts of 1922 and 1930.

[5] Ad valorem reduced to 40 percent effective Sept. 22, 1924.

[6] Duty reduced to 20 percent ad valorem and 3½ cents per pound

effective Nov. 30, 1927.

[7] Preliminary.

Source: Foreign Commerce and Navigation of the United States.

TABLE 63.—_All distillates of tar yielding below 190° C. an amount of

tar acids equal to or more than 5 percent: United States imports for

consumption, 1918-37_

---------+----------------------+--------+------+----------+----------

---------+----------------------+--------+------+----------+----------

1918 |15 percent + 2½ cents | 1,550|$2,008| $1.30| 16.93

1919 | do | 3,170| 4,587| 1.45| 16.73

1920 | do | 85,474|36,041| .422| 20.93

1921 | do | 16,240|11,811| .727| 18.43

1922 |([1]) | 350,764|42,912| .122| 46.27

1923 |55 percent + 7 cents | 245,119|30,328| .124| 111.58

1924 |([3]) | 662,938|49,380| .074| 134.43

1925 |40 percent + 7 cents | 252,382|15,441| .061| 154.41

1926 | do | 1,102| 5,236| 4.75| 41.47

1927 |([4]) | 2| 16| 8.00| 40.88

1928-37 | | None| | |

---------+----------------------+--------+------+----------+----------

[1] 55 percent ad valorem and 7 cents per pound, effective Sept.

22, 1922.

[2] Ad valorem based on American selling price or United States

value under acts of 1922 and 1930.

[3] Ad valorem reduced to 40 percent, effective Sept. 22, 1924.

[4] Duty reduced to 20 percent ad valorem and 3½ cents per pound,

effective Nov. 30, 1927.

Source: Foreign Commerce and Navigation of the United States.

United States exports.

Exports of phenol have not been separately shown in official statistics

since 1924. In that year they went chiefly to Panama, Japan, Cuba, and

Mexico. Table 64 shows exports from 1918 to 1924, inclusive, as furnished

by the Department of Commerce.

TABLE 64.—_Phenol: United States exports, 1918-24_

----+---------+----------+----------

Year| Quantity| Value |Unit value

----+---------+----------+----------

| _Pounds_| |

1918|6,477,841|$2,666,634| $0.412

1919|1,243,841| 363,744| .292

1920|2,151,475| 388,047| .180

1921| 249,658| 35,994| .144

1922| 223,146| 23,223| .104

1923| 232,830| 34,389| .148

1924| 51,364| 8,016| .156

----+---------+----------+----------

Source: Commerce and Navigation of the United States.

Synthetic resins and their raw materials A survey of the types and uses of synthetic resins, the organization of the industry, and the trade in resins and raw materials, with particular references to factors essential to tariff consideration. Under the general provisions of section 332, title III, part II, Tariff act of 1930. · 第 15 / 22 段