Document L3NeGRkn50OK0MwqOn4Zq3ng

chemical HAMEs vinyl Chloride syhomymsi Chloroethene, Chloroethylene CHEMICAL FORMULAt cJ HH CHEMICAL C . C - Cl STRUCTURE! j H FIRE -'ROPERTIES (1) Appearance ........................................................................... ............................. Colorless gas j Molecular weight .......................................................................................... 62.5 i ] i Flammability limits, vol. X,upper................................. 33.0 (2) lower......................................................... 3.6 (2) Flash point, open cup, C ............................................... ......................... <&18 (cO'F) closed cup, C........................ ................................................. -78 (-108F) (3) Autoignition temperature In air, C .................................................... 472 (882F) ( Bolling point at 760 mm Hg, C .............................................................. -13.8 (4) at 10 irni Hg, "C............................................................ .. _88.0 Freezing point, C ........................................................................................ -153.8 Vapor pressure, irni Hg at 20C ................................................................ 2,550 (4) Solubility, wt. * in water................................ i.................................... 0.7 (20*0 water in....................................................................... 0.1 Specific gravity at 20/20C ..................................................................... 0.9121 (4) Heat of vaporization at 1 atm. Btu/lb (-13.8C)............................ 153 (4) iI Coefficient of expansion at 20C vol,/C ......................................... 0.00203 Viscosity at -10C, cps .............................................................................. 0.25 Revised 4/17/72 ucc 037879 REACTIVE d HAZARDOUS CHEMICALS MANUAL VINYL CHLORIDE J !LACfiVJ Tf Vinyl chloride Is a reactive monomer containing an ethylenlc double bond. It will polymerize if activated by light, oxygen, peroxides, or other polymerization catalysts. Because vinyl chloride will polymerize, it is assigned a stability hazard rating of 3_ In the UCC hazard signal system. General Reaction Characteristics - Vinyl chloride will undergo the usual addition and polymerization reactions which are characteristic of the ethylenlc double bond under the proper conditions of temperature and pressure and In the presence of proper catalysts. Under normal conditions of handling and storage, however, vinyl chloride Is relatively stable. In laboratory stability experiments, un inhibited vinyl chloride was heated rapidly In a closed vessel to a temperature of 260C before evidence of exothermic reaction was observed. Holding at 170*C for 14 hours did not produce measurable exothermic activity (5). Polymerization - By far, the most Important use of vinyl chloride Is In the production of polyvinyl chloride (PVC) polymers. Vinyl chloride In pure form (unInhibited and In the absence of catalysts) may polymerize very slowly at ambient temperatures, but the rate Is so slow that no hazard or safety problems arise during handling and storage under normal conditions of temperature and pressure. Heat alone does not initiate hazardous polymerization of vinyl chloride until temperatures of 250C or more are reached as noted In the proceeding paragraph. , > In the presence of catalysts, vinyl chloride will polymerize at ambient temperatures (20 to 50C) and the rate can become violent with Increasing tempera ture. The exothermic heat of polymerization is about 730 Btu per lb of monomer reacted (7). The reaction Is Initiated by free radical catalysts such as light, oxygen, peroxides, and similar polymerization catalysts. The amount of catalyst required is usually less than 0.1 per cent (6). Inhibitors - Phenol, amines, hydroqulnone, phenothlazlne,t-butyl catechol, and styrene effectively Inhibit vinyl chloride against polymerization reactions. Phenol, especially, was used to Inhibit vinyl chloride during storage and shipping In the early years of Industrial production. In more recent years, Inhibitors have found to be unnecessary and the majority of vinyl chloride production is handled without Inhibition (8). Control - Where the polymerization of vinyl chloride is desirable, the rate can be controlled by controlling the temperature of the reaction and the amount and type of catalyst. Also, In certain operations, the concentration of monomer can be controlled as In solution or suspension polymerization processes. Thus, the polymerization of vinyl chloride Is amenable to large-scale, commercial production and can be operated safely If properly controlled (6). , Revised 4/17/72 REACTIVE and HAZARDOUS CHEMICALS MANUAL -4- VINYL CHLORIDE Vinyl chloride Is a gas at normal temperatures and pressures which possesses a faint, pleasant odor and presents a relatively low toxicity hazard. The UCC Manual of Hazards to Health from Chemicals rating for vinyl chloride Is 3. in the UCC hazard signal system. The Occupational Safety"and Health Act of 1970 states that employees shall at no time be exposed to concentrations of vinyl chloride In air exceeding 500 ppm by volume (11). Eye Hazard - The Health Manual hazard rating for eye exposure to vapors of vinyl chloride is 2 which Indicates that minor Injury may occur from accidental ex posure If no treatment Is applied. Liquid vinyl chloride would be very cold under normal conditions (-13.8C), so exposure to liquid In the eyes could result in painful and possibly serious Injury from freezing. Avoid exposure to the eyes by wearing proper eye protection. In case of accidental contact, flush with water and report to the Medical Department. Skin Contact - The Health Manual hazard rating for exposure of skin to vinyl chloride is 2 which indicates that minor Injury may occur from accidental ex posure if no~treatnent is applied. Liquid vinyl chloride would evaporate quickly in contact with the skin but may cause painful Injury due to freezing by the cold liquid (-13.8C). If liquid vinyl chloride Is spilled on the skin, allow to evaporate and wash with water. Breathing - The Health Manual hazard rating for Inhalation of vinyl chloride vapors is 2 which means that minor Injury may occur In spite of prompt treatment. The Occupational Safety and Health Act of 1970 states that employees shall at no time be exposed to concentrations of vinyl chloride In air exceeding 500 ppm by volune (11). The long-range effects of continuous exposure to vinyl chloride vapors have not been fully determined, but recent evidence seem to Indicate that maximum concentrations for long-term exposure (years) should be considerably lower than 500 ppm and possibly as low as 50 ppm (12). Vinyl chloride vapors may have an anesthetic effect and exposure to high concentrations (>2.5 per cent) may produce dizziness and disorientation. Lung irritation and some edema may occur from acute vapor exposure (13). The lowest concentration at which odor can be detected by man Is about 4100 ppm. Exposure to 6600 ppm for one-half hour causes sleepiness, dizziness, and distinct odor Is detected (13). Revised 4/17/72 UCC 037881 REACTIVE nd HAZARDOUS CHEMICALS MAHUAL - 3-- VINYL CHLORIDE Addition Reactions (9) - The carbon-carbon double bond In vinyl chloride will undergo addition reactions which are characteristic of the ethvlenic func tional group. Two of the most common reactions involve: 1) the addition of chlorine to yield 1,1,2-trichloroethane, and 2) the addition of hydrogen chloride to form 1,1-dichloroethane. .. .. 1) h2c C-C1 + Cl2 A Cl 2) H2C 9-ci H Cl 3C - fc Cl H Other less familiar addition reactions of vinyl chloride are the following: Sulfuryl chloride (S02C12), In the presence of pyridine, reacts with vinyl chloride, at ordinary temperature, to give 1,1,2-trichloroethane and 2-2-dichloroethane sulfonyl chloride. Hypochlorous acid and vinyl chloride ( react to yield chloroacetaldehyde, C1CH2CH0. In the presence of anhydrous aluminum chloride, vinyl chloride condenses with ethyl chloride, at 50C, yielding the products, 1,1-dichloroethane and 1,1,3-trichlorobutane. At 0-5C, vinyl chloride reacts with benzene in the presence of alunlnum chloride, to give a mixture of chioroethylbenzene and 1,1-diphenyl ethane. Isopropyl chloride combines with vinyl chloride. In the presence of Friedel-Crafts catalysts, to give 4,4-dichioro-2-methylbutane. Glycerol-l,2-dichlorohydrin, CH20HCHC1CH2C1, and 3,3-dlchloro-npropyl alcohol, CH20HCH2CHC12, result from condensation of vinyl chloride with formaldehyde and hydrogen chloride. Ethyl vinyl ether is produced when vinyl chloride Is heated, under pres sure, with an alcoholic solution of sodium ethoxide. A wide variety of alcoholates and phenates can take part In this vinyl ether-forming reaction. Generally, the yields obtained from the phenates are low. Hazardous Reactions - In sunmary, the polymerization of vinyl chloride can be hazardous if not properly controlled Inasmuch as the heat of reaction is approx imately 730 Btu per pound of material polymerized. The reaction can be prevented by eliminating catalysts. The addition reactions generally require catalysts and/or high tempera tures and are not considered hazardous except possibly the addition of chlorine which occurs at ambient temperatures and can be violent .In the presence of light. Revised 4/17/72 ucc 037882 REACTIVE on4 HAZARDOUS CHEMICALS MAHUAL -5- VINYL CHLORIDE Protective equipment such as air-supplied mask should be used when high concentrations of vinyl chloride vapors are encountered. In case of exposure, re move the patient to fresh air; administer artificial respiration If needed; and obtain medical attention. Swallowing - Inasmuch as vinyl chloride Is a gas at normal temperatures. It Is unllkely that It could be swallowed by accident. It Is also Insoluble (el per cent) In water, so solutions containing harmful amounts of vinyl chloride could not be swallowed. Protective Equipment - When handling vinyl chloride, follow the usual safety precautions Including the wearing of safety glasses. Have air-supplied mask avail able for use If high vapor concentrations are encountered. Organic vapor cannlsters have been shown to be undependable and Ineffective against vinyl chloride vapors (18). Safety showers and eyebaths must be available. Revised 4/17/72 IjrV: 037883 REACTIVE mrf HAZARDOUS CHEMICALS MANUAL -6i VINYL CHLORIDE to. Vinyl chloride Is a.gas at normal temperatures and has a flash point below 0F. It has been assigned a fire hazard rating of 4 In the UCC hazard signal system and Is classified as highly flammablp by the National Fire Code. Vinyl chloride vapors will Ignite In the presence of cannon Ignition sources such as fires* sparks* hot surfaces, elec* trical discharges, etc. Methods of extinguishing vinyl chloride fires are the same as those used for most flammable gases. Dry chemical, carbon dioxide, and "alcohol"-type foams are among the most effective extinguishing agents. Water spray Is usually recom mended for fire exposure protection. Fire fighting personnel should be protected against possible release of hydrogen chloride gas. Water Spray - Vinyl chloride is a gas which Is nearly Insoluble In water. Therefore, water may be Ineffective In attempting to extinguish large fires Involving vinyl chloride except In massive quantities. Water spray Is usually reconvnended for fire exposure protection. _ .^ "Alcohol"-Type Foam - Large fires Involving vinyl chloride may be extinguished by the use of 11 alcohol "-type foam. An application rate of at least 0.15 gpm per square foot of area Is reconvnended. Prolonged application may be required because of the volatility of vinyl chloride. Small Fires Involving vinyl chloride may be extinguished with carbon dioxide extinguishers or with dry chemicals If properly applied. Areas In which vinyl chloride Is stored or handled should be provided with adequate fire fighting equipment, both fixed and portable. Automatic water sprays should be provided for cooling tanks and equipment In case of nearby fires. Hydrogen chloride (HC1) gas Is generated when ylnyl chloride Is burned. Fire fighting personnel should be aware of this hazard and should use proper personal protective equipment. Concern about the production of phosgene during burning of vinyl chloride has been shown to be unfounded In recent experimental tests. Research data have shown that phosgene Is not produced during burning of vinyl chloride except under carefully controlled laboratory conditions and then only In very small amounts (a few ppm). (15) Revised 4/17/72 UCC 037884 c 7 REACTIVE and HAZARDOUS CHEMICALS MAHUAL VINYL CHLORIDE A. Vinyl chloride is not an especially toxic material. Published data indicate that vinyl chloride is not toxic to fish in concentrations up to the limit of solubility in water (0.7 per cent) (16) and also not toxic to humans in concentra tions up to 0.66 volume per cent In air (13). However, dis posal of waste streams, spills, or leakage must be handled to avoid pollution of the environment. This can best be done by consultation with the authorized Environmental Protection Department. Indiscriminate dunplng to the atmosphere or sewers must be avoided. Incineration - The preferred method of disposal of vinyl chloride is by in cineration. This material Is a gas at normal temperatures and pressures and has a flash point below 0F. Burning, therefore, must be conducted in proper equipment and under careful supervision. Inasmuch as hydrogen chloride is a product of combustion of vinyl chloride, the Incineration must be done in a closed system equipped with vent scrubbers to neutralize and remove the HC1 gas. Biological Treatment - Biodegradability data show that vinyl chloride is re sistant to bio-oxidation; therefore, significant quantities should not be dis charged to biological waste treatment facilities. Chemical Landfill - Since vinyl chloride Is a gas at normal temperatures and pressures, It Is not amenable to disposal by chemical landfill procedures. I ti 1!' f Revised 4/17/72 ucc 037885 REACTIVE 9*4 HAZARDOUS CHEMICALS MANUAL 8- VINYL CHLORIDE ; a i;: t- , -- --Ml I Vinyl chloride Is a highly flammable gas which presents a relatively-low toxicity hazard to personnel. Areas In which vinyl chloride is handled should be well ventilated, preferably open structured, to prevent accunulatlon of vapors. Normal protection against exposure to fires and other Ignition sources should be maintained. Exposure to air or oxi dizing materials should be avoided. Vinyl chloride is not particularly corrosive to metals and can be handled In most common materials of construction. Buildings and Equipment - All buildings used for processing, handling, and storage of vinyl chloride should be constructed of flre-reslstapt materials In accordance with the building code of the appropriate state regulatpry agency. Adequate ventilation must be provided In enclosed areas to maintain the concentration of vinyl chloride vapors below the Threshold Limit Value (500 ppm) to protect the health of personnel and below the lower explosive limit to protect against fire hazard. Open structures are preferred where possible to prevent accumulation of vapors. Steel Is normally an acceptable material of construction for storage tanks, piping, and other equipment used In handling vinyl chloride. Other accept able materials are listed In Section G. Aluminun and copper should not be used (see note, Section G). Construction should be In accordance with ASME standards. Electrical Protection - Electric motors, lights, pumps, and other electrical equipment used in areas In which vinyl chloride Is handled should be In compliance with National Electrical Code, Class I, Group D, Division I or II. Metal tanks, columns, piping, loading racks, pumps, drums, and other similar metallic equipment should be provided with proper electrical grounding In accordance with the applicable elec trical standards of the Engineering Standards Manual. Vents and Safety Valves - All tanks, processing vessels, pumps, reactors, heat exchangers, ana similar equipment should be protected by adequate emergency vent relief devices such as safety valves, rupture discs, vent units, etc. In accord ance with standard engineering practice (17). All safety devices should be discharged to safe locations to avoid pollution of the environment. Impingement upon equipment, or* hazard to personnel. Revised 4/17/72 Ucc 037836 r REACTIVE ond HAZARDOUS CHEMICALS MANUAL - 9- VINYL CHLORIDE Storaqe - Vinyl chloride, in pure form free of air contamination, may be stored for reasonable periods of time (one year) without danger from hazardous decom position or polymerization. It is normally stored under its own vapor pressure, although sometimes nitrogen blanketing my be employed to increase the storage pressure in order to facilitate pimping out of the tank. The temperature should be maintained below 50C and preferably at 0 to 20C. Refrigeration Is generally used to maintain the temperature at a reasonable level. Inasmuch as vinyl chloride boils at -13.8C, a positive pressure will be exerted at ambient tempera tures (33 pslg at 70 F). The design pressure for storage systems should be 100 psig with 150 psig flanges, fittings, etc.(8). Water spray protection should be provided for all storage tanks containing vinyl chloride. Air (oxygen) and oxidizing materials and water should be excluded from all equipment in which vinyl chloride is handled by use of inert gas (nitrogen) purge and blanketing. A level ofdOOO ppm by volune of oxygen is reconmended (8). Experience has shown that Inhibitors are not needed in storing vinyl chloride. In years past some manufacturers used Inhibitors, particularly phenol in storing vinyl chloride (8). Tests have shown, however, that they are not needed, and most viqyl chloride Is currently stored and shipped uninhibited (18). Revised 4/17/72 ucc 037887  Y REACTIVE m4 HAZARDOUS CHEMICALS MANUAL - 10 - VINYL CHLORIDE The materials of construction listed below have been examined by the Materials Technology Group of the Engineering Department for handling vinyl chloride In most common pieces of equipment encountered In plant production such as tanks, pipes, pumps, bearings, seals, gaskets, etc. The materials marked OK are considered satisfactory for this service in contact with vinyl chloride from the standpoint of both corrosion and product quality. Those marked NG are not approved for this service. Materials that may be hazardous because of the reactivity of the product In the presence of the material are marked UNSAFE. For more detailed comments on materials of construction for particular items of equipment, consult the appropriate Engineering Department Design Report issued for the specific operating unit. For specific shipping recomnendatlons, refer to the "Group I Shipping Data - Container Manual". Materl al_______ Recomnendatlon Steel Stainless steel Aluminum 3003 Nickel Zinc Baked phenolic coatings Other organic coatings Other non-metal lies OK OK UNSAFE OK UNSAFE OK NG (1) (1) Glass, Teflon, compressed asbestos and ceramics are approved. No elastomeric materials are adequately resistant. NOTE: Copper and copper-bearing alloys should be excluded from vinyl chloride service due to the poslblllty of traces of acetylene reacting with the copper to form acetyl Ides. Al uninun and al uni nun alloys, zinc and zinc alloys must be excluded due to their reactivity with vinyl chloride (8). Revised 4/17/72 ) Ucc 037888 - n.;- REACTIVE ond HAZARDOUS CHEMICALS MANUAL VINYL CHLORIDE [ (1) Tables of Physical Properties. Laboratory Manaul, Vol. 40, UCC Research and Development Department, 1964.. ' (2) Bureau of Mines Bulletin No. 627, Flawnabllltv Characteristics of Com bustible Gases and Vapors (1965). (3) Laboratory Waste Disposal Manual, Manufacturing Chemists Association (1970), 1825 Connecticut Avenue, N.W., Washington, D. C. 20009. (4) Shank, R. L., Thermodynamic Properties of VIhyI Chloride, UCC Research and Development Department Report, File No. 4211,June 21, 1965. (5) Snyder, 6. E., Vinyl Chloride, Thermal Stability. R&D Department Project Report, January 31, 1972, File No. 16747. (6) Encyclopedia of Polymer Science and Technology, Vol. 14, p. 321, Interscience Publishers, 1971. (7) Cox, J. D. and Pilcher, G., Thermochemistry of Organic and Organometalllc Compounds. Academic Press, N. Y, (1970). p. 504. (8) Shelley, P. G., and Sills, E. J., Monomer Storage and Protection. Chem, Eng. Progress, Vol. 65, No. 4, April, 1969, pp. 32-34. (9) Kirk-Othmer, Encyclopedia of Chemical Technology. Vol. 5, pp. 172-173, Interscience Publishers. (10) Manual of Hazards to Health from Chemicals, UCC Industrial Medicine and Toxicology Department, Third Edition, 1965. (11) Federal Register. Vol. 36, No. 157, August 13, 1971, p. 15102. Threshold Limit Value. American Conferences of Governmental Industrial Hygienists, 1970. (12) Private Conmunication from R. N. Wheeler, January, 1972. (13) Patty, F. A., Industrial Hygiene and Toxicology. Vol. II, Second Edition, 1962, Interscience Publishers, p. 1304. (14) Chemical Safety Data Sheet SD-56. Manufacturing Chemists Association, 1825 Connecticut Avenue, N.W., Washington, D. C. 20009. (15) Dowell, E. L., Handling Vinyl Chloride Emergencies. Loss Prevention, Vol. C, ( CEP Technical Manual, 1971. ,, Revised 4/17/72 UCC 037889 J REACTIVE nd HAZARDOUS CHEMICALS MANUAL - 12 - VINYL CHLORIDE (16) Evaluation of Hazards of Bulk Water Transportation of Industrial Chemicals, U. S. Department of Comnerce/Natlonal Bureau of Standards* 1970. (17) Process Safety and Fire Protection Manual. Vol. I. Group I Safety Department (1971). (18) Canterbury, J. C., Storage and Shipment of Uninhibited Vinyl Chloride, R&D Department, 1971. (19) Materials of Construction Manual, Materials Technology Group, UCC Engineering Department, 1971 i !, i j: .vv.. 1 . .?',! Revised 4/17/72 ... UCC 037890