Document 7M08EV6dg8w2RKmJxb2RX7E5j

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Iirnnl ( VINYL PLASTICS Thir Dermatological end Chemical Aspects GEORGE E. | MORRIS, M.D. BOSTON DURING the past 12 years there has been a fivefold increase in the number of dermatoses caused by the chemicals used in the manufacture of plastics,1 New plastics are being developed each year, and it is necessary that the industrial phy sician and dermatologist know the fundamentals of the chemistry of the different plastics, so that lie will lie able to judge correctly any case that comes to him for judgment concerning causal relationship with the work, j The patient knows little about his job except that he uses "raw stock" or "over| lav" decorative, that lie "spreads vinyl onto cloth" or that he "dips a plastic pencil I into a solvent known as MICK." The examining physician should know what the I chemical of the "raw stock" can he.- He should know something about the chemistry of the vinyls and should have a speaking acquaintance with such things as MEK I (methylethy! ketone), TCP (tricresyl phosphate), DOP (dioctyl phosphate), etc. | Plastics, in general, may he divided into five groups or classes: 1. Condensation 2. Vinyl (or irolymemation) 3. Cellulose 4. Synthetic rubbers 5. Miscellaneous Polymerization resins may be divided into six groups: 1, Polyvinyl resins 2. Polyacrylate resins 3. Polyvinylidene resins 4. Polyethylene resins i 5- Polystyrene resins 0. Cournarone and imlene resins j Polymerization is the chemical union of two or more molecules of a substance to j form a new compound without the elimination of a secondary compound. A monomer j is a substance consisting of a single part; a dimer is a substance consisting of two I parts, etc. I ji Morris is Assistant Clinical Professor of Dermatology, Tufts College Medical School. I 1. Morris, G. K.: Condensation Plastics: Their Dermatological and Chemical Aspects. * C\ M. A. Arch. Inch Hvg. 5:37-43 (Jan.) 1952. I d.Ab-f 'frc*i t Occ^p t` 515-535, TT BpG03658 20497001 536 INDUSTRIAL HYGIENE AND OCCUPATIONAL MEDICINE The polymerization resins .are almost always compounded with other ingredients to produce the finished plastics. Compounding ingredients include plasticizers, stabi lizers, pigments and dyes, lubricants, and fillers. POLYVrNYL RESINS2 Vinyl resins contain the vinyl linkage, --CH2 --CHX. X must be a strongly negative group--chloride, acetate, butyrate, alcohol, or acetal. Vinyl chloride monomer CH a CH Acetylene + HCI--------------------------------- * CH, s= CHC1 Hydrochloric acid Vinyl chloride CH = CHC1 -+ [ Heat J Pressurei Catalyst CH,--CH -- CH, CH-- -- CH,-- CH -- d di ci Copolymers Vinyl chloride polymer CH, = CHCI CH* = CHOCOCH, Vinyl chloride 80-98% Vinyl acetate 2-207c -- CH -- CH -- CH, -- CH -- CH, -- CH -- CH, Cl Cl O-C--O-CH, CHI --CH, I Cl Polyacryla; derivatives: CH,= t CH, = ' CH, = < CH, = Methyl Acryla CH, CN-- CH Ethylene c; The polyn ( The trade coatings, leal! Only a fe\ Monon Polymeriz It is often vinyl chlorid- Dermatitis in a coaler of vinyl plastics. The more vinyl acetate that is used, the more soluble is the product and so the more useful for coatings (see "Flow Chart"). The trade names include Vinylite, (jeon, Koroseal, Sallcx, Marvinol, etc. They are used as moulding compounds, adhe sives, fabrics, cable coverings, floor tile, belts, raincoats, toys, etc. I have not >cen any eruption from the finished product, but the Figure shows an eruption from vinvl latex used for coating artificial leather. 2. Slircve, R. N.: Chemical Process Industries, \'ew York, McGraw-Hill Book Company, Inc., 1945. The trade n;. covers, pipe. ro Cracked p<o C5 The trade n; of blown bo: O o cable insula1 BFG03659 MORRIS--yiSYL PLASTICS 537 POLYACRYLATE RESINS Polyacrylate resins are formed from the polymerization of acrylic acid and its derivatives: Cll.a CHCOOH CH,= CHCOOCH, CH,= C(CH,)COOH CH*= C(CH)COOCH, Acrylic acid Methyl acrylate Methacrylic acid Methyl methacrylate Methyl Acrylate Polymerization Cracking Petroleum------- process -- CH* = CH* Ethylene H*0 CHj = CH* ---------------------Cl CH*CL CHjOH 4- NaCN -- Ethylene chlorohydrin catalyst CHj CN -- CH*OH + CH,OH------------------------------------ Ethylene cyanohydrin Methanol CH.CHOCOCH, The j>olymer is --CH, --CH--[CH,--CHU --CH, --CH 0 = C --OCH, O --C --OCH, O --d--OCH. The trade names are Plexiglas and Lucite. They are used as dentures, adhesives, coatings, leather finishes, optical novelties, etc. Only a few cases of stomatitis have been seen from acrylic dental plates. POLYVINYLIDENE RESINS Monomer--vinylidene chloride CH- -- C Cl- Polymerizes Cl Cl --CH,--C -- il CH, --C -- Cl Cl I CH, --C -- I Cl Tt is often copolymerized with vinyl chloride (10% vinylidene chloride and 90% vinyl chloride). H|f Cl H J1 C11l H11 Cl Hi1 Cj l H i -- C -- Ci1 -- C i -- c11 -- C1 -- C i -- CtI -- C -- C I -- . ir H H Cl H Cl H Cl H The trade name is Saran. It is used in the manufacture of upholstery fabrics, seat covers, pipe, tubes, battery cases, belts, suspenders, etc. POLYETHYLENE RESINS Cracked petroleum Heat CH,= CH,----------------------- Kthyknc Pressure ' H HHH 1111 --C--C--C--C- i[I ! HHHH Polyethylene The trade names are Polythene and DYXF Resin. The resins are used in the form of blown bottles, tubing, tape, sheeting, lilm, and tor packaging, tableware, wire and cable insulation, molded closures, etc. BFG03660 538 INDUSTRIAL HYGIENE AND OCCUPATIONAL MEDICINE Occasional sensitization to these resins occurs, especially in workers coating the resins before complete polymerization has occurred. Styrene POLYSTYRENE RESINS f^s-CH=CHa fc-- Polymerizes as follows: *r Vinyl r A and H ma\ D ma\ CH, -- Cl The trade names are Lttstron, Lustrex, Polystyrene, Styratnic and Plexene. They are used as bottles, jars, closures, tableware, toitet articles, wall tile, brushes, etc. COUMARONE AND INDENE RESINS These are coal tar derivatives. CH,--C--{` CH. CH, CC.' Cf The jx for shipnn tization d* The polymerization is similar to that of styrene. The trade names are Cumar, Nevillae, and Nypene. These are used for coatings, varnishes, printing inks, tile, rubber compounding, and chewing gum. The comiMjitnds added- to the resins include plasticizers, stabilizers, lubricants, colorants and fillers. Plasticizers are chemicals which render the finished product more plastic. They make.up 10% to 50% of the weight of the finished product. They include the follow ing: phosphates (tricresyl phosphate--TCP); phthalates (dioctyl phthalate-- DOP); ricinoleic acid derivatives; sehacic acid derivatives; azelates; polyesters; nitrile rubbers; petroleum derivatives: chlorinated aromatic hydrocarbons. Stabilizers arc substances which prevent decomjjosition from heat and sunlight. They make up 2 to 5% by weight. They include lead compounds (basic white lead carbonate and basic white lead silicate) ; tin compounds, epoxides, phosphates, and metallic soaps. Lubricants are added to plastics and make for ease of flow (internal and exter nal). They include fatty acids, waxes, oils, and metallic soaps. The colors used include dyes and pigments. Fillers are added to confer chemical resistance, mechanical strength, electrical properties, and thermal resistance, 'idle mineral fillers are commonly used and include clays, mica, asbestos, limestone, and diatomaceous earth. BFG03661 4 o CO 3 2 ( ng the They l`?s etc. XeviJ' iihher !bants, They iolluw- ilate-- .inters; 'lalight. ii' lead < and cxterused .ctrical 'l and MOKFttS--riNYl. PLASTICS SUMMARY Vinyl resins are formed by the {jolymerization of RH BH r BH I i 111! A--C=C--D--------------------- * --C--C-- C--C II II AD AD AH II -C--C-- II BD 539 :\ and li are preferably hydrogen, occasionally FI or Cl. H may he hydrogen, Cl, F, CN, or CH3. D may be hydrogen or COOH, Cl, F, CN, COOR, C,,H5, -- O--R,-- CH, -- CH CH*--C--(CHs) CH.CM, CCX CCl H C.H. Cl OR O COCHj F COOH CN COOH COOCH, CN Cl CN Ethylene Styrene Vinyl chloride Vinyl ether Vinyl acetate Vinyl fluoride Acrylic acid Acrylonitrile Methacrylic acid Methyl methacrylate Vinylidene cyanide Vinylidene chloride Chloroacrylonitrile The polymerization resins are handled by enclosed processes until they are ready for shipment. Workers handling the partially polymerized resins may develop sensi tization dermatitis. Eruptions caused by the finished products are rare but do occur. 20497005 BFG03662 Reference la made to your letter of May 0 regarding tne xvo resins, Geon 103EP and Geon 404, which were discussed with Mr. Phllfrcdc Dr* Lehman's group on May 5* Resins such as your Geon IO3EP consisting of polyvinyl chloride and Geon 1*04 consisting of Hycar rubber and polyvinyl chloride are acceptable for use In contact with product prepared under Federal meat Inspection. Very truly yours. E. M. Mehurln, Chief Laboratory Divieion Meat Inspection 20498001 BFG03663 May 8, 1953 Dr. R. A. Mehurin, Chief laboratory Section Meat Inspection Division Bureau of Animal Industry 0.S. Dept, of Agriculture Washington, D. C. Deer Dr. Mshuriai In our conference with llr. Fbllbeck end Dr. Lehman on May 5, 1953 ee dlecueeed the uee of two resine as manufactured by / The B. F. Goodrich Company. these ere Identified ee Oeon lOJgP end Oeon liOU. The oonpoeitloa of theee ie ee fallowss Oeon 103BP - Polyrinylahloridej Oeon IfOh - Rycor Bobber end F$2y- 1 vioylohlorld*. V; ; i ' i It wee the oonsensus of opinion of tbeoonfsreee in our neetlng thet approval of theee two resins would be granted for food ; purposes* You say regard this letter ee ea application for approval of these two material* ee Ingredients of food wrappers in Federally inspected neat handling establishment#. Very truly yours. WEU W. S McCorniok Department of Industrial Hygiene and Toxicology 20498002 BFG03664 T