EPA 560/5-78-001 A STUDY OF INDUSTRIAL DATA ON CANDIDATE CHEMICALS FOR TESTING April 1978 Research Request No. 2 FINAL REPORT Office of Toxic Substances U.S. Environmental Protection Agency Washington, D.C. 20460 ------- EPA 560/5-78-001 April 1978 A STUDY OF INDUSTRIAL DATA ON CANDIDATE CHEMICALS FOR TESTING by Susanne Urso and Kirtland E. McCaleb Chemical-Environmental Program Contract No. 68-01-4109 Research Request No. 2 Project Officer: James Darr Prepared for Office of Toxic Substances U.S. Environmental Protection Agency Washington, D.C. 20460 333 Ravenswood Ave. • Menlo Park, California 94025 (415) 326-6200 • Cable: STANRES, Menlo Park • TWX: 910-373-1246 ------- NOTICE This report has been reviewed by the Office of Toxic Substances, EPA, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. iii ------- CONTENTS LIST OF TABLES vi I. INTRODUCTION .................... , , i^1 II. SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS ....... 2-1 III. STUDY OF TWELVE CHEMICALS OF INTEREST TO EPA-OTS ...................... • • 3-1 l,5-Bis(chlorendo)cyclooctane ......... • • 3~3 Bis (2-chloroethyl) ether .............. 3-6 Bromoform ................... • • 3-8 2-Chloroethanol .................. 3-9 Diethyl N , N-bis ( 2-hydroxyethyl ) amino- phosphonate .................... 3-11 N-l , 3-Dimethylbutyl-N-phenyl-p- phenylenediamine ................. 3-13 4-Methyl-7-diethylaminocoumarin ........ . . 3-16 Sodium fluoride .................. 3-19 Sodium fluorosilicate ............... 3-21 Stannous chloride ................. 3-23 Vinyl pyridine .................. 3-25 Vinyl pyrrolidone . . . . .^ ............ 3-27 IV. REFERENCES ........ , ........ , . . . , 4-1 ------- LIST OF TABLES III-l Twelve Chemicals Studied in Research Request No. 2 3-2 III-2 Possible Substitutes for Dechlorane 25 3-4 III-3 Possible Substitutes for Diethyl N,N- bis(2-hydroxyethyl)aminomethylphosphonate . . 3-11 III-4 Possible Substitutes for N-l,3-Dimethyl- butyl-N-phenyl-p-phenylenediamine 3-14 III-5 Possible Substitutes for 4-Methyl-7- diethylaminocoumarin 3-18 III-6 Possible Substitutes for Sodium Fluoride 3-20 III-7 Possible Substitutes for Sodium Fluorosilicate .... 3-22 vi ------- I. INTRODUCTION A. Background The Office of Toxic Substances of the Environmental Protection Agency needs to produce information packages as a basis for decisions about testing chemicals for unreasonable risk to human health or the environment. Contract No. 68-01-4109 with SRI International (formerly Stanford Research Institute) was established as a first step in pro- ducing these packages. It calls for SRI to provide, in answer to Research Requests provided by the Project Officer, selected economic, chemical, and biological information on selected commercial chemicals. B. Objectives The objectives of this study were to provide selected economic information on twelve chemicals of interest, designated by the Project Officer, in the form of a tabular summary and prepare market forecasts for each chemical. 1-1 ------- II. SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS A. Summary This report describes the work carried out on Research Request No. 2 as specified by the Project Officer. Data were collected on production and trade statistics, past and current uses, possible substitutes (including price information), and trends in production for twelve chemicals designated by the Project Officer. Some of these data appear in a concise tabular summary of the chemicals in alphabetical order, followed by market forecasts on each chemical, which include a complete discussion of all the information obtained in the study. B. Conclusions and Recommendations Because Research Request No. 2 was designed to provide certain specified information on selected chemicals, no conclusions were drawn from the studies performed, nor are any recommendations appropriate. 2-1 ------- III. STUDY OF TWELVE CHEMICALS OF INTEREST TO EPA-OTS A. Tabular Summary The Project Officer requested a tabular summary of the twelve chemicals in alphabetical order using the chemicals names designated by EPA-OTS. This summary is presented in Table III-l. After each chemical name is listed the Chemical Abstracts Service Registry Number (CAS number), the most recent reported or estimated production level in millions of pounds and kilograms, the current price in cents per pound for large lots, and the total market value in millions of dollars (production level x price). B. Market Forecasts Market forecasts were prepared for each chemical and include a discussion of economic information requested by the Project Officer. The information presented for each chemical includes the following: production and trade statistics; a discussion of current uses, and in some cases, past uses; possible substitute products for the chemical in specific applications, and the current price of those substitutes; trends in production levels (i.e., future growth rates); and factors affecting growth in the market for the chemical. These market forecasts follow Table III-l, and are presented in alphabetical order by chemical name. 3-1 ------- Table III-I TWELVE CHEMICALS STUDIED IN RESEARCH REQUEST NO. 2 Estimated Production Chemical Name 1 , 5-Bis {chlorendo) cyclooctane Bis { 2-chloroethyl) ether BroROfonn 2-Chloroethanol Diethyl N,N-bis{2-hydroxyethyl}- aminophosphonate N-l» 3-Diaethylbutyl-N-phenyl- p-phenylenediamine 4-Methyl-7-diethylamino- coumarin Sodium fluoride Sodium fluorosilicate Stannous chloride Vinyl pyridine 2-Vinyl pyridine 4-Vinyl pyridine CAS Number 13560-89-9 1 n-44-4 75-25-2 107-07-3 2781-11-5 793-24-8 91-44-1 7681-49-4 16893-85-9 7772-99-8 1337-81-1 Year 1976 1976 1976 recent years 1977 1976 1976 1972 1976 1976 1976 Millions of pounds <17.3* >0.005 >0.001 30 4-8* 36 0.085 12.3 114.1 ND 4.5 >0.005 Millions of kilograms <8 >0.002 > 0.0004 54 13.6 1.8-3.6 16.4 0.0386 5.6 51.9 ND 2.0 >0.002 Current Price cents/lb . 170 9* 270 {pharma- ceutical grade) ND 88 187-190 f lakes t 197-200 850 (crude) 31-32 114 CUSP grade) 12-13 469 (anhydrous) 490 (hydrated) 159 314 Total Market Value Millions of dollars <29 >0. 00045 > 0.0027 — 3.5-7.0 68.4 0.72 3.8-3.9 13.7-14.8 .- -— 7.2 >0.016 Vinyl pyrrolidone 88-12-0 1974 10-12 4.5-5.5 97 9.7-11.6 * Consumption -i- Price quoted in 1971 (most recent available figure) ND= No data ------- 1,5-BIS(CHLORENDO)CYCLOOCTANE l,5-Bis(chlorendo)cyclooctane is a chlorinated cycloaliphatic flame retardant additive used in plastics. It is believed to be commercially marketed in the U.S. by one company as one of several chemicals covered by the tradename Dechlorane . Although the producing company has not divulged the chemical structure of the compounds marketed in the ® Dechlorane product line, a survey of the literature indicates that the adduct of 2 moles of hexachlorocyclopentadiene + 1 mole of 1,5-cyclo- octadiene, i.e., 1,5-bis(chlorendo)cyclooctane has the same physico- chemical properties as the commercially available product, Dechlorane 25 (also known as Dechlorane Plus 25), and probably has the same structure. Information on U.S. production of Dechlorane 25 is not available from the U.S. International Trade Commission. Industry sources estimate that 35.2 million Ibs. (16 million kg) of "chlorinated paraffins and cyclo- aliphatics" (.including Dechlorane 25) were used as flame retardant additives in 1977, and 33 million Ibs. (15 million kg) in 1976.^ Chlorinated paraffins used as flame retardant additives generally contain at least 65% chlorine. U.S. production of chlorinated paraffins contain- ing >65% chlorine combined with those containing <35% chlorine was re- ported to have been 15.7 million Ibs. (7.1 million kg) in 1976.2 It is believed that chlorinated paraffins containing >65% chlorine make up the bulk of this class. Therefore, subtracting the assumed 15.7 million Ibs. of chlorinated paraffins produced in 1976 from the total estimated 33 million Ibs. of chlorinated paraffins and cycloaliphatics used in 1976, indicates that as much as 17.3 million Ibs. (8 million kg) of chlorinated ® cycloaliphatics, including Dechlorane 25 could have been used as flame retardants in plastics in 1976. U.S. imports and exports data for ® Dechlorane 25 are not available. ® Dechlorane 25 is added, commonly in combination with inorganic fillers (especially antimony trioxide), to polymers to impart flame retardancy. It is widely used in polypropylene (especially in wire and cable and UL-94 applications which cover parts and devices in appliances). Other polymers in which it is reportedly consumed include ABS, acrylic, epoxy, and phenolic resins, nylon, polyester, polyethylene, polystyrene, polyvinyl acetate, and polyvinyl chloride.3 3-3 ------- Because flame retardant additives affect the processing properties of the polymer, selection of a specific additive for a specific plastic depends upon the properties required by a particular polymer system. The selection of substitutes for Dechlorane 25, therefore, depends not only on cost and flame retardant performance, but also on the specific polymer processing conditions. Possible substitutes for Dechlorane 25 reported in the trade literature, the polymers in which they are used, and their prices are listed in Table III-2. ' Table III-2 Possible Substitutes for Dechlorane 25 Product Chlorinated parraffins, for example: Chlorowax 70 Chlorowax 70S Halorez 70S Applicable Polymers ABS; acrylics, epoxy, nylon; phenolic; polyester; polyolefins; polystyrene; polyvinyl acetate; polyvinyl chloride Price (cents/lbs) 45.5 49.5 49.5 Citex BC-26 Citex BT-93 ABS; acrylics, polypropylene; polystyrene; polyvinyl acetate Polypropylene; impact-modified polystyrene Great Lakes DE-83R ABS; epoxy; phenolic; polyester; (decabromodiphenyloxide) polyolefins; polystyrene; poly- vinyl acetate; polyvinylchloride Hi Flame-Out 103 (trichlorotetrabromo- toluene) Hi Flame-Out 104 (pentabromophenyl- benzoate) Hi Flame-Out 105 (pentabromoethyl- benzene) Pyro-Chek 77B ABS; polyester; polyolefins for wire and cable; polystyrene 190 175 132-140 150 Nylon; polyolefins 150 3-4 ------- Although the company which produces Dechlorane w 25 has already eliminated one product.from the Dechlorane ® line due to government regulations on its effluent discharges into waterways, as of late 1977, it planned to continue producing Dechlorane ® 25. Dechlorane 25 availability has, however, been limited recently due to the shut-down of a hexachlorocyclopentadiene production plant resulting in customer allocation based on 70% of 1976 usage. The projected 1977-1982 growth rate for products such as Dechlorane ® 25 is estimated at 3-5% per year by industry sources. 3-5 ------- BIS(2-CHLOROETHYL)ETHER Bis(2-ahloroethyl)ether was formerly produced as a by-product of the ethylene chlorohydrin route to ethylene oxide. The chlorohydrin route was the main method of ethylene oxide manufacture until 1957. As companies began using direct ethylene oxidation, production via the chlorohydrin route declined and dropped to zero in 1973 and 1974. One U.S. company did resume production of ethylene oxide via the > chlorohydrin route in 1975 and 1976 due to unusual circumstances, however, this situation is not expected to recur in the future. U.S. production figures for bis(2-chloroethyl)ether were last reported in 1960 and amounted to 26.6 million Ibs. (12 million kg), c. - with sales amounting to 15.4 million Ibs. U.S. sales during 1961-1965 were reported as follows: ^ Yeai: Sales (millions of Ibs.) 1961 8.9 1962 7.3 1963 11.8 1964 8.8 1965 2.0 Two companies reported commercial production of bis(2-chloroethyl)ether to the U.S. International Trade Commission during 1966-1969, and only one company reported it during 1970-1973 and in 1976. Commercial production was not reported in 1974 and 1975. Since only one U.S. company reported commercial production of bis(2-chloroethyl)ether in 1976, this indicates that at least 5,000 Ibs. (2,272 kg) or $5,000 2 worth of bis(2-chloroethyl)ether were produced. One other company is also believed to be producing bis(2-chloroethyl)ether in the U.S.; however, no data are available on its production capacity. No evidence was found to indicate that bis(2-chloroethyl)ether is currently marketed commercially in the U.S. It is believed that the producing companies consume it internally as a solvent in chemical processes and as a chemical intermediate for the production of pro- prietary products. Data on U.S. imports and exports of bis (2-chloroethyl) ether are not available. 3-6 ------- Since bis(2-chloroethyl)ether is used in proprietary processes by the producing companies, no information is available to describe the specific end-uses that are in current practice. In the past, it has been used in a variety of applications described as follows: as a solvent for fats, waxes, and grease; as a scouring agent for textiles to remove paint and tar brand marks from raw wool and oil and grease spots from cloth; as a chemical intermediate in the pro- duction of alkyl aryl ether sulfate or sulfonate type anionic surface- active agents (which have been used in kier-boiling, desizing, and scouring operations, as emulsifiers in cosmetics, as detergents and lathering agents in shampoo and cleansing cream bases, and in metal cleaning operations); as a solvent for the separation of butadiene from butylene; in the synthesis of morpholine and N-substituted morpholine derivatives (N-hexadecyl morpholine); as a chemical inter- mediate in divinyl ether synthesis; as a chemical intermediate in the manufacture of resins and plasticizers, textile chemicals, Pharmaceu- ticals, insecticides, rubber chemicals, and lubricating oil additives; in a mixture with nitrobenzene for use as a solvent in the fractiona- tion of wax-containing mixtures; as a component of anti-knock compounds (lead scavenger); as a selective solvent in the production of high-grade lubricants and other naphthenic crude oils; as an insecticide sprayed on corn silk to control earworms; and as a soil fumigant.12-13 A discussion of specific substitutes for bis(2-chloroethyl)ether in its current applications is not possible, due to the proprietary nature of its usage. Although data are not available to quantitatively assess or forecast the U.S. market for bis(2-chloroethyl)ether, it appears that because of the chemicalls limited usage, future consumption will remain static or continue to decline. If ethylene oxide pro- duction via the chlorhydrin route is permanently discontinued under all circumstances, future production levels of bis(2-chloroethyl)ether will probably be very small, since it will no longer be available as a byproduct. 3-7 ------- BROMOFORM Only one U.S. company reports commercial production of bromoform to the U.S. International Trade Commission. This implies that a minimum of 1,000 Ibs. (454 kg) or $1,000 worth of bromoform is produced annually in the U.S. Data on U.S. imports and exports of bromoform are not available. Although bromoform is classified under the Medicinal section — "General Antiseptic and Antibacterial Agents" — by the U.S. International Trade Commission, no evidence was found to indicate that It is actually used for those applications. Bromoform had been used in the past as an antitussive/sedative for the treatment of whooping cough and seasickness.1 Because the market for bromoform is relatively small, little information is available on its end uses. Bromoform is believed to be used as a chemical intermediate for the manufacture of Pharmaceuticals; in geological assaying for the separation of minerals; as an ingredient in fire-resistant chemicals and gauge fluids; as a solvent for waxes, greases and oils; and as an intermediate in organic synthesis.15-16 No information is available to form a basis for discussion on bromoform substitutes. No data is available to quantitatively assess the future growth of the U.S. bromoform market. However, because the market is small and specialized, it would appear likely that the market for bromoform will remain relatively static. 3-8 ------- 2-CHLOROETHANOL 2-Chloroethanol , more connnonly known as ethylene chlorohydrin , is a chemical intermediate that has been used for the production of many chemicals. Prior to 1972, 2-chloroethanol was produced in large quantities (200-500 million Ibs.) (90-227 million kg) as an unisolated intermediate in the production of ethylene oxide. This production dropped to zero in 1973 and 1974 when the chlorohydrin route to ethylene oxide became economically unattractive. However, in 1975 and 1976, one U.S. company did produce significant quantities (about 50 million Ibs. or 23 million kg) of 2-chloroethanol for use as an unisolated intermediate for ethylene oxide production due to unusual circumstances. This situation is not expected to resume in the future so that all U.S. ethylene oxide pro- duction will be derived by direct oxidation of ethylene. Since only one U.S. company reported production of 2-chloroethanol in 1976, pro- duction data are not available from the U.S. International Trade Commission.2 However, based on the estimated quantity of ethylene oxide (derived from direct oxidation of ethylene) used to produce 2-chloro- ethanol in recent years (probably by reaction with a metal chloride) , an estimated 30 million Ibs. (13.6 million kg) of isolated 2-chloroethanol has been available. However, the one U,S. company which reported pro- duction in 1976 has apparently discontinued production of 2-chloroethanol since then. U.S. imports of 2-chloroethanol amounted to 2,200 Ibs. (1,000 kg) in 1976 (from Japan), 1.8 million Ibs. (0.8 million kg) in 1975 (over 96% from Japan), and 2,200 Ibs. (1,000 kg) in 1974 (from unspecified countries). 17-19 Data on w s_ exports are not available. 2-Chloroethanol is used as a raw material along with formaldehyde to produce bis (2-chloroethyl) formal which is used to produce polysulfide elastomers (used in printing rollers, hose, and gaskets where sblvent resistance is critical) r° 2-Chloroethanol reportedly can also be used as a chemical intermediate for anthraquinone dyes, B-phenylethanol (synthetic oil of rose) , choline (a B vitamin essential for egg pro- duction in chickens) , and a variety of other types of specialty chemicals It is used primarily to introduce a hydroxyethyl group into other organic compounds. 2^ 3-9 ------- Due to the limited market for 2-chloroethanol, information on specific substitutes is not readily available. It is believed that about 95% of commercially available polysulfide polymers are based on the bis(2- chloroethyl)formal derived from 2-chloroethanol. Ethylene dichloride is also used in polysulfide elastomers as well as small amounts of 1,2,3-trichloropropane, bis(4-chlorobutyl)ether, and bis(4-chlorobutyl) formal, however, bis(2-chloroethyl)formal appears to be a necessary 9O component for polysulfide polymers. Industry sources estimate that future consumption of ethylene oxide for the production of 2-chloroethanol will not exceed an annual average growth rate of 8.5% through 1983.22 3-10 ------- DIETHYL N,N-BIS(2-HYDROXYETHYL)AMINOMETHYLPHOSPHONATE Diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate is a reactive polyol used in the production of flame retardant rigid polyurethane foam. It is commonly known by its trade name, Fyrol 6. Since only one company produces it in the U.S., production data are not available from the U.S. International Trade Commission. Industry sources estimate that 15.4 million Ibs. (7 million kg) of "urethane intermediates (rigid foam)" (including Fyrol 6) were used as flame retardants in the pro- duction of rigid polyurethane foam in 1977, an increase of 16.7% from 1976 consumption levels. It is estimated that Fyrol® 6 accounts for about 4-8 million Ibs. (1.8-3.6 million kg) of that market. Data on U.S. imports and exports of Fyrol 6 are not available. Fyrol 6 is widely used in flame retardant rigid polyurethane foams at levels of 5 to 15%, where it reacts as a polyol and replaces part of the polyether in the foam formulation?3 Rigid polyurethane foams are primarily used as insulating material in construction, refrigera- tors and freezers, and truck and trailer bodies. They are also used in the manufacture of ornamental trim molding for furniture. Flame retardant rigid polyurethane foams are particularly important in the building and construction industry. A number of other reactive flame retardants are commercially available for use in rigid polyurethane foams. Some mentioned in the trade literature are included in Table III-3.3 Table III-3 Possible Substitutes for Diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate Compound Price (cents/lb.)4 Brominex 257 70 Chlorendic anhydride (HET Acid and 82 Anhydride) 2,3-Dibromo-2-butene-l,4-diol not available 3-11 ------- Table 111-3 (Continued) Compound Dibromobutendiol acetate Dibromoneopentyl glycol (FR-1138) Di- (polyoxyethylene)hydromethyl- phosphonate (Fyrol HMP) Tetrachlorophthalic anhydride (Tetrathal) Thermolin RF-230 Tribromoneopentyl alcohol (FR-1360; FR-2249) Vircol 82 Price (cents/lb.)' not available not available 260 72 75 not available 78 Many new reactive flame retardants are reportedly under development by ® the industry. Selecting a specific substitute for Fyrol 6 would be dependent upon the specific cost/performance characteristics exhibited by other products as well as the processing conditions required for its application. Future growth in the usage of reactive flame retardants for rigid ® polyurethane foams, including Fyrol 6, will depend upon the building and construction codes set for the industry. The projected 1977-1982 growth rate for products such as Fyrol® 6 is estimated at 6-10% per year by industry sources. 3-12 ------- N-l,3-DIMETHYLBUTYL-N-PHENYL-P-PHENYLENEDIAMINE N-l,3-Dimethylbutyl-N-phenyl-p-phenylenediamine is used as an antioxidant and antiozonant in rubber processing. U.S. production of this chemical reported to the U.S. International Trade Commission amounted to 37.5 million Ibs. (17 million kg) in 1974 and 30.5 million Ibs. (13.9 million 24-25 kg) in 1975. Although three companies reported production in 1976, a 2 separate production figure was not reported. Since it accounted for about 50% of the total production reported for the class "substituted p-phenylenediamines" in 1974 and 1975, and production of the class was 71.78 million Ibs. in 1976, production of this chemical in 1976 is estimated to have been about 36 million Ibs. (16.4 million kg). U.S. imports of N-l,3-dimethylbutyl-N-phenyl-p-phenylenediamine through prin- 26—29 cipal U.S. customs districts in recent years were reported as follows: Year Quantity (Ibs.) 1973 287,636 1974 117,563 1975 258,380 1976 380,506 Data on U.S. exports of N-l,3-dimethylbutyl-N-phenyl-p-phenylenediamine are not available. N-l,3-dimethylbutyl-N-phenyl-p-phenylenediamine is a protective additive compounded into rubber to provide resistance to ozone, fatigue, and aging degradation under static and dynamic conditions. It is recommended for use as an antiozonant and antioxidant in rubber based on isoprene (natural and synthetic), butadiene, and styrene-butadiene, particularly for protection against crack formation and crack growth. It is also used to inhibit degradation caused by copper and manganese contaminants. Major types of rubber products employing N-l,3-dimethyl- butyl-N-phenyl-p-phenylenediamine include carbon black-filled tires and mechanical goods. Selection of a specific substitute for N-l,3-dimethylbutyl-N- phenyl-p-phenylenediamine depends upon the specific properties of the potential antiozonant, as well as cost/performance considerations. 3-13 ------- Since most antiozonants are generally also useful as antioxidants but many antioxidants do not possess the ability to protect against ozone degradation, antiozonant properties are the most important consideration in choosing a substitute. The specific properties of a substitute which would have to be considered include volatility, solubility, chemical stability, physical state, and toxicity. In addition, specific types of antiozonants are only compatible with certain types of rubber. Some possible substitutes for N-l,3-dimethylbutyl-N-phenyl-p-phenylenediamine are listed in Table III-4. y Table III-4 Possible Substitutes for N-l,3-dimethylbutyl-N-phenyl-p-phenylenediame Compound Price* (cents/lb.) N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine (Flexzone 4L; Santoflex 77) 179-182 N,N'-Bis(l-ethyl-3-methylpentyl)-p-phenylenediame (Flexzone 8L) 179-182 Blend of alkyl & aryl derivatives of p-phenylene- diamine (Flexzone 10L; Flexzone 11L; Flexone 12L) 183-190 1/1/1 Blend of dioctyl-, phenylhexyl-, and phenyl- octyl-p-phenylenediamine (Anto3 C) 184-187 Diheptyl-p-phenylenediamine (Anto3 G) 179-182 N,N'-Di-3(5-methylheptyl-p-phenylenediamine) (Antozite 2) 181-184 Dioctyl-p-phenylenediamine (Anto3 D; Antozite 1) 174-177 6-Ethoxy-l,2-dihydro-2,2,4-trimethylquinoline (Santoflex AW) 129-132 N-Isopropyl-N'-pheny1-p-phenylenediamine (Flexzone 3-C; Santoflex IP) 193-196 Phenyl, hexy1-p-phenylenediamine (Ante3 E) 197-200 Phenyl, octyl-p-phenylenediamine (Anto3 F) 187-190 * Taken from November, 1977 issue of "Rubber World" 3-14 ------- Although the market for rubber processing chemicals such as N-1,3- dimethylbutyl-N-phenyl-p-phenylenediamine is believed to have grown by about 10% in 1977, prospects for long-term growth are relatively poor. Growth in this market is tied to growth in U.S. rubber consumption, and industry sources expect U.S. rubber consumption to grow at only about 3% per year, with tire consumption (the most important market for N-1,3- dimethylbutyl-N-phenyl-p-phenylenediamine) growing by as little as less than 2% per year. This outlook results from the move to smaller cars; smaller tires; radial tires; and lowered speed limits. Some new growth may occur in the market for rubber processing chemicals as a result of the shift to more durable tires, which will consume larger amounts 32 of processing chemicals to meet higher performance requirements. 3-15 ------- 4-METHYL-7-DIETHYLAMINOCOUMARIN 4-Methyl-7-diethylaminocoumarin is an optical brightener used primarily in the textile and detergent industries to increase the white- ness and brightness of fibers and clothes. Since only two companies reported commercial production of crude 4-methyl-7-diethylaminocoumarin to the U.S. International Trade Commission in 1976, separate production figures are not available. However, based on reporting minimums established by the commission, 1976 U.S. production of this chemical o exceeded 10,000 Ibs. (4,500 kg) or $10,000 in value. The Society of Dyers and Colourists has classified all the optical brighteners developed for use in the textile industry, and the U.S. International Trade Commission reports production of specific brighteners based on their nomenclature. Although the specific brighteners are numbered (e.g., Fluorescent Brightening Agent 55), the Society of Dyers and Colourists does not disclose the chemical identity of each agent, revealing only the general chemical class to which it belongs (e.g., aminocoumarin). Based on evidence discovered in the literature, it appears that 4-methyl-7-diethylaminocoumarin is the major component of 33—35 Fluorescent Brightening Agent 61. U.S. production of Fluorescent Brightening Agent 61 amounted to 33,000 Ibs. (15,000 kg) in 1975 and 85,000 Ibs. (38,600 kg) in 1976?'25 It is not known whether 4-methyl-7- diethylaminocoumarin is a component of any other fluorescent brightening agents. Data on U.S. imports and exports of either 4-methyl-7- diethylaminocoumarin or Fluorescent Brightening Agent 61 are not available. 4-Methyl-7-diethylaminocoumarin is used as an optical brightener by the textile industry for wool, nylon, and acetate fibers, and as an ingredient in fine-fabric laundering compositions which are not used in 36—38 the presence of chlorine bleach. It is also used as an optical brightener in pigmented coatings and solvent and water-based coatings.39 4-Methyl-7-diethylaminocoumarin is an important laser dye standard in the blue and green region of the spectrum; however, the laser grade is very expensive and only a few milligrams are required for its use.40 3-16 ------- Other reported uses for 4-methyl-7-diethylaminocoumarin which could not be verified as being commercial include: as an optical brightener for paper, labels and book covers; to lighten plastics and resins', and as an invisible marking agent. One U.S. patent describes a potential use in a fluorescent skin-marking composition for animals and humans to indicate 33 areas of skin to be subjected to radiation therapy. A reference text on optical brighteners has reported that although brighteners with better properties have been developed, products con- 41 taining 4- methyl-diethylaminocoumarin are still in common usage. In 1976, 4-methyl-7-diethylaminocouinarin is estimated to have accounted for less than 0.2% of the total reported U.S. production of optical 2 brighteners (43.4 million Ibs. or 19.7 million kg). Almost 300 fluore- scent brighteners have been developed, of which the most important compo- sitions cover at least 14 different structural types: 4,4-bis-(tri- azinylamino) -stillbene-2,2' -disulfonic acids; 4,4-bis- (v-triazol-2-yl) - stilbene-2,2'-disulfonic acids; 4,4'-bis-(diphenyltriazinyl)-stilbenes; 4,4'-distyry] -biphenyls; 4-phenyl-4'^benzoxazolyl-stilbenes; stilbenyl- naphthotriazoles; 4-styryl-stilbenes; bis-(benzoxazol-2-yl)-derivatives; bis-(benzimidazol-2-yl)-derivatives; coumarins; pyrazolins; naphthali- mides; triazinyl-pyrenes; and 2-styryl-benzoxazoles and naphthoxazoles.3^ Of the 19 fluorescent brightening agents specifically listed as being commercially produced in the U.S. in 1976 by the U.S. International Trade Commission, nine compositions have applications similar to 4- methyl-7-diethylaminocoumarin. These brighteners are listed in Table III-5 as possible substitutes.34'39 3-17 ------- Table m-5 Possible Substitutes For 4-Methyl-7-diethylaminocoumarin Textile Uses Applicable to 4-Methyl-7- diethylamino- coumarin Wool Fluorescent Brighteners 25 (Blancophor SV) 28 (Calcofluor White PMS, PMW, ST) Chemical Class Stilbcno 4,4' -Bis ((anilino-rfylon; laundry 6-(bis(2-hydroxy- formulations ethyl(amino)-s- triazin-2-yl) amino)-2,2'- stilbenedisulfonic acid 49 (Leucophor BS) 52 (Leucophor WS; Leucopur Base) Bistriazinyl- aminostilbene Coumarin derivative 54 (Tinopal WG) Not known Nylon Acetate; nylon Nylon 59 (Tinopal RBN) 125 (Calcofluor White EDW, PUM) 130 (Calcofluor White LD) Stilbene-triazole Nylon sulfonic acid derivative Triazinylstilbene Nylon derivative Coumarin derivative 134 (Uvitex CF) Stilbene Wool, nylon, acetate, deter- gent formulations Nylon, wool Price (cents/lb.)' 342 84 120 120 not available not available not available 1100 not available No information was available on which to forecast the future growth of 4-methyl-7-diethylaminocoumarin production in the U.S. 3-18 ------- SODIUM FLUORIDE Four companies are currently believed to be producing commercial quantities of sodium fluoride in the U.S. Production figures for sodium fluoride are not available; however, based on hydrofluoric acid consumption for the production of fluoride salts, sodium fluoride pro- duction is estimated to have been less than 13 million Ibs.(6 million kg) in 1976 . In 1972, the U.S. Bureau of the Census reported production 42 of 12.3 million Ibs. (5.6 million kg) of sodium fluoride. Data on U.S. imports and exports of sodium fluoride are not available. Sodium fluoride was primarily used in the past for the fluoridation of municipal drinking water supplies; however, it has been replaced by most communities with hydrofluosilicic acid and sodium fluorosilicate which are much cheaper. Very small communities may still be using it because it is easy to handle. Sodium fluoride is also used in the following applications: in the pickling of stainless steel to remove scale; in exothermic mixtures (heat producing materials) to keep molten metal from solidifying, e.g., during the casting of iron, steel, or aluminum; as a fluxing agent in aluminum resmelting to clean and cover the metal and to modify or grain refine the metal structure; for the surface treatment of metals to obtain a satin finish; as a degassing agent in the manufacture of rimmed steel; as a frosting agent in glass manufacture; as a preservative in casein, glue, and starch adhesives; and as a dental caries prophylactic (in tablet, liquid, capsule, and gel form).43-45 other reported uses for sodium fluoride include use as an antiseptic in breweries and distilleries; in heat treating salts; and in the manufacture of coated papers. Sodium fluoride has been used as a component of wood preservatives for protection against fungal rot and decay used for mine timbers, pilings, posts, poles, and other wood structures and in insecticide compositions for cockroaches, ants, silverfish, centipedes, crickets, spiders, sowbugs, and termites. It is not known whether it is still being used for all of these applications. ' 3-19 ------- In general, applications for sodium fluoride can be served by other fluoride compounds. Possible substitutes for sodium fluoride are listed in Table IH-6. All of these chemicals are used in the applications described, and in some cases are consumed to a greater extent than sodium fluoride. 43 Compound Fluorspar Table III-6 Possible Substitutes for Sodium fluoride Application Fluxing agent in aluminum resmelting Hydrofluoric acid Hydrofluosilicic acid Potassium fluoroborate Sodium fluoroborate Sodium fluorosilicate Pickling stainless steel; frosting glass; metal surface treatment to obtain satin finish Water fluoridation Fluxing agent in aluminum resmelting Fluxing agent in aluminum resmelting Water fluoridation; in exothermic 12 - 13 mixtures to keep molten metal from solidifying « • 48 Price (cents/lb.) 4.8-5.0 (value) 33.8 (70% basis) 3.75 (23% basis) 37>s - 49 - 46 Because sodium fluoride is an expensive chemical, relative to other fluorides, demand has been declining due to the availability of cheaper substitutes. It is not known whether this decline has levelled off or is still falling; however, prospects for market growth are dim. 3-20 ------- SODIUM FLUOROSILICATE Six companies produce commercial quantities of sodium fluorosilicate in the U.S. U.S. production figures reported by the U.S. Bureau of the Census in recent years are as follows: ' Year Production (million Ibs.) 1976 114.1 1975 97.0 1974 103.2 1973 108.0 1972 114.7 1971 120.8 U.S. imports of sodium fluorosilicate amounted to 12.0 million Ibs. in 1976, 18.3 in 1975, 15.4 in 1974, and 9.4 in 1973?-7"19'50 Data on U,S. exports of sodium fluorosilicate are not available. Sodium fluorosilicate is primarily used for the fluoridation of municipal drinking water supplies by small communities which do not want to invest in the liquid metering equipment necessary for the use of hydrofluosilicic acid. Sodium fluorosilicate has numerous other uses including the following: as a flux in aluminum refining; in exothermic mixtures (heat producing materials) to keep molten metal from solidifyinq; as an opacifier in the production of opal glass; as a constituent of vitreous enamel frits where it acts as a flux during smelting and contributes greater opacity in the final enamel coating; in enamel glazes for chinaware; in the metallurgy of beryllium and zirconium; as a laundry scouring agent; in the manufacture of acid-resistant cement; in lead refining; as a gelling agent for natural isoprene rubber latex foam; as a mothproofing agent for woolen fabrics, carpets, feathers, and furs; as a preservative to prevent mold in glue, starch sizes and leather processing; as a slime control agent in paper manufacture; as a rodent repellent in paperboard shipping containers; and as an insecticide for earwigs, cutworms, sowbugs, strawberry root weevil, ants, centipedes, cockroaches, crickets, and silverfish,30'43"44'47 3-21 ------- In general, applications for sodium fluorosilicate can be served by other fluoride compounds. Possible substitutes are listed in Table III-7. ' All of these chemicals are used in the applications described, and in some cases are consumed to a greater extent than sodium fluoro- silicate. Table III-7 Possible Substitutes for Sodium Fluorosilicate Compound Ammonium nitrate Ammonium sulfate Diphenylguanidine Di-ortho-tolyguanidine Application Gelling agent for natural isoprene rubber latex foam Fluorspar (metallurgical and acid grade) Price (cents/lbs) 4.5 - 5.75 (33.5% basis) 3 - 4.5 182 - 192 117 - 120 4.8-5.0 (value) 48 Hydrofluosilicic acid Potassium fluorosilicate Sodium fluoride 3.75 (23% basis) 11.5 - 15 31 - 32 Flux in aluminum refining; opacifier in production of opal glass Fluoridation of municipal water supplies Flux for vitreous enamel frits Fluoridation of municipal water supplies; in exothermic mixtures to keep molten metal from solidifying Information is not available on which to base a quantitative fore- cast of the future growth in sodium fluorosilicate production. An important factor in the future consumption of sodium fluorosilicate will be the future status of municipal water fluoridation programs, the safety of which has been under review by the Food and Drug Administration. 3-22 ------- STANNOUS CHLORIDE No information was available to indicate the size of the U.S. stannous chloride market. Only two companies produce commercial quantities of stannous chloride in the U.S. It is available in an- hydrous and hydrated forms. Stannous chloride is primarily used in metal plating applications. It is believed that about 70% of U.S. stannous chloride consumption is used in the electrotinning of steel strip via the halogen process. In simple terms, steel strip is tinplated by electrolytically oxidizing metallic tin (the anode) in an electrolytic plating solution to cause metallic tin to be deposited on the steel strip (the cathode) moving through plating unit. In the halogen process the plating bath electro- lyte consists of an aqueous solution of stannous chloride and alkali metal fluorides. There are two other tinplating processes which are commonly used; one uses a plating bath electrolyte containing a solution of stannous sulfate and phenolsulfonic acid, and the other uses an electrolyte based on a solution of sodium stannate and sodium hydroxide. Tinplated steel strip is used primarily in the manufacture of metal cans, especially for the food industry. The steel provides container strength and the tinplate provides resistance to corrosion. Stannous chloride is also used in tin-nickel plating (65% tin and 35% nickel). These coatings are used for printed circuit boards, watch parts, drawing instruments, scientific apparatus, refrigeration equip- co ment, musical instruments, and handbag frames. Stannous chloride is also used in numerous other applications including the following: as a sensitizer for the silvering of plastics and mirrors; in a tin coating for sensitized paper; as an intermediate for tin chemicals manufacturing; as an antisludge agent for oils; as an additive to drilling muds; as a soldering flux; as a food additive to protect and enhance flavors, prevent corrosion, and maintain food colors in canned food, especially in carbonated soft drinks (at levels of 11 ppm), and also for asparagus (20 ppm) and other foods (15 ppm); as a 3-23 ------- tanning agent for leather; as a stabilizer for perfumes in toilet soaps; as a mordant in printing dyes; as an antioxidant; as a catalyst in organic reactions (e.g., it has been used with phenolic resins to cure butyl rubber ); as a reducing agent in laboratory procedures (e.g., in the preparation of aryldichlorostibines by reduction of the corres- ponding stibonic acid in hydrochloric acid solution); as an analytical reagent; and in the manufacture of pigments and Pharmaceuticals. Selecting a substitute for stannous chloride in its most important application, tinplating, would depend on the cost/performance character- istics of other plating processes. As described previously, other tinplating processes are in common usage which use electrolytes that are not based on stannous chloride. Other types of steel which resist corrosion are also available, primarily, tin-free steel in which chromium is electrolytically plated on black plate steel or blackplate steel coated with suitable organic coatings. Aluminum cans are making inroads into the major market for tinplated steel, metal cans, primarily 58 in beverage container applications. Consumption of tin for use in chemicals such as organotin compounds and inorganics, including stannous chloride, has grown at an average annual rate of 8.5% since 1970, according to the U.S. Department of Commerce, and will grow by 5% in 1978. Shipments of metal cans (major market for tinplate) are expected to grow by 2.2%/year reaching 97 billion cans by 1982, with beverage cans accounting for most of the growth. By 1980, aluminum cans are expected to account for 75% of the beverage can market. The use of all metal cans could be adversely affected by legislation restricting the use of nonreturnable beverage containers. 3-24 ------- VINYL PYRIDINE Vinyl pyridine is commercially available in the U.S. in the form of two isomers, 2- and 4-vinyl pyridine. Since only one U.S. company reports commercial production of 2- and 4-vinyl pyridine, production data are not available from the U.S. International Trade Commission. Virtually all the U.S. production of 2-vinyl pyridine is used in the production of styrene-butadiene-vinyl pyridine terpolymer elastomers. Based on industry-wide usage of about 15 wt. % 2-vinyl pyridine in these products, U.S. consumption of 2-vinyl pyridine is estimated at 4.5 million Ibs. (2 million kg) in 1976. U.S. production of 4-vinyl pyridine (based on U.S. International Trade Commission reporting minimums) exceeds 2 5,000 Ibs. (2,272 kg) or $5,000 in sales value. Data on U.S. imports and exports of 2- and 4-vinyl pyridine are not available. Almost all U.S. consumption of 2-vinyl pyridine is used to produce styrene-butadiene-vinyl pyridine elastomer latex. The latex is used in an adhesive dip along with a resorcinol and formaldehyde resin (11 parts resorcinol to 6 parts formaldehyde). The dip usually contains 17 parts resorcinol-formaldehyde resin and 100 parts latex and is used to bond nylon, rayon, polyester, and fiberglass (or other fibers or textile fabrics) to rubber; these cord- or fabric-reinforced rubber products include tires (major market), industrial belting, and V-belts. Rayon fibers only require a latex containing about 50% of the vinyl pyridine terpolymer, with the rest made up of styrene-butadiene copolymer latex. Nylon fibers require 75-100% vinyl pyridine terpolymer in the latex, and polyester and fiberglass dips contain 100% vinyl pyridine terpolymer in the latex. Polyester fibers also require either: (1) addition of a proprietary modified resorcinol-formaldehyde resin to the adhesive dip; or (2) a two step process in which the fibers are first dipped in a reactive polymer based on a mixture of isocyanates and epoxy resins followed by dipping in the conventional resorcinol-formaldehyde-latex dip. U.S. production of styrene-butadiene-vinyl pyridine elastomer dropped from a high of 38.2 million Ibs. (17.3 million kg) in 1972 to 29.8 3-25 ------- million Ibs. (13.6 million kg) in 1976, a decrease of 22%.2'59 This decline is primarily a result of increased usage of steel-belted tires, which uses different rubber processing technology and does not consume styrene- butadiene-vinyl pyridine elastomer latex. Another factor contributing to the decline is increased usage of polyester tire cord which requires less of the styrene-butadiene-vinyl pyridine elastomer latex dip than the older nylon and rayon cords. It is believed that the decline in styrene-butadiene-vinyl pyridine elastomer consumption has bottomed out and will remain at the 1976 level through 1985. Therefore, production of 2-vinyl pyridine is expected to remain at about 4.5 million Ibs. per year during that time period. Although styrene-butadiene latex is also used to some extent in rayon and nylon bonding, the vinyl pyridine terpolymer latex appears to be necessary for tire performance. Other reported uses specifically mentioned for the 2-isomer of vinyl pyridine include: (1) as an intermediate, via addition of methanol, to 2-3-methoxyethylpyridine (methyridine) used as a sheep and cattle anthelmintic; (2) as a dye assistant incorporated into acrylic fibers at levels of less than 5% of the polymer to promote acid dyeing (2- methy1-5-vinyl pyridine is also reportedly used); and (3) polymerization to polyvinyl pyridine for use as an element in photographic film. The market for 4-vinyl pyridine has not been well defined. It has reported use: (1) as a textile dyeing assistant for synthetic fibers under acid dyeing conditions; (2) for the preparation of copolymers with styrene and acrylonitrile; (3) in the manufacture of synthetic elastomers and photographic chemicals; (4) as a starting material for the synthesis of pyridine derivatives; (5) as a comonomer for the produttion of polyelectrolytes used in ion exchange resins and as flocculants and emulsifiers; and (6) in the preparation of polyvinylpyridium salts which are used as flocculants. (2-Vinyl pyridine has also been mentioned for 62-64 use in the applications lasted above.) No information was available on which to forecast the future growth of 4-vinyl pyridine production in the U.S. 3-26 ------- VINYL PYRROLIDONE Vinyl pyrrolidone is used as a monomer and as a chemical intermediate. Since only one company produces it in the U.S., production data are not available from the U.S. International Trade Commission. U.S. consump- tion of vinyl pyrrolidone (based on acetylene usage) is estimated to have been 10-12 million Ibs. (4.5-5.5 million kg) in 1974. U.S. imports of vinyl pyrrolidone and its homopolymer, polyvinyl pyrrolidone combined amounted to 1.6 million Ibs. (0.7 million kg) in 1976 and were from the Federal Republic of Germany (95%), France (2.5%), the German Democratic Republic (2.2%), and Sweden (0.3%). Data on U.S. exports of vinyl pyrrolidone are not available. Vinyl pyr*rolidone is used primarily as a monomer for the manufacture of its homopolymer, polyvinyl pyrrolidone. Polyvinyl pyrrolidone is a unique polymer used in many industrial applications due to its wide range of properties as a film-former, adhesive, protective colloid, dispersant, stabilizer, binder, complexing agent and detoxicant. It is used in a wide variety of industrial and consumer products including: cosmetics (hairwave sets, aerosol hair sprays, shampoo, make-up, etc.); soaps and detergents; adhesives; ball-point pen and printing inks; paints and varnishes; paper and paper coatings; textile processing chemicals; printing plates; agricultural formulations; antifreeze sprays; and waxes and polishes. Polyvinyl pyrrolidone is used in pharmaceutical applications as a: tablet coating agent and binder; blood plasma extender for emergency use; tablet disintegrator; detoxifier; antidiarrhea agent; in injections, topical applications, and medicinal aerosols; and as a dialyzing medium. Polyvinyl pyrrolidone is also used as a beverage clarifier and stabilizer in beer, wine, whiskey, vinegar, fruit juices, and tea.65"67- Copolymers are made using vinyl pyrrolidone (usually at a concen- tration of 1-20%) with many other comonomers (e.g., vinyl acetate, ethyl acrylate, and styrene) for diverse applications, including: drilling fluids, paints, lube oil additives, adhesives, coatings, cosmetics, textile finishes, synthetic fibers, protective colloids, etc.67~69 3-27 ------- Hydrogels based on crosslinked copolymers of vinyl pyrrolidone and 2-hydroxyethyl methacrylate are used in soft contact lenses. Vinyl pyrrolidone is also reportedly used as an intermediate for the production of modified phenolic resins used as plasticizers, dye intermediates, and textile assistants. There do not appear to be any likely substitutes in the primary uses of vinyl pyrrolidone as a monomer. Although substitutes exist for the use of vinyl pyrrolidone homopolymer and copolymers in end-use applications, due to the wide variety of these applications, a sub- stantive discussion of such products is not possible. The projected growth rate for the production of vinyl pyrrolidone is estimated at about 6-7% per year. 3-28 ------- IV. REFERENCES 1. Anon. (1977) Flame Retardants. Modern Plastics, September issue, pp. 58-60 2. US International Trade Commission (1977) Synthetic Organic Chemicals, US Production and Sales, 1976, USITC Publication 833, Washington, B.C., US Government Printing Office 3. Agranoff, J., ed. (1977) Modern Plastics Encyclopedia 1977-1978, October, Vol. 53, Number 10A, New York, McGraw-Hill Publications Co. 4. Prices for large lots of a chemical were obtained through contact with manufacturers and/or distributors. 5. Kidder, R.C. (1977) Additives for plastics - flame retardants. Plastics Engineering, February issue, pp. 38-42 6. US Tariff Commission (1961) Synthetic Organic Chemicals, US Production and Sales, 1960, TC Publication 34, Washington, D.C., US Government Printing Office 7. US Tariff Commission (1962) Synthetic Organic Chemicals, US Production and Sales, 1961, TC Publication 72, Washington, D.C., US Government Printing Office 8. US Tariff Commission (.1963) Synthetic Organic Chemicals, US Production and Sales, 1962, TC Publication 114, Washington, D.C., US Government Printing Office 9. US Tariff Commission (1964) Synthetic Organic Chemicals, US Production and Sales, 1963, TC Publication 143, Washington, D.C., US Government Printing Office 10. US Tariff Commission (1965) Synthetic Organic Chemicals, US Production and Sales, 1964, TC Publication 167, Washington, D.C., US Government Printing Office 11. US Tariff Commission (1967) Synthetic Organic Chemicals, US Production and Sales, 1965, TC Publication 206, Washington, D.C., US Government Printing Office 12. Union Carbide Chemicals Company (1959) Ethers and Oxides- product bulletin, p.12 13. Berg, G.L,, ed. (1977) 1977 Farm Chemicals Handbook, Willoughby, Ohio» Meister Publishing Co., p. D87 14. Swinyard, E.A., & Harvey, S.C. (1965) Sedatives and Hypnotics. In: Martin, E.W., ed,, Remington's Pharmaceutical Sciences, 13th ed., Easton, Pennsylvania, Mack Publishing Co., p.1157 15. National Academy of Sciences (1977) Drinking Water and Health, Washington, D.C., Safe Drinking Water Committee, p. 695 4-1 ------- 16. Hawley, G.G., ed. (1971) The Condensed Chemical Dictionary, 8th ed., New York, Van Nostrand-Reinhold Co., p.130 17. US Bureau of the Census (1977) US Imports For Consumption And General Imports, FT246/Annual 1976, Washington, D.C., US Government Printing Office 18. US Bureau of the Census (1976) US Imports for Consumption And General Imports, FT246/Annual 1975, Washington, D.C., US Government Printing Office 19. US Bureau of the Census (1976) US Imports for Consumption And General Imports, FT246/Annual 1974, Washington, D.C., US Government Printing Office 20. Berenbaum, M.B. (1969) Polysulfide Polymers. In: Bikales, N.M., ed., Encyclopedia of Polymer Science and Technology/ Vol. 11, New York, Interscience Publishers, pp. 425-447 21. Union Carbide Corp. (1966) Ethylene Chlorohydrin Product. Bulletin, New York 22. Anon. (1977) Can oxide makers close the gap? Chemical Week, April 6, pp. 40-47 /R\ 23. Stauffer Chemical Co. (date not available) Product data sheet - Fyrol w 6. Westport, Connecticut 24. US International Trade Commission (1976) Synthetic Organic Chemicals, US Production and Sales, 1974, USITC Publication 776, Washington, D.C., US Government Printing Office 25. US International Trade Commission (1977) Synthetic Organic Chemicals/ US Production and Sales/ 1975, USITC Publication 804, Washington, D.C., US Government Printing Office 26. US Tariff Commission (1974) Imports of Benzenoid Chemicals and Products, 1973, TC Publication 688, Washington, D.C., US Government Printing Office 27. US International Trade Commission (1976) Imports of Benzenoid Chemicals and Products, 1974, USITC Publication 762, Washington, D.C., US Government Printing Office 28. US International Trade Commission (1977) Imports of Benzenoid Chemicals And Products, 1975, USITC Publication 806, Washington, D.C., US Government Printing Office 29. US International Trade Commission (1977) Imports of Benzenoid Chemicals And Products, 1976, USITC Publication 828, Washington, D.C., US Government Printing Office 4-2 ------- 30. Anon. (1975) Materials and Compounding Ingredients For Rubber (Blue Book), New York, Rubber World Magazine 31. Parks, C.R., & Spacht, R.B. (1977) Antioxidants in compounding. Elastomerics, May issue, pp. 25-34 32. Webber, D.S. (1977) Rubber chemical producers survive recession and strike. Chemical Marketing Reporter, May 16, pp. 45 and 46 33. Stewart, D.J. (1972) Fluorescent skin-marking compositions. US Patent 3,640,889. Chem. Abstr., 76, 142497k 34. Society of Dyers and Colourists (1971 and 1975) The Colour Index, 2nd ed., Yorkshire, England 35. Schulze, J., Polcaro, T., & Stensby, P. (1974) Analysis of fluorescent whitening agents in US home laundry detergents. Soaps/Cosmetics/ Chemical Specialties, November issue, pp. 46-52 36. Stensby, P. (1968) Optical brighteners as detergent additives. Journal of the American Oil Chemists' Society, 45, p.499 37. Billington, R.G., ed. (1973) Review 1973/1. Ciba-Geigy Ltd. 38. Zweidler, R., & Hausermann, H. (1964) Brighteners, Optical. In: Kirk- Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 3, New York, John Wiley & Sons, Inc., pp. 737-750 39. Franklin Institute Laboratories (1975) Preliminary Study of Selected Potential Environmental Contaminants, PB-243 910, Environmental Protection Agency, (Distributed by NTIS) 40. Drexhage, K.H. (1976) Fluorescence efficiency of laser dyes. J. Res. Nat'-l. Bur, of Standards, 80A (3) , pp. 421-428 41. Anliker, R., & Mtfller, G., eds. (1975) Fluorescent Whitening Agents. Stuttgart, Georg Thieme, dist* by. Academic Press 42. US Bureau of the Census (1976) Current Industrial Reports, Inorganic Chemicals, 1975, Series M28A(75)-14, Washington, D.C., p.8 43. Burgess, G.C. (1974) The Diverse Uses of Inorganic Fluorides. Int'1. Technico Economical Symp ., Oct. 23/24, Brussels 44. Olin Corp. (1962) Chemicals for Industry- product bulletin 45. Kastrup, E.K., ed. (1977) Facts and Comparisons, St. Louis, Missouri, Facts and Comparisons, Inc., pp. 13 and 13a 46. Griswold, J. (1966) Fluorine Compounds, Inorganic, Sodium Fluoride. In: KirkK)thmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 9, New York, John Wiley & Sons, Inc., pp. 662-663 4-3 ------- 47. US Environmental Protection Agency (1973 & 1974) EPA Compendium of Re- gistered Pesticides, Vol. II, Fungicides and Nematicides and Vol. Ill Insecticides, Ascaricides, Molluscicides and Antifouling Compounds, Washington, D.C., US Government Printing Office 48. Anon. (1978) Current prices of chemicals and related materials, as of Feb. 17, 1978, Chem. Mktg. Reptr., Feb. 20 issue 49. US Bureau of the Census (1977) Current Industrial Reports, Inorganic Chemicals, 1976. M28A(76)-14, Washington, D.C. 50. US Bureau of the Census (1974) US Imports For Consumption And General Imports, FT246/Annual 1973, Washington, D.C., US Government Print- ing Office 51. McGannon, H.E., ed. (1971) The Making, Shaping and Treating of Steel, 9th ed., United States Steel, pp. 996-1011 52. Banks, C.K. (1969) Tin and Tin Alloys. In: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 20, New York, John Wiley & Sons, Inc., pp. 288-289 53. M&T Chemicals Inc. (undated) Specialty chemicals from M&T that can make you look good. Rahway, N.J. 54. Vulcan Materials Co. (undated) Chemical Product Guide 55. M&T Chemicals Inc. (1974) M&T Tin Chemicals 56. Keutgen, W.A. (1968) Phenolic Resins. In: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 15, New York, John Wiley & Sons, Inc., p.186 57. Doak, G.O., Freedman, L.D., & Long, G.G. (1963) Antimony Compounds. In: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 2, New York, John Wiley & Sons, Inc., pp. 582-583 58. US Department of Commerce (1978) 1978 U.S. Industrial Outlook, Washington, D.C., US Government Printing Office, pp. 80-83 and 207-210 59. US Tariff Commission (1974) Synthetic Organic Chemicals, US Production and Sales, 1972, TC Publication 681, Washington, D.C., US Govern- ment Printing Office 60. Arnall, P. (1961) Pyridine and its homologues as chemical raw materials. reprint from Chemical Products, November issue 61. Abramovitch, R.A. (1968) Pyridine. In: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 16, New York, John Wiley & Sons, Inc., p.803 4-4 ------- 62. Reilly Tar & Chemical Corp. (undated) Reiily Product. Information— 4-Vinylpyridine 63. Armstrong, R.W., & Strauss, U.P. (1969) Polyelectrolytes. In: Encyclopedia of Polymer Science and Technology/ Vol. 10, New York, Interscience Publishers, p.784 64. Tazuke, S., & Okamura, S. (1971) Vinylpyridine Polymers. In: Encyclopedia of Polymer Science and Technology, Vol. 14, New York, Interscience Publishers, p. 657-660 65. Lorenz, D.H. (1971) N-Vinyl Amide Polymers. In: Encyclopedia of Polymer Science and Technology, Vol. 14, New York, Interscience Publishers, pp. 239-251 66. Wood, A.S. (1970) Vinyl Polymers (Pyrrolidone). In: Kirk-Othmer Encyclo- pedia of Chemical Technology, 2nd ed., Vol. 21, New York, John Wiley & Sons, Inc., pp. 427-440 67. GAF Corporation (1973) Chemical Catalog, pp.2-6 68. Huebotter, E.E., Si Gray, G.R. (1965) Drilling Fluids. In: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Vol. 7, New York, John Wiley & Sons, Inc., pp. 300-301 69. Hort, E.V., & Smith, R.F. (1968) Pyrrole and Pyrrole Derivatives. In: Kirk-Othmer Encyclopediaof Chemical Technology, 2nd ed., Vol. 16, New York, John Wiley & Sons, Inc., p.853 70, Halpern, B.D., & Karo, W. (1977) Medical Applications. In: Encyclopedia of Polymer Science and Technology, Supplement Vol. 2, New York, Interscience Publishers, p.391 4-5 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1. REPORT NO. EPA 560/5-78-001 3. RECIPIENT'S ACCESSION NO. 4. TITLE AND SUBTITLE A Study of Industrial Data on Candidate Chemicals for Testing 5. REPORT DATE April 1978 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) Susanne Urso and Kirtland E. McCaleb 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS SRI International 333 Ravenswood Avenue Menlo Park, California 94025 10. PROGRAM ELEMENT NO. MEU - 5722 11. CONTRACT/GRANT NO. 68-01-4109 Research Request No. 2 12. SPONSORING AGENCY NAME AND ADDRESS Office of Toxic Substances U.S. Environmental Protection Agency Washington, D.C. 20460 13. TYPE OF REPORT AND PERIOD COVERED Final Report 14. SPONSORING AGENCY CODE 16. SUPPLEMENTARY NOTES 16. ABSTRACT This report describes the work carried out on Research Request No. 2 as specified by the Project Officer. Market forecasts were prepared for 12 chemicals specified by the Project Officer and include a discussion of economic information for each chemical: l,5-bis(chlorendo)cyclooctane, bis(2-chloroethyl) ether, bromoform, 2- chloroethanol, diethyl N,N-bis(2-hydroxyethyl)aminophosphonate, N-1,3- dimethylbutyl-N-phenyl-p-phenylenediamine, 4-methyl-7-diethylamino- coumarin, sodium fluoride, sodium fluorosilicate, stannous chloride, vinyl pyridine, and vinyl pyrrolidone. The information presented includes the following: production and trade statistics; a discussion of current uses, and in some cases, past uses; possible substitute products for the chemical in specific applications, and the current price of those substitutes; trends in production levels (i.e., future growth rates); and factors affecting growth in the market for the chemical. 17. KEY WORDS AND DOCUMENT ANALYSIS a. DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group Chemical Industry Organic Compounds Inorganic Salts Inorganic Silicates Flame Retardants Optical Brighteners Antiozonants Production Consumption Trends Market Forecasts Industrial Chemicals Chemical Economics 05/03 07/02 07/03 18. DISTRIBUTION STATEMENT Release unlimited 19. SECURITY CLASS (This Report) 21. NO. OF PAGES 4O 20. SECURITY CLASS (This page) 22. PRICE EPA Form 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE ------- |