Document ZGKVjB15eRjJm1r3Evzzv6ep

* E N R Y L 01 A M O N 0 Albert j. beveridge, sx Gary H, BAISE NAROLO HIMMELMAN CHRISTOPHER h BUCKLEY, jR STEPHEN L- GOROON ALCXANOCR w, 3IERCK JOHN FRENCH m JOHN N HANSON ANDREW E. MISHKIN WILLIAM N.MEOCMAN'JR GAINES GWATHMCY.HI CYNTHIA A LEWIS KARL 5. BOURQEAU JOHN S' GUTTMANN DON G. SCROGGIN GARY J. SMITH BENJAMIN F. WILSON AMY L. COWARDS ROBERTBRAGER RICHARO 5. 0AVI3 THOMAS RlCHICHl DEANM CANNON VIRGINIA S ALBRECHT PAUL SHORB.ICC ROBERT H, SINGLETARY, JR. DONALD J. PATTERSON, JR MARK A, TURCO BRENDA MALLORY THOMAS C- JACKSON KATHRYN C- S1M U SZ KO VICZ MAROLO L- SEGALL PETER j SACRIPANTI* dustin p. oroway KENNETH S, KAUFMAN Charles f gauvin MARC A- ZCPRETELLO* JOHN O. GlGLIO* ELLIOT 0- EOCR * SUSANJ KOROSTOFF* AMY L, COM STOCK * NOT AOMITTCO in d.c. LAW OFFICES Beveridge & Diamond, R C, 1333 New Hampshire Avenue, N.W. Washington, D. C. 20036 (202) 826-0200 TELECOPIER (202) S2S-023-* TELEX 3725536 BCVOIA WSH WRITER'S DIRECT OI*L NUMBER (202) 828-0281 April 23, 1987 l OI PARK AVENUE NEW YORK, N, Y. I O I 7 S (Z\Z) SS7-3355 BEVERIDGE & diamond ONE BRIDGE PLAZa FORT LEE.N, J. 0702* (2 01) 5SS-SI62 CARL EAROLEY OF COUNSEL JIM j. TOZZI CONSULTING ECONOMIST George A. Fisher Clerk, United States Court of Appeals for the District of Columbia Circuit United States Courthouse, Room 5411 333 Constitution Avenue Washington, D.C. 20001 Re: Natural Resources Defense Council, Inc. v. U.S. Environmental Protection Agency, et al., No. 85-1150: Errata to Brief for Intervenor The Vinyl Institute Dear Mr. Fisher: Enclosed please find the original and 30 copies of a new first page to the Table of Contents; the page filed with our brief inadvertently contained two typgraphical errors. Please distribute the new page to the judges. Copies have been served on counsel of record in this action. Thank you for your attention to this matter. Sincerely RB/bjd Enc. 768F Rob Brager CMA 015462 TABLE OF CONTENTS TABLE OF AUTHORITIES...................................................................................... ISSUES PRESENTED................................................................................................ INTRODUCTION.......................................................................................................... SUMMARY OF ARGUMENT ...................................................................................... ARGUMENT.................................................................................................................... I, SECTION 112 PERMITS THE ADMINISTRATOR TO CONSIDER TECHNOLOGICAL FEASIBILITY WHEN SETTING EMISSION STANDARDS SO LONG AS THE STANDARDS PROVIDE THE PUBLIC WITH AN AMPLE MARGIN OF SAFETY...................................................................................... A. By Considering Technological Feasibility, the Administrator May Rationally Regulate Hazardous Air Pollutants ...................................................................................... 1. Selection of appropriate standards. ... 2. Ensuring that an ample margin of safety is attained........................................................ 3. Mitigating adverse consequences of regulation.................................................................. 4. Resolving enforcement issues............................... B. EPA Has the Same Authority to Consider Technological Feasibility Under Section 112 That the States Have, and at Times Even EPA Has, Under Section 110....................................................................... C. The Court Should Uphold the Vinyl Chloride Standard Because the Administrator's Consideration of Technological Feasibility Did Not Interfere with His Ability to Provide an Ample Margin of Safety to Protect the Public Health........................................... PAGE iii 1 1 8 9 9 9 9 14 16 18 20 24 CMA 015463 Chemical Safety Data Sheet SD-56 PROPERTIES AND ESSENTIAL INFORMATION FOR t SAFE HANDLING AND USE OF VINYL CHLORIDE ADOPTED 1954 Chemicals in any form con be safely stored, handled or used if the physical, chemical and hazardous properties or* fully under stood and th necessary precautions, including the use of proper safeguards and personal protective equipment, are observed. Manufacturing Chemists' Association, Inc. 1625 Eye Street, N. W., Washington 6, D. C. CMA 015464 Copyright 1964 by Manufacturing Chemiat*' Association. Inc. CMA 015465 CHEMICAL SAFETY DATA SHEET VINYL CHLORIDE SUMMARY Vinyl chloride is a highly volatile extremely FLAMMABLE compressed gas which is ordinarily handled in liquefied form under pressure. It has a mild anesthetic action in concentrations above 500 ppm. and its vapors- are irritating to the eyes. Precautions necessary in handling the material are detailed in the body of the Safety Data Sheet. Key points to consider for safe handling include: 1. Keep away from heat, sparks and open flame. 2. Provide adequate ventilation. 3. Ground equipment and containers before discharging to reduce danger of ignition from static sparks. 4. In discharging do not heat containers above 50'C. (122F,). No heat should be applied to tank cars. 5. All equipment should be of steel and have a designed working pressure of at least 100-150 psi. 6. In the event of accidental leaks, spills or whenever excessive vapor con centrations may be encountered only personnel equipped with approved respiratory protection should be permitted in the contaminated area. 7. Chemical safety goggles should be worn when discharging containers or tank cars or whenever there is a danger of the liquid or saturated vapor coming in contact with the eyes. 8. Waste disposal should be away from any source of ignition. Dilute phenolic residues before discharging to sewer. In case of fire use carbon dioxide or dry chemical extinguishing equip ment. In the event of contact with the liquid remove contaminated clothing immediately. For eyes flush immediately with large quantities of water for at least 15 minutes while medical attention is being sought. CMA 015466 TABLE OF CONTENTS Page 1. NAME ____________ ________________ --------------- --------- ---------------- --- -- 5 2. PROPERTIES ................... ...... ............... --__----------------------------------------------2.1 Grade .................... ..... _....................... --...... --------- ------ ----- -------------------2.2 Important Physical and Chemical Properties................................. ..... ..... 2.3 Hazardous PropertiesTM----- ----------------------------------------------- ------------- ------- 5 5 5 6 3. UStlAL SHIPPING CONTAINERS................................. __.........------ -------------- 6 3.1 Type and Size.____________________________._____________________________ 6 3.2 Label or Identification......................... ---------------- ----............... ............-- 6 3.3 Disposal and Return Precautions..... ---------------------- ------------------------------- 7 4. UNLOADING AND EMPTYING......... ....................... .................. ................... ....... 7 4.1 Health Hazards________________--.... .......---------- ------ ------------------------- 7 4.2 Fire and Explosion HazardsTM-------- ---- ----------------------- ------ ------------------ 7 4.3 Cylinders ___ _____ ___ _____ ----------------------------- ---------------------- -- 7 4.4 Tank Cars --.................................................... ----------------- 8 5. STORAGE8 5.1 Hazards ....... ............ ....... -...............-- ------------------------------------------------ 8 5.2 Conditions of Storage--------------------------------------------------------------------------8 6. HANDLING9 6.1 Health Hazards........................ 9 6.2 Fire, Explosion, and Polymerization Hazards____ __ _____________ 9 6.3 Spills and Leakage_____________________________ ________________ 10 6.4 Employee Education and Training---_-------------------------- 10 6.5 Personal Protective EquipmentTM.____________ ____ 11 6.6 Engineering Controls-------------------- ---- ---................................. .................. 13 6.7 Ventilation _____________ ----------------------------------------- ----------------------13 6.8 Tank and Equipment Cleaning and Repairs----------------------...--13 6.9 Repackaging----------------------------------------------------------------------------------------- 14 7. WASTE DISPOSAL....................... ......... ................................................................... 14 8. HEALTH HAZARDS AND THEIR CONTROL................. .................................. 15 8.1 Hazards ---------------------------------- - --15 8.2 Prevention and Control.................... ......... ... ... ..... ....... .... ............... -- ........ 15 8.3 Personal Protective Equipment_____________________ 15 8.4 First Aid and Medical Care................................................... 16 The information and recommendations contained in this publication have been compiled from eources believed to be reliable and to repreeent the best current opinion on the subject, No warranty, guarantee or representation is made by the Association as to the absolute correctness or sufficiency of any representation contained in this and other Safety Data Sheets and Manuals, and the Manufacturing Chemists' Association assumes no responsibility in connection therewith; nor can it be assumed that all acceptable safety measures are contained in this and other Safety Data Sheets and Manuals, or that other or additional measures may not be required under particular or exceptional con ditions or circumstances. CMA 0X5467 Chemical Safety Data Sheet Manual Sheet SD-56 VINYL CHLORIDE Adopted February, 1954 1. NAME Chemical Names: Common Name: Formula: Vinyl Chloride Chloroethylene Chloroethene Vinyl Chloride CHaCHCl 2.1 Grade: 2. PROPERTIES Technical with inhibitor. (Purity of sample 99.42%) 2.2 Important Physical and Chemical Properties:* Boiling Point__________ _____________________ _____ --13.8C. (+7F.) ColorColorless or water white Corrosivity.___ Noncorrosive at normal atmospheric tem peratures when dry (moisture free). In con tact with water at elevated temperatures vinyl chloride accelerates corrosion of iron or steel. Explosive Limits (Percent by Volume in Air)-------- Lower 4% ; Upper 22% Flash Point_______--78C. (--108.4F.), Open-Cup HygroscopicityNo Critical Pressure _________________________ _52.7 Atmospheres Critical Temperature _______________ 158.4C. (317F.) Deliquescence___________ No Ignition Temperature, Autogenous------------------------472.22C. (882F.) (Vapors above --60F.) Light Sensitivity---------------------------------- -----------------Not a factor in handling inhibited vinyl chloride Melting Point___ ._ 153.71C. (--245F.) (Freezing Point) Molecular Weight_ .62.50 Odor_______________ .Sweet smelling gas Physical State_____ .Gas at ordinary temperature and pressure. Liquid under pressure in cylinders or pres sure vessels at room temperature. Reactivity. Polymerizes readily in presence of air, sun light, oxygen or heat. This behavior is due to the presence of a double bond. Otherwise vinyl chloride is quite stable. Specific Gravity ..9121 @ 20/20C. (Water = 1.00) Vapor Density.__ .2.15 (Air = 1.00) Vapor Pressure.. .2580 mm. of mercury 20 "C. (68F.) Many of the data recorded under this paragraph were determined in the research laboratory of one of the large producers of vinyl chloride and are based on a technical grade material having a purity of 99.42%. Materials from other sources may vary in accordance with the nature of the impurities or the character of the inhibitor present. 5 CMA 015468 Manual Sheet SD-56 Manufacturing Chemists' Association. Inc. Vinyl Chloride 2.3 Hazardous Properties 2.3.1 HEALTH HAZARDS (See 8. Health Hazards and Their Control) Aside from the risk of fire and explosion, vinyl chloride presents no other very serious problem in general handling. The presently ac cepted upper limit of safety as a health hazard is 500 ppm. 2.3.2 FIRE HAZARD Vinyl chloride vapors form flammable mix tures with air at all temperatures above --78C. (--108.4F.) 3. USUAL SHIPPING CONTAINERS 3.1 Type and Size 3.1.1 Approved ICC cylinders and tank cars designed to carry liquid gases under pressure and equipped with safety relief devices. 3.1.2 All parts of valve and safety devices in contact with contents of containers must be of metal or other material, suitably treated if necessary, which will not cause formation of any acetylides. A good practice is to dismantle all valves for inspection before each loading. Approved cylinders include ICC-4B300, ICC4BA300, ICC-3A300, and ICC-3AA300. Cylin ders with brazed seams are not permitted. 3.1.3 Some types of tank cars are ICC-106A500, ICC-106A500X, ICC-105A300 and ICC105A300W, Maximum permitted filling density is 84 % for cylinders and for Class ICC-106A cars and for Class ICC-105A cars 87%. 3.1.4 Filling density is defined as the per cent ratio of the weight of chemical in the tank to the weight of water that the tank or cylinder will hold. 3.1.5 ICC Regulations require that vinyl chloride must be inhibited for the purpose of transportation (See 6.2.3). 3.2 Label or Identification 3.2.1 Each container of vinyl chloride (in cluding tank cars) should carry an identifying label or stencil. 3.2.2 The Manufacturing Chemists' Association recommends the following in addition to, or in combination with, any label warnings or other statements required by statutes, regula tions, or ordinances: " VINYL CHLORIDE DANGER! EXTREMELY FLAMMABLE Keep away from heat, sparks, and open flame. Keep container closed. Use with adequate ventilation. Avoid prolonged breathing of vapor. 6 CMA 015469 Vinyl Chloride Mmnufmcturing Chemitti' Association, Inc. Manual Sheet SD-56 3.2.3 Each shipping container must bear the ICC red label for FLAMMABLE com pressed gases. 3.2.4 Tank cars and railroad cars carrying one or more containers of vinyl chloride must bear the ICC DANGEROUS placard. 3.3 Disposal and Return Precautions 3.3.1 Small containers (ICC-4B300 and ICC4BA300, without brazed seams, ICC-3A300, ICC-3AA300) should be drained free of liquid vinyl chloride and the valves closed tightly be fore they are returned to the supplier. No air should be permitted to enter the container (See 4.3). 3.3.2 In addition, the following precautions must be taken: 3.3.2.1 Return of Small Containers The cylinder valve protection cap or out let cap must be securely replaced. The lower portion of the ICC shipping tag, if attached to the cylinder, must be removed. In other cases, applicable to ICC Regulations, compliance is essential. Bill of lading should give the cylinder identification number (which appears on the shoulder of cylinder) for each cylinder shipped, show name of consignee and indicate that the cylinders are empty (See 3.3.5). Full or partly emptied cylinders should not be returned without permission of the sup plier. Such cylinders must be shipped as full cylinders and correspondingly labeled and tagged (See 3.2). All empty cylinders should be returned promptly. 3.3.3 Tank cars (ICC-106A500, ICC-106A500X, ICC-105A300, and ICC-105A300W) should be drained free of liquid vinyl chloride, the valves should be securely closed and the valve plugs replaced. No air should be per mitted to enter the vessel. The inert gas used for the unloading procedures (See 4.4 Tank Cars) should be left in the vessel at a pressure not to exceed the service pressure for which the car is authorized. . 3.3.4 In addition, the following precautions must be taken: 3.3.4.1 Return of Tank Cars As soon as a tank car is completely un loaded, all valves must be made tight, the un loading connections must be removed and all closures made tight, except that heater coil inlet and outlet pipes (if any) must be left open for drainage. Heater coils must never be used in unloading vinyl chloride. Empty tank cars should be returned as promptly as possible, in accordance with instructions re ceived from shipper. 3.3.5 Follow ICC Regulations regarding the replacement of closures, condition and labeling of empty containers; condition of empty cars and placard requirements before returning to shipper. The ICC DANGEROUS placards on sides and ends of tank cars must be removed, or reversed (if in metal placard holders) by the party discharging the tank car. The empty car must be offered to the receiving carrier either without placards, or preferably with four (4) DANGEROUS-EMPTY placards. 4. UNLOADING AND EMPTYING 4.1 Health Hazards (See 8. Health Hazards and Their Control) 4.1.1 Aside from the risk of fire and explo sion, vinyl chloride presents no other very seri ous problem in general handling. The presently accepted upper limit of safety as a health haz ard is 500 ppm. 4.2 Fire and Explosion Hazards 4.2.1 Vinyl chloride should always be handled with full recognition of its flamma bility. Precautions should be taken both to keep the material enclosed and to eliminate sources of ignition. Reliance must be placed upon the elimination of all sources of ignition and on the provision of sufficient ventilation to keep escaping vapors at nonflammable levels (See 6.2). 4.3 Cylinders 4.3.1 Precautions generally applied to use of cylinders (ICC-4B300 and ICC-4BA300, without brazed seams, ICC-3A300, ICC-3AA300) for flammable liquefied gases should be "Used. 4.3.2 A water bath heated to a maximum of 50C. (122F.) may be used to empty cylinders by means of the vapor pressure of the vinyl chloride. 4.3.3 Check valves must be installed in feed lines from the cylinder to prevent the reactants from entering the cylinder. 4.3.4 When the cylinder is empty, the valve should be securely closed. Air should not be allowed to enter the container. 7 CMA 015470 Manual Shet SD-5S Manufacturing Chemists' Association, Inc. Viyl Chlorid* 4.3.5 Valve protective caps should be kept in place on cylinders except when the cylinders are connected for discharge. 4.3.6 Cylinders must not be filled except by or with the consent of the owner, and then only in accordance with the Regulations of the In terstate Commerce Commission. 4.3.7 No attempt should ever be made to mix gases or liquids in a cylinder. 4.4 Tank Cars 4.4.1 Applicable instructions for unloading tank cars containing flammable liquids are set forth in MCA Manual Sheet TC-4. (Also see ICC Regulations, Sec. 74.560 to 74.563 inclu sive, for unloading tank cars.) 4.4.2 Shipper's instructions should always be followed and all caution markings on both sides of tank and dome should be read and observed. 4.4.3 In the event of a tank car fitting fail ure or leak, the shipper should be telephoned or wired immediately for instructions (See 6.3). 4.4.4 Tank cars should be electrically grounded to dissipate static or induced light ning charges. 4.4.5 No heat should be applied to the tank car. An inert gas line or compressed vinyl chloride gas line should be attached to vent connection of the tank car to provide a pressure for transfer of the liquid vinyl chloride from tank car to receiving tank. Cylinder nitrogen (inert gas) is often used as the pressuring medium in the event vinyl chloride gas is not available. Larger in stallations may have a suction line connected from the storage tank to a compressor which discharges compressed vinyl chloride gas to vent connection on tank car. The pressure on the car should never exceed the service pressure at which the safety valve is set to operate. 4.4.6 Some tank cars in vinyl chloride serv ice are equipped with excess flow check valves. A too rapid opening of the discharge valves will cause the check valves to close. If this should occur, the outlet valve should be closed until the pressure is equalized and the excess flow valve opens. 4.4.7 Positive vinyl chloride or inert gas pressure should be left in car. No air should be allowed to enter car (See 3.3.3). 5. STORAGE 5.1 Hazards (See 8. Health Hazards andu TLhneeiirf 5.1.1 Aside from the risk of fire and explosion, vinyl chloride presents no other very seri ous problem in general handling. The presently accepted upper limit of safety as a health haz ard is 500 ppm. 5.1.2 Vinyl chloride should always be handled with full recognition of its flamma bihty. Precautions should be taken both to keep the material enclosed and to eliminate sources of ignition. If there should be any unavoidable leaks, reliance must be placed upon the elimination of all sources of ignition and on the provision of sufficient ventilation to keep escaping vapors at nonflammable levels (See 6.2). 5.1.3 CORROSION Vinyl chloride is noncorrosive at normal atmospheric temperatures when dry (moisture free). In contact with water at elevated-tem peratures vinyl chloride accelerates corrosion of iron or steel. 5.1.4 VOLATILITY Vinyl chloride is very volatile and is a gas at normal atmospheric conditions. Containers used for handling vinyl chloride at atmospheric temperature are always under pressure. 5.1.5 TEMPERATURE REQUIREMENTS Inhibited vinyl chloride may be stored at normal atmospheric conditions in suitable pres sure vessel. Uninhibited vinyl chloride may be stored either under refrigeration or at normal atmos pheric temperature in the absence of air or sunlight but only for a duration of a few days. If for longer periods, regular checks should be made for the presence of polymers. 5.2 Conditions of Storage 5.2.1 TYPE OF CONSTRUCTION All piping (including instrument leads), storage tanks, relief devices and equipment employed to handle vinyl chloride should be of steel and designed to have a working pressure of at least 100-150 psi with a safety factor con forming to the A.S.M.E. code for unfired pres sure vessels or any code applying to locale of planned storage. Shut-off valves and control 8 CMA 015471 Vinyl Chloride Manufacturing Chemists' Association. Inc- Manual Sheet SD-56 valves should be of steel or a suitable alloy not bearing copper, designed for working pres sures of 150 psi or over. All-welded construc tion is preferred to riveted construction. It is recommended wherever possible that all liquid inlet lines enter the bottom or extend to the bottom of the vessel. This guards against the accumulation of static electricity. All equipment should be properly grounded with resistance to ground never exceeding 25 ohms. An efficient water spray system should be in stalled or made available. Adequate diking and drainage should be provided under tank area to confine and dispose of the liquid in case of vessel rupture. Any cylinders used to store vinyl chloride must meet ICC Specifications. 5.2.2 ISOLATION Storage areas should be selected in ac cordance with local codes or authorities having jurisdiction. (Assistance may be obtained from such organizations as National Board of Fire Underwriters, Factory Insurance Associa tion, Associated Factory Mutual Fire Insurance Companies.) For highly volatile and flammable material, storage should be located outside of buildings. Cylinders containing vinyl chloride should be stored always in a vertical position, outside of buildings, and in an isolated and well ventilated area. It is preferable to store cylinders in the open, but provision should be made to shield them from the direct rays of the sun and prevent accumulation of dirt, snow, water, or ice on valves or safety devices. 5.2.3 COMPATIBLE AND DANGEROUS LY REACTIVE MATERIALS Tanks in vinyl chloride service should be used only for the storage of vinyl chloride (See 6.8). Before vinyl chloride is placed in a tank, the vessel should be purged with an inert gas until free of air. Vinyl chloride is generally noncorrosive at normal atmospheric tempera tures when dry (moisture free). However, mild to appreciable corrosion has been noted even at ordinary temperature. This may be due to .the presence of impurities. In contact with water at elevated temperatures vinyl chloride accelerates corrosion of iron or steel. Acetylene as an impurity'in vinyl chloride may form an explosive compound (acetylide) when exposed to copper or possibly copper alloys. 5.2.4 VAPOR-PROOF OR EXPLOSIONPROOF REQUIREMENTS All electrical equipment, motors, lights, and flashlights used in an area in which vinyl chloride is stored or handled should conform to the National Electrical Code (Class I, Divi sion II for storage; and Class I, Division I for use). 5.2.5 VENTING REQUIREMENTS An adequate system for normal and emer gency venting should be installed. All vent lines should extend to a safe area free of any source of ignition. The point of outlet should be equipped with an approved flame arrestor. Relief valves should be installed in pairs, par allel, using transflow valving to facilitate periodic testing and repairing. 5.2.6 VENTILATION All storage areas should be provided with continuous ventilation. Pits, depressions and basements should be avoided. 5.2.7 PROTECTION FROM ELECTRICAL STORMS Storage tanks for vinyl chloride should be protected from electrical storms and induced static electricity by grounding of all equip ment. 5.2.8 PROTECTION FROM INTERNAL'' EXPLOSIVE MIXTURES Storage tanks and other vessels should be maintained under positive pressure utilizing an inert gas when necessary or vapor pressure of the vinyl chloride. Vessels should be pro vided with bottom inlets under the liquid, or dip pipe extending from the top of the vessel to within inches of the bottom of the vessel to protect against a static discharge. 6. HANDLING 6.1 Health Hazards (See 8. Health Hazards and Their Control) 6.1.1 Aside from the risk of fire and explo sion, vinyl chloride presents no other very seri ous problem in general handling. The presently ~ accepted upper limit of safety as a health haz ard is 500 ppm. 6.2 Fire, Explosion, and Polymerization Haz ards 6.2.1 FIRE HAZARDS Vinyl chloride should always be handled with full recognition of its volatility and its flammability. In general, precautions should be taken both to keep the material enclosed and to eliminate all sources of ignition. In small 9 CMA 015472 Manual Sheet SD-56 Manufacturing Chemwts' Association. Inc. Vinyl Chloride laboratory operations, where vinyl chloride vapors may escape, reliance must be placed upon the elimination of sources of ignition and the provision of sufficient ventilation to keep escaping vapors at non-flammable levels. Vinyl chloride vapors can form flammable mixtures with air at all temperatures above --78C. (--108.4F.). Fires involving large quantities of liquid are difficult to extinguish since vinyl chloride is not miscible with water and is lighter than water (will float on top of water). Most small fires can be extinguished with carbon dioxide or dry chemical agents if properly applied. Ade quate fire extinguishing equipment of carbon dioxide or dry chemical type, fixed and portable, should be provided. Water spray is also satis factory for extinguishing fires. Diking and drainage should be provided for confining and disposing of the liquid in case of tank rupture or spills. Precautions should be taken to guard against vinyl chloride entering general sewer system (See 6.3). 6.3 Spills and Leakage 6.3.1 Frequent inspections of equipment and vessels containing vinyl chloride should be made to detect or prevent leaks. 6.3.2 If spills or leaks occur, ail sources of ignition if required to be present in the area and adjacent areas must be shut off immedi ately. Only necessary and properly protected personnel should remain in the area (See 6.5), 6.3.3 Spills, unless very large, usually eva porate rather rapidly and do little damage, but ample ventilation should be provided to prevent the formation of toxic and explosive mixtures. Spills should be guarded and controlled im mediately. All openings in sewer system should be trapped for segregation and extinguishment. All sources of ignition should be removed (See 6.2.1). 6.3.4 If possible, increased forced ventila tion should be provided. Inhalation of vapors should be avoided (See 8). 6.3.5 Leaking cylinders in any enclosure- I In event of a fire no unauthorized person should be removed to an isolated, well-ventilated should be permitted to enter an unventilated area until the space has been thoroughly area and the contents transferred to other suitable containers (See 4.3 and 5.2.2). sprayed with water to remove gases such as hydrogen chloride, phosgene, carbon monoxide, 6.3.6 The detection of leaks in equipment etc. generated from the fire. of vinyl chloride can best be accomplished by the use of a flammable gas indicator, or by 6.2.2 EXPLOSION HAZARDS inspection for the presence of vapors and frost ing on the surfaces of the equipment. Vinyl chloride is a gas at normal atmos pheric temperature and pressure. The gas will burn very readily in proper mixtures of air or oxygen. The explosive limits are: lower 4.0%, upper 22.0% by volume in air. An explosion hazard can exist when drawing samples or venting to the atmosphere. Open flames, local hot spots, friction, any spark producing equip 6.3.7 In the event of a tank car leakage, utilize necessary personal protective equipment and make emergency repairs, if possible. The supplier should be telephoned or wired im mediately for specific instructions. Guard against the fire hazard or explosion hazard (See 6.2). ment, and static electricity are to be avoided 6.3.8 Clothing contaminated with vinyl when handling this material. chloride should be removed immediately and the body washed thoroughly to remove any mate 6.2.3 POLYMERIZATION HAZARDS rial which may have penetrated to the skin. Clothing should be washed before reuse. If Vinyl chloride does not form peroxides by necessary shoes should be replaced with new autoxidation as readily as many other monom ones. Disposal of the contaminated shoes is ers. Aside from,polymerization, vinyl chloride recommended if the spilled vinyl chloride con is chemically quite stable (See 2.2 Reactivity). tained a toxic inhibitor, like phenol. Vinyl chloride can be satisfactorily stored without an inhibitor for short periods if it is 6.4 Employee Education and Training kept in steel tanks under refrigeration or at / normal atmospheric temperature in the absence 6.4.1 Safety in handling vinyl chloride and of air and sunlight. For shipping purposes other hazardous chemicals depends upon the inhibitors are employed. Inhibitors, like phenol, effectiveness of employee education, training, when present have hazards of their own, being and the safety instructions incorporated into very toxic (See 7.5). job instruction manuals. 10 CMA 015473 V Vinyl Chloride Manufacturing Chemiatt' Association. Inc. Manual Sheet SD-5S 6.4.2 The education and training of em ployees to work safely and to use the personal protective equipment or other safeguards pro vided for them is a responsibility of supervision. 6.4.3 Employee education and training should emphasize the need of handling vinyl chloride according to the methods outlined in this data sheet. 6.4.4 Before being placed on the job, new or transferred employees should be thoroughly instructed and questioned in respect to the proper handling of vinyl chloride. Employees on the job should be reinstructed periodically. 6.4.5 Each employee should know the loca tion, purpose, use and maintenance of personal protective equipment and be thoroughly trained in when and how to use the equipment (See 6.5). 6.4.6 Each employee should know the loca tion of safety showers, eye baths, bubbler drinking fountains, faucets or fire extinguish ing equipment. 6.4.7 Only reliable, properly trained em ployees should be given the responsibility of operating valves which control the flow of vinyl chloride to and from storage tanks, tank cars, and cylinders, or drawing samples and venting to the atmosphere. 6.4.8 Employees should be trained to report to the proper authority all suspected leaks or equipment failures and any signs of illness of personnel. 6.4.9 Each employee should know what to do in case of an emergency, in rendering first aid measures, and should realize the necessity for prompt administration of artificial resusci tation when overcome by vinyl chloride vapors (See 8.4.2.1). 6.5 Personal Protective Equipment 6.5.1 AVAILABILITY AND USE ' Personal protective equipment is not an adequate substitute for good, safe, working conditions, adequate ventilation, and intelligent conduct on the part of employees working with vinyl chloride. Such equipment may protect the individual wearing it while others in the area may be exposed to danger. The correct usage of personal protective equipment requires the education of the worker in the proper em ployment of the equipment available to him (See 6.4). Under conditions which are suffi ciently hazardous to require protective equip ment, the use of it should be supervised. In all cases, the type of protective equipment selected should depend upon the nature and degree of the hazards existing. The following personal protective equip ment should always be used for the purposes mentioned and as specified in Section 8. Health Hazards and Their Control, and in other sec tions of this data sheet: 6.5.2 EYE PROTECTION 6.5.2.1 Chemical Safety Goggles: cuptype or rubber-framed goggles, equipped with approved impact resistant glass or plastic lenses, should be worn whenever there is danger of the vinyl chloride (in liquid or saturated vapor form) coming in contact with eyes. Gog gles should be carefully fitted by adjusting the nose piece and head band to ensure maxi mum protection and comfort. 6.5.2.2 Spectacle-type Safety Goggles: metal or plastic rim safety spectacles with per forated side shields which can be obtained with prescription safety lenses or suitable all plastic safety goggles may be used where continuous eye protection is desirable. These types, how ever, should not be used where complete eye protection against chemicals is needed. ,, - 6.5.2.3 Face Shields: plastic shields (full length, eight inch minimum) with forehead protection may be worn in lieu of, or in addition to, chemical safety goggles where complete face protection is desirable. Chemical safety goggles should always be worn as added protection where there is danger of vinyl chloride striking the eyes from underneath or around the sides of the face shield. 6.5.2.4 Each employee should know the location of safety showers, eye baths, and bubbler drinking fountains for flushing the eyes. 6.5.3 RESPIRATORY PROTECTION Respiratory protective equipment must be carefully maintained, inspected, cleaned, and sterilized at regular intervals, and always be fore use by another person. Personnel wearing such equipment must be carefully instructed as to its operation and limitations. 6.5.3.1 Air or Oxygen Supplied Masks 6.5.3.1.1 Air or oxygen supplied masks, equipped with full face pieces and approved by the U. S. Bureau of Mines for this purpose, should be used under the following conditions, 11 CMA 015474 Manual Sheet SD-56 Manufacturing Chmiat*` Association, Inc, Vinyl Chloride and the manufacturer's instructions must be carefully followed: (a) In emergencies, when the vapor concentration is not definitely known. (b) When the harmful vapor concen tration is over 2 per cent by volume. (c) When the oxygen content of the air may be less than 16 per cent by volume. (d) When the exposure period is to be over 30 minutes duration. (e) In tank and equipment cleaning and repair work under conditions outlined in (a), (b), (c) and (d). 6.5.3.1.2 Types Generally Available In clude: (a) Air-Line Masks supplied by plant compressed air are suitable for use only where conditions will permit safe escape in case of failure of the compressed air supply. Such masks should be used only in conjunction with a suitable reducing or demand-type valve, ex cess pressure relief valve, and filter. The com pressed air should be checked frequently to make certain that harmful gases from the de composition of the lubricating oil used in the compressor, or impure air supply, are not present. (b) Positive Pressure Hose Masks supplied by externally lubricated blowers are usually preferred to the air-line type. Since these masks also depend on a remote air supply, they should be used only where conditions will permit safe escape in the event of air supply failure. Care must be taken to locate the blower air source in an area which is free of air con taminants. (c) Self-contained Breathing Appara tus which permits the wearer to carry a supply of oxygen or air compressed in the cylinder, and the self-generating type which produces oxygen chemically, allow for greater mobility. The length of time a self-contained breathing apparatus provides protection varies according to the amount of air or oxygen supply carried. In tank work, fohere small manholes are en countered, a self-contained breathing apparatus is usually unsuitable because of its bulk. 6.5.3.2 Industrial Canister Type Gas Masks equipped with full face pieces and ap proved by the U. S. Bureau of Mines, fitted with the proper canister for absorbing vinyl chloride vapor (or gas), will afford protection against concentrations not exceeding 2 per cent by volume when used in accordance with the manu facturer's instructions. The oxygen content of the air must be not less than 16 per cent bv volume. The masks should be used for rela tively short exposure periods only, i.e., less than 30 minutes. They may not be suitable for use in an emergency since, at that time, the actual vapor concentration is unknown and it may be very high. The wearer must be warned to leave the contaminated area immediately on detecting the odor of vinyl chloride. This is an indication that the mask is not functioning properly or that the vapor concentration is too high. NOTE: Where carbon monoxide may be en countered in addition to vinyl chloride, the mask should be equipped with an "All Purpose Canister" and a "Timing Device" as approved by the U. S. Bureau of Mines. 6.5.3.3 Chemical Cartridge Respirators approved by the U. S. Bureau of Mines may be used to avoid inhaling disagreeable butharmless concentrations of vinyl chloride vapor. These respirators, however, are not recom- mended for protection where toxic quantities of an air contaminator may be encountered. 6.5.4 HEAD PROTECTION 6.5.4.1 Safety or "hard" hats will pro vide protection against accidental liquid leaks, falling tools, and other objects. 6.5.4.2 Brimmed felt hats may be sub stituted for a safety hat where danger of fall ing objects is remote. 6.5.5 FOOT PROTECTION High leather or synthetic rubber safety shoes with built-in steel toe caps are recom mended where there is danger of heavy objects falling on workman's foot. Liquid vinyl chloride penetrates leather, and shoes wet with vinyl chloride should be replaced. - 6.5.6 BODY, SKIN AND HAND PROTEC TION 6.5.6.1 Any work gloves, clothing or wearing apparel which becomes contaminated with vinyl chloride should be removed im mediately, and the body should be thoroughly washed. All contaminated work gloves, clothing or wearing apparel should be thoroughly washed, and dried before reuse. For care of contaminated shoes see 6.5.5. 6.5.6.2 When cleaning, inspecting, or re pairing tanks, safety equipment such as safety 12 015475 Vinyl Chloride Manufacturing Chemuti' Association. Inc- Manual Sheet SD-56 belts, rescue harness, lifeline, clothing and gas masks should be worn as required by the speci fic nature of the work and the hazards involved, 6.5.6.3 Frequent inspections and neces sary repairs should be made to all personal protective equipment so that it is always ready to give proper protection to the wearer. 6.5.6.4 Facilities for personal cleanliness should be provided and time allowed for thor ough washing before lunch and at the end of the work day. 6.6 Engineering Controls 6.6.1 Selection of a site or location for ap paratus or equipment to ship, handle, store or manufacture vinyl chloride should be made by the direction of chemical engineers or mechani cal engineers fully aware of the hazards en countered in dealing with vinyl chloride (See 5,2.2). 6.6.2 Processes should be designed so that the operating personnel will not be exposed to direct contact with vinyl chloride or its vapor. The technical problems of designing equipment, providing adequate ventilation, and formulating operational procedures which promise maximum security and economy, can be handled best by engineers or other competent personnel. The manufacturers of vinyl chloride, and of the equipment in which it is to be used, are always prepared to help with these prob lems (See 5.2.1). 6.6.3 In the handling of vinyl chloride or operation of any type of vinyl chloride system, all valves, pipe lines, vents, safety devices, etc., should be so located that they can be readily in spected and repaired. They should always be in proper order and condition before the opera tion is started. All handling and storage equip ment should be located away from any source of sparks, flames, heated surfaces and all sources of ignition which might cause fires or explosions. All charging and discharging pipes should enter through, or extend to, the bottom of all containers to minimize vaporization of the liquid and possible generation of static electricity. 6.6.4 It is essential for safety that equip ment will be used and maintained as recom mended by the manufacturer and that a periodic test schedule of the equipment, including safety devices, should be followed. All vent lines should extend outdoors to an area free of any source of ignition for discharge. 6.6.5 All electrical installations should con form with the National Electrical Code. All equipment should be properly grounded to pre vent accumulation of static. 6.7 Ventilation 6.7.1 If the workroom or operating area is separate from vinyl chloride storage or pro cessing equipment, general ventilation is ade quate. For emergencies, however, the area should be provided with mechanical exhaust ventilation to maintain concentrations below flammable limits. 6.7.2 In the processing or storage area, if outside location is impracticable, special emer gency equipment for ventilation is necessary under abnormal conditions, such as leaks or spills. 6.7.3 Six or more changes of air per hour are considered adequate for buildings housing storage or processing equipment for flammable liquids, vapors, or gases under pressure. 6.7.4 Buildings of substantial construction should have at least one square foot of door, window, or nonrigid roof area for each 35 cubic feet of volume to prevent serious struc tural damage in the event of explosion within the building. 6.7.5 The most important consideration in ventilation is to ensure an adequate air flow away from the work area. 6.7.6 All ventilating systems should be in spected periodically and maintained in a safe and efficient working condition. 6.7.7 Under abnormal conditions, such as when leaks or spills occur, all available ventila tion should be used. 6.8 Tank and Equipment Cleaning and Repairs 6.8.1 The hazardous nature of tank or vessel inspections, cleaning, and repairs requires that the foreman and crew be selected, trained, and drilled carefully. They should be fully familiar with the hazards and safeguards necessary for the safe performance of the work. Use only spark-resistant tools. 6.8.2 Wherever possible, vessels should be cleaned from the outside, using cleanout man holes or openings provided for this purpose. 6.8.3 First consideration in vessel entry work requires the vessel be properly isolated 13 CMA 015476 Manual Shet SD-56 Manufacturing Ch*mtet*' Association, Inc. v'inyl Chloridt from any process equipment, pipe lines, or ap paratus. These process lines, pipe lines, and apparatus should be disconnected, preferably by removing a complete small section and pro viding a blank flange on the open end to protect against human error and unsuspected leaks. Valves and plug cocks in the process lines, pipe lines, or apparatus should not be relied upon to prevent leakage into vessel being cleaned. 6.8.4 Electrical switches should be locked in the "OFF" position and tagged with a warn ing that they are not to be opened. Where pos sible, the fuses should be pulled. Drive belts should be removed and all other precautions taken to ensure against the accidental starting of agitating equipment or other moving parts inside the vessel or adjacent to the entrance. 6.8.5 Before entering a tank, it should be empty, purged, and tested for flammable resi dues. Caution should be exercised in checking for trapped vapors in any semi-solid or solid residues. In purging a vessel, an inert gas (carbon dioxide or nitrogen) is recommended. The inert gas must be displaced before allow ing entry into a vessel. When air is used for purging a vessel, there is a period when an explosive mixture is present (mixture contains by volume between 4-22% gas). For this rea son it is best to avoid the use of air in removing flammable vapors. 6.8.6 Warning signs should be placed indi cating nature of hazard present during pre paration of vessel for entry or repair. 6.8.7 Before entering a vessel and during the course of the work, tests should be made by a qualified person to determine that no further purging or washing is necessary, that no oxygen deficiency exists, and that no harm ful gas or vapor is present. 6.8.8 Special ventilation and a continuous fresh air purging of vessel is recommended during the entire time men are cleaning, in specting, or repairing vessel. 6.8.9 Proper personal protective equipment such as a safety belt, rescue harness, lifeline, or mask as required should be worn by anyone entering a vessel after preparation for inspec tion, and/or repairs (See 6.5). 6.8.10 An attendant should be stationed outside the vessel in such a position as to keep workmen within the vessel under constant ob servation. He should serve as the lifeline tender and be ready at all times to summon help or other required aid. He should never abandon the lifeline while workmen are in the vessel. 6.8.11 A self-contained breathing apparatus or an air-supplied mask should be located im mediately adjacent to vessel repair area for any emergency situation during vessel entry work. In addition a lifeline and safety harness should be on hand. 6.8.12 The portable electric lights and power tools should be in good condition, grounded and approved by competent persons for use in exposures of this nature. 6.8.13 Before reuse, the vessel should be purged free of air by using an inert gas such as carbon dioxide or nitrogen. 6.9 Repackaging 6.9.1 Only clean, ICC Specification cylinders or tank cars should be used (See 3.1). 6.9.2 Adequate ventilation should be pro vided and all sources of ignition removed from transfer area. 6.9.3 Proper personal protective equipment should be used (See 6.5). Transferring Vfnyl chloride from cylinders by the use of an un controlled heating method is not recommended because it is unsafe, wasteful, and time con suming. Temperatures of over 50 C. (122F.) should not be applied to any part of a cylinder containing compressed gas. Excessive heating weakens the structural characteristics of the metal and may seriously damage the cylinder. Low melting safety devices may reach the fus ing point by the application of excessive heat to a cylinder. Never apply direct flame to a cylinder. A definite fire hazard is created. For recommended practice to transfer contents of a cylinder see 4.3. 6.9.4 For recommended practice to transfer contents of tank car see 4.4. 6.9.5 The appropriate labels should be ap plied to the filled cylinders or tank cars (See 3.2). 7. WASTE DISPOSAL 7.1 All Federal, State, and local regulations regarding health and pollution should be ob served. Disposal of waste material, however, depends to a great extent upon surroundings and weather conditions. 7.2 When it becomes necessary to dispose of vinyl chloride as such, it is preferable to do so as a vapor, venting to an area free of any source of ignition (See 5.2.5 and 5.2.6). 14 CMA 015477 Vinyl Chloride Minufieturine Chemuu' Association. Inc. Manual Sheet SD-5G 7.3 When a waste disposal problem arises as a result of a major spill or equipment rupture, only properly protected and qualified personnel should remain in the area (See 6.3 and 6.5). 7.4 Waste mixtures containing vinyl chloride should not be allowed to enter drains or sewers as serious explosion in such systems may re sult (See 6.3). 7.5 Removal of inhibitor, such as phenol in form of sodium phenolate, should be done by dilution to approximately 1% solution (See SD-4, Part 7. Waste-Disposal). 8. HEALTH HAZARDS AND THEIR CONTROL 8.1 Hazards 8.1.1 GENERAL Aside from the risk of fire or explosion, vinyl chloride presents no other very serious problem in general handling. The presently ac cepted maximum allowable concentration is 500 ppm. 8.1.2 SYSTEMIC EFFECTS In concentrations well above 500 ppm. vinyl chloride acts as a mild general anesthetic. 8.1.3 LOCAL EFFECTS In contact with the skin vinyl chloride is irritating. Prolonged contact will result in re frigeration and freezing. 8.2 Prevention and Control Vinyl chloride is not a serious industrial hazard provided precautions are taken to avoid leaks or spills which might provide a fire or explosion hazard. Where serious leaks or spills do occur, the workmen present in the area should be evacuated, and persons returning to the area to repair or clean up equipment should be provided with appropriate gas masks, selfcontained oxygen units, or air supplied hoods. 8.2.1 EMPLOYEE EDUCATION (See 6.4 Employee Education and Training) Employees working in areas where vinyl chloride is handled or stored should be thor oughly and repeatedly warned of the anes thetic properties of vinyl chloride gas and in structed as to what to do if anesthetic effects are detected in themselves or in others (See 8.4.2.1). Emphasis in training should be placed on: 1. The use of artificial respiration in cases where breathing has stopped because of deep anesthesia. 2. The necessity of immediate removal of contaminated clothing and shoes in case of liquid spills. 3. Repeated washing of the eyes with copious amounts of xoater in case of liquid splashes. 8.2.2 VENTILATION Work areas where vinyl chloride is handled or stored should be provided with adequate ventilation. The concentration of vinyl chloride should be kept below the upper safe limit of 500 ppm. at all times. 8.3 Personal Protective Equipment 8.3.1 No personal protective equipment is an adequate substitute for safe working condi tions and intelligent conduct on the part of employees who work with vinyl chloride. Furthermore, the correct usage of personal protective equipment requires education of the worker in the proper employment of the mate rials available to him. Under conditions which are sufficiently hazardous to require personal protective equipment, the use of it should be supervised. 8.3.2 Employees who may be subjected to severe exposure to vinyl chloride, as in tank and equipment cleaning and repairs, in decon taminating extensive areas after large spillage, or in cases of failure of piping or equipment, should be provided, when indicated, with proper eye, respiratory, skin, and mucous membrane protection as follows: (a) Suitable gas tight safety goggles. (b) Rescue harness and life line for those entering tank or enclosed storage space (See 6.7). (c) Hose masks with hose inlet in a vaporfree atmosphere, air line masks with proper reducing valve and filter, suitable for use only where conditions will permit safe escape in case of failure of the com pressed air supply, or self-contained breathing equipment with stored oxygen or air (such equipment allows greater mobility but usually requires more highly trained men). 15 CMA 015478 Manual Sheet SD-56 Mrui(*c'urius Chemists' Association. inc. Vinyl Chloride 8.3.3 Facilities for washing eyes and skin with large quantities of water should be readily available (See 6.5.2.4). 8.4 First Aid and Medical Care 8.4.1 GENERAL PRINCIPLES 8.4.1.1 As in exposure to any odorless or mildly scented anesthetic gas, a recognition of the presenting symptoms and signs in oneself and in others is very important. The anes thetic properties of vinyl chloride are mild in degree and slow in developing. Detection of symptoms except in very high concentrations permits ample warning and sufficient time for escape from the environment provided the warning is heeded and escape is possible. 8.4.1.2 As in any skin contact with ir ritating or harmful materials, speed in remov ing the contaminant from the skin is of primary importance. Vinyl chloride is very volatile and simple exposure to air will usually effect ade quate removal. Clothing, shoes, bandages, or other articles by which vinyl chloride might be held in contact with the skin should be im mediately removed to decrease the freezing effect. 8.4.2 SPECIFIC ACTIONS 8.4.2.1 Inhalation Continued exposure to atmospheres con taining vinyl chloride in concentrations of 1000 ppm. or over will slowly produce evidences of mild anesthesia: (1) a sensation of drowsiness and inability to concentrate, (2) a blurring of vision--at first readily cleared by conscious effort--later controlled only with difficulty or not at all, (3) staggering gait, (4) sensation of numbness or tingling in feet or hands or both. These symptoms may be readily detected by the employee himself if he has been alerted to the possibility of their arising from over exposure to vinyl chloride. They may also be noted in fellow employees. When such symptoms arise, they are definite warning of a hazardousexposure to vinyl chloride, and all personnel should be immediately evacuated from the area until the leark or spill has been located and corrected and until complete recovery from all symptoms has occurred. Because of the mildness and slow de velopment of symptoms, it is very unlikely that any workman will be overcome to the point where he will require help in escaping the environment or medical care following ex posure. Any person with evidence of intoxica tion from vinyl chloride should be put at rest, either seated or lying, in an uncontaminated atmosphere. If trapped in an area of high concentra tion where escape is impossible, deep anesthesia can result. If such an exposure has occurred, the patient should be placed in bed, preferably with the head slightly lowered and with no pillows. If respirations have ceased, artificial respiration will be required. In any case, medi cal attention should be obtained immediately. 5.4.2.2 Contact with Skin Liquid vinyl chloride is a primary irri tant to intact skin. If sufficient quantities re main long enough in contact with the skin, the rapid evaporation may result in freezing or "frost bite". Consequently, anything which tends to hold vinyl chloride in contact with the skin, such as clothing, shoes, or bandages, in creases the risk of freezing. If spills occur, all contaminated clothing should be removed immediately and the con taminated area washed copiously in running water. If mild irritation has occurred, no further treatment may be required. If inflam mation is severe, loose dressings of petroleum jelly should be applied and the patient placed in the care of a physician. If freezing has occurred, the area should be loosely covered with a clean, preferably sterile, gauze or towel and placed in the care of a physician. 8.4.2.3 Contact with Eyes Vinyl chloride which has gotten into the eyes should be washed out immediately with copious amounts of flowing water. Water at room temperature will produce less pain than very cold water, but in an emergency a drinking fountain is a satisfactory source of water. The washing should continue for at least 15 minutes. If injury is apparent in the tissues of the eye after 15 minutes of irrigation, the washing should be continued for another 15 minutes. I:1, all cases except of very minor irritation, the patient should be placed in the care of an ophthalmologist immediately. The medical information in this publication has been supplied by the Medical Advisory Committee of the Manufacturing Chemists' Association, Inc. 16 CMA 015479 Chemical Safety Data Sheet SD-56 PROPERTIES AND ESSENTIAL INFORMATION ^ FOR SAFE HANDLING AND USE OF VINYL CHLORIDE Chemicals in any form can fa safely stored, handled or usd if th* physical, chemical and hazardous properties or* fully under stood and th* necessary precautions, including th* us* of proper safeguard* and p*r*onal protective equipment, or* observed. REVISED 1972 MANUFACTURING CHEMISTS ASSOCIATION 1825 CONNECTICUT AVENUE. N. W. WASHINGTON. D. C. 20009 CMA 015480 1 Published as an activity of the Association's Safety and Fire Protection Committee. Other MCA committees which have cooperated in its preparation include: Air Quality Committee Chemical Packaging Committee Labels and Precautionary Information Committee Occupational Health Committee Transportation Equipment Committee Water Resources Committee Address correspondence to staff editor--F. G, Stephenson, Manufacturing Chemists Association, 1825 Connecticut Avenue, Washington, D. C. 20009. 1972 by Manufacturing Chemists' Association, Inc. < II >1 i; > I` The information and recommendations contained in this Chemical Safety Data Sheet have been compiled from sources believed to be reliable and to represent the best opinion on the subject as of 1972. However, no warranty, guarantee, or representation is made by the Manufacturing Chemists Association as to the correctness or sufficiency of any information or recommendation herein, and the Association assumes no responsibility in connection therewith; nor can it be assumed that all necessary warnings and precautionary measures are contained in this Chemical Safety Data Sheet, or that other or additional information or measures may not be required or desirable because of particular or exceptional conditions or circumstances, or because of applicable federal, state, or local law. CMA 015481 TABLE OF CONTENTS Page Preface ............................................................................................................................. 4 1. NAMES ............................................................................................................................. 5 2. PROPERTIES ................................................................................................................... 5 3. HAZARDS 3.1 Health Hazards .................................................................................................. 3.2 Fire'and Explosion Hazards .......................................................................... 3.3 Stability Hazards .............................................................................................. 6 6 6 4. ENGINEERING CONTROL OF HAZARDS 4.1 Building Design .................................................................................................. 4.2 Equipment Design ...................................................... 4.3 Ventilation .......................................................................................................... 4.4 Air Analysis ....................................................................................................... 4.5 Electrical Equipment ................ 6 7 7 7 8 5. EMPLOYEE SAFETY 5.1 Employee Education and Training ....................................................... 5.2 Personal Protective Equipment ...................................................................... 8 8 6. FIRE FIGHTING .............................................................................. 10 7. SHIPPING, LABELING, HANDLINGAND STORAGE 7.1 Shipping ............................................................................................................... 10 7.2 Labeling ...................................... 10 7.3 Cylinders ............................... 12 7.4 Tank Cars .................................................................................. 12 7.5 Transportation Emergencies ........................................................................ 13 7.6 Storage .................................................................................................................. 15 7.7 Repackaging ....................................................................................................... 15 8. TANK AND EQUIPMENT CLEANING AND REPAIRS ........................................... 16 9. WASTE DISPOSAL .......................................................................................................... 17 10. MEDICAL MANAGEMENT 10.1 Health Hazards ........... .......... .......77................................................................ 17 10-2, Preventive Measures ....................................................................................... 17 10,3 Suggestions to Physicians ............................................................................. 18 11. FIRST AID ........................................................................................................................ 18 CMA 015482 Chemical Safety Data Sheet VINYL CHLORIDE PREFACE Vinyl chloride monomer is classified by the U.S. Department of Transportation as a flammable compressed gas. It is easily ignited, producing hazardous combustion gases largely composed of hydrogen chloride and carbon monoxide. The primary health hazard of VCM is associated with excessive respiratory exposure. In acute overexposures the primary effect is on the central nervous system, producing intoxication and dulling of visual and auditory responses. Excessive chronic exposure may pro duce liver injury. The full text of this chemical safety data sheet should be consulted for details of the hazards of vinyl chloride monomer and suggestions for their control. * FIRST AID-SEE PAGE 18 For assistance in the event of any emergency involving this chemical in transportation, call MCA's Chemical Transportation Emergency Center. CHEMTREC (800) 424-9300 * (Use 483-7616 in District of Columbia) Toll-free, day or night 4 Um long distonco accost ntimbsr if roqoirod. In CANADA, call Canadian Chemical Producers Association's TEAP (Transportation Emergency Assistance Plan) 4 CMA 015483 Chemical Safety Data Sheet VINYL CHLORIDE Manual Sh*r SD-56 1. NAMES Chemical Names: Common Name: Formula: Vinyl Chloride Monomer Chloroethylene Chloroethene Vinyl Chloride, VCM CH-CHCl 2. PROPERTIES 2.1 GRADE: Commercial, sometimes referred to as Technical 2.2 IMPORTANT PHYSICAL AND CHEMICAL PROPERTIES: Boiling Point at 1 atm, Color____ __________ Corrosivity............... . Explosive Limits (Percent by Volume in Air) Flash Point (Open Cup)................................. Hygroscopicity................ ................................. Critical Pressure, psia.................. ............ ...... Critical Temperature .............................. ........ Ignition Temperature, Autogenous................ Light Sensitivity............. . ................................. Melting Point at 1 atm___________ ________ (Freezing Point) Molecular Weight................. ........................... Odor Physical State..... .......................... ................... Reactivity............. ..... ,,.... Specific Gravity of liquid @ 4C. (Water ^ 1)............ ..................... Vapor Density of gas (Air = 1)___ Vapor Pressure ffi) 68F................... Density, liquid, lb./cu. ft. at 70F__________ ________ at 105F.... ........ ...................... at 115F.___________________ at 130F................................... Threshold Limit Value (ceiling)..... ....-- 13.8C. (+ 7F.) ...Colorless or water white ...Noncorrosive at normal atmospheric temperatures when dry (moisture free). In contact with water at elevated, temperatures vinyl chloride accelerates corrosion of iron or steel. ...Lower 3.6%; upper, 26.4% .... -- 78C. (-- 108.4F.) _No ....775 _158.4C. (317F.) ____472.22C. (882F.) ....Uninhibited VCM is light sensitive ....-- 153.71 C. (-- 245F.) __62.50 __Sweet smelling gas. Inhibited VCM may have faint phenolic odor. ....Gas at ordinary temperature and pressure. Liquid under pressure in cylinder or pressure vessel at room tem perature. ....Polymerizes readily in presence of air, sunlight, oxygen Ur heat. This behavior is due to the presence of a dou. ble bond. Otherwise vinyl chloride is quite stable. .... 0.9121 ....2.15 ---35 psig ....56.71 ....54.38 ....53.69 .....52.61 ....500 ppm or 1300 mg/M3 5 CMA 015484 Manuel 5h*#t SD-56 Manufacturing Chemists Association Vinyl Chloride 3. HAZARDS 3.1 HEALTH HAZARDS (See Section 10 MEDI CAL MANAGEMENT) 10 ppm. Only in the very near vicinity of a VC. ! fire would significant amounts of phosgene be present. 3.1.1 The primary hazard of vinyl chloride is associated with excessive respiratory exposure. Ex posure to high levels may produce some lung irritation. Chronic overexposure may produce liver injury. When inhaled it acts primarily as an anes thetic. The odor is pleasant to most individuals and. therefore, acutely dangerous levels may be easily tolerated. e. The main sources of danger to personnel result from the massive formation of hydrogen chloride gas and from carbon monoxide. However, the puneent odor of hydrogen chloride acts as a warning to clear the area or to obtain the necessary breathing ap paratus before attempting any fire control measures. See MCA Chemical Safety Data Sheet. SD-39, Hy drochloric Acid (Aqueous) and Hydrogen Chloride (Anhydrous). 3.1.2 Warning Properties 3.3 STABILITY HAZARDS The lowest concentration of VCM at which its l odor can be detected is reported to be 260 ppm. Olfactory fatigue, however, may occur and the sense Vinyl chloride is shipped and used in both the in hibited and uninhibited state. In the uninhibite of smell cannot be relied upon as a warning for ex state, high purity must be maintained since contam; cessive low grade exposures. nants may catalyze polymerization or cause decom position of the VCM, liberating hydrogen chloride. Prior to shipment, uninhibited VCM should be tested 3.2 FIRE AND EXPLOSION HAZARDS for stability under shipping and storage conditions. 3.2.1 Vinyl chloride is a gas at normal atmos pheric temperature and pressure. The gas will bum very readily in proper mixtures of air or oxygen. An explosion hazard can exist when drawing samples or venting to the atmosphere. Open flames, local hot Cleanliness of shipping containers is of prime im portance when shipping uninhibited VCM. Vinyl chloride may polymerize as a result of ex posure to air, oxygen or sunlight at ambient or higher temperatures. spots, friction, any spark producing equipment, and Vinyl chloride does not form peroxides by autoxi- static electricity are to be avoided when handling this dation as readily as many other monomers. material. In the absence of an initiator, VCM is chemically i 3.2.2 Combustion Products of Vinyl Chloride Monomer quite stable. Commercial VCM, uninhibited, is stored and shipped in steel containers under conditions which avoid exposure to air and sunlight. For large Analysis of a combustion gas sample obtained volume, long term storage, refrigeration is sometimes immediately above a flame of vinyl chloride monomer employed to maintain the temperature at about 203 burning in air shows presence of hydrogen chloride C, maximum, to minimize the formation of haze, (27,000 ppm), carbon dioxide (58,000 ppm), car a condition caused by a small degree of polymeriza bon monoxide (9,500 ppm) and phosgene less than tion. 4. ENGINEERING CONTROL OF HAZARDS 4.1 BUILDING DESIGN Equipment and vessels containing VCM should preferably be isolated from other facilities by walls and floors of tftfe resistive construction. Standard fire walls are recommended for the iso lation of larger equipment and storage tanks, while partitions of plaster on expanded metal lath may be used to isolate smaller equipment from other com bustible materials. Not less than two means of exit should be provided from each separate room or building in which VCM is stored, handled or used. No portions of such a room or building should be farther than 75 feet from the nearest exit. Additional exits should be provided depending upon the number of persons in the build ing. (See NFPA Standard =5101 Life Safety Code.) All exit doors should open out in the direction of travel and should be provided with panic hardware. Fire doors should open out in' the direction of travel and be of an approved type. Operations where large quantities of VCM are used should preferably be housed in one story build ings. 6 CMA 015485 Vinyl Chloride Manufacturing Chemists Association Manual $h*t SD-56 Explosion vents may be used to reduce destructive damage to buildings, ducts, mixers, blenders, driers and similar equipment in which flammable vapors are liable to concentrate. Explosion venting windows, roof and wall panels, skylights, light windows, diaphragms, etc., may be used to minimize building damage auc to explosion pressures. Since the required area of explosion vents depends upon such factors as the intensity of an explosion, vapor temperature, type of structure, the type of vent closure, etc., the determination of vent ratios should be made by experienced engineers and safety and fire protection specialists. Consideration may be given to explosion suppression systems. (Reference: NFPA Fire Codes, Vol, 9--#68). The question of adequate spacing of chemical stor age buildings from other buildings and processing equipment should be considered. A fire resistive stairwell with self-closing fire doors may be specified for hazardous operations on upper floors. The need for segregating floor drains from sanitary or process sewer systems should be considered. 4.2 EQUIPMENT DESIGN 4.2.1 Processes should be designed so that op erating personnel will not be exposed to direct con tact with vinyl chloride or its vapor. The technical problems of designing equipment, providing adequate ventilation, and formulating operational procedures which promise maximum security and economy, can be handled best by engineers or other competent per sonnel. The manufacturers of vinyl chloride, and of the equipment in which it is to be used, are always prepared to help with these problems. 4.2.2 In the handling of vinyl chloride or opera tion of any type of vinyl chloride system, all valves, pipe lines, vents, safety devices, etc., should be so located that they can be readily inspected and re paired. They should always be in proper order and condition before the operation is started. All handling and storage equipment should be located away from any source of sparks, flames, heated surfaces and all sources of ignition which might cause fires or~explosions. All charging and discharging pipes should enter through, or extend to, the bottom of all con tainers to minimize vaporization of the liquid. Use of excess flow valves and valves with fusible links should be considered on storage tanks and other large vessels in case of fires or leaks near these vessels. 4.2.3 It is essential for safety that equipment be used and maintained as recommended by the manu facturer and that a periodic test schedule of the equipment, including safety devices, should be fol lowed. All vent lines should extend outdoors to an area free of any source of ignition for discharge. Vents and vent lines should have flash arresters. 4.2.4 Material of copper or copper-bearing alloy should not be used in contact with vinyl chloride due to the possible presence of acetylene and the forma tion of explosive acetylides. 4.3 VENTILATION 4.3.1 Ventilation should be adequate to maintain exposures below the ceiling value of 500 ppm recom mended by the U.S. Department of Labor. 4.3.2 If the workroom or operating area is sep arate from vinyl chloride storage or processing equip ment, general ventilation is usually adequate. For emergencies, however, the area may be provided with mechanical exhaust ventilation to maintain con centrations below 500 ppm. Mechanical ventilators should be of the nonsparking or explosion-proof type and should have motors conforming to the National Electrical Code (Class I, Division I). 4.3.3 In the processing or storage area, if outside location is impracticable, special emergency equip ment for ventilation is necessary under abnormal conditions, such as leaks or spills. 4.3.4 The most important consideration in ven tilation is to ensure an adequate air flow away from the work area. 4.3.5 All ventilating systems should be inspected periodically and maintained in a safe and efficient working condition. 4.3.6 Under abnormal conditions, such as when leaks or spills occur, all available ventilation should be used. 4.4 AIR ANALYSIS 4.4.1 Analysis of the air for vinyl chloride in the work area will give a measure of the effectiveness of engineering control of the vapors. It may be per formed to detect leakage of vapors from equipment and also to ascertain the order of magnitude of the health and fire hazard existing in work areas. 4.4.2 It should be kept firmly in mind that the use of the following instruments and test procedures for the detection of VCM in the air requires specially trained personnel. 4.4.3 Vinyl chloride vapor concentrations in air near or within the explosive range are most easily determined by the use of a standard combustible gas indicator. The concentration of vapor may be read directly on the meter which is usually graduated in percent of the lower flammable limit. The above should not be used for the detection of health haz ards. 7 CMA 015486 Manual Sh*t SD-54 Manufacturing Chemists Association Vinyl Chloride 4 4.4 A specially calibrated indicator is commer cially available for vinyl chloride monomer deter minations within the toxic range. Ampules which change color on exposure to VCM vapors are also commercially available and may also be employed for the detection of low level concentrations. 4.5 ELECTRICAL EQUIPMENT All electrical equipment, motors, lights, and tlc,,,ilights used in an area in which vinyl chloride i$ stored or handled should conform to the National Electrical Code. 5. EMPLOY EE SAFETY 5.1 EMPLOYEE EDUCATION AND TRAINING 5.1.1 Before-ijjndertaldng any training of the em ployees who are engaged in handling or processing vinyl chloride the supervisor should be thoroughly familiar with the contents of this data sheet. MCA Case Histories describe accidents and injuries that have occurred while handling or processing vinyl chloride monomer. Safety specialists and suppliers may also be consulted. 5.1.2 After becoming thoroughly familiar with the hazardous characteristics of vinyl chloride mono mer, the supervisor should review each procedure where the material is to be used and preferably with the assistance of the workers directly involved. Dur ing the review all danger points should be identified and the precautionary measures determined. The review should not only be concerned with the dangers of contact or exposure to vinyl chloride monomer, but also those which may be involved in handling containers, operating equipment and other aspects of the work. Procedures for all forseeablc emergencies should be established including the location and op eration of safety showers, fire extinguishers, alarms, etc. and the need for personal protective equipment. 5.1.3 During the safety review of the operations it may become apparent that some danger points can be eliminated. Possibly additional ventilation, ma chine guarding or modifying the method of handling the material or containers can avoid potential haz ards. Process changes, however, should never be made without the approval of those who have de veloped the process and other knowledgeable per sons. In chemical processing even a slight deviation might have disastrous results. _ 5.1.4 All significant hazards which cannot be satisfactorily guarded by rearrangement or other modification should be explained together with the precautions fd be followed in the standard operating procedures. Preferably these safety precautions should be an integral part of the operating instruc tions. For example, if eye protection is required while taking a sample the standard operating proce dure might read, "Wear goggles and take sample from Still No. 000." This type of instruction is pre ferable to explaining to the worker the need to take a sample and in another part of standard operating procedure having a notation to the effect that he is to wear eye protection when sampling. 5.1.5 If there are extremely critical steps in the process where, for example, over charge or under charge may cause uncontrollable reaction, considera tions should be given to making these supervisors' check points. In such instances the standard operaing procedure should specify that the employee mu. notify his supervisor before proceeding further or as in this example, prior to charging the material to the reactor. It then becomes the supervisor's responsibil ity to verify that the employee has followed the proper procedure before undertaking the critical^step. 5.1.6 The safety review described should be re peated periodically for all chemical processing opera tions and always following a significant change in the process. 5.2PERSONAL PROTECTIVE EQUIPMENT 5.2.1 Availability and Use Personal protective equipment is not an ade quate substitute for good, safe working conditions, adequate ventilation, and intelligent conduct on the part of employees working with VCM. It is, how ever, in some instances the only practical means of protecting the worker, particularly in emergency sit uations. One should appreciate that personal protec tive equipment protects only the worker wearing it, and other unprotected workers in the area may be exposed to danger. The effectiveness of personal protective equip ment requires the training of workers in its proper use and care. The following personal protective equipment should be used when indicated: 5.2.2 Eye Protection Chemical Safety Goggles Cup-type plastic or rubber framed goggles, equipped with the approved impact resistant glass or plastic lenses, should be worn whenever there is danger of the material coming in contact with the eyes. Goggles should be carefully fitted. 5.2.3 Spectacle-Type Safety Goggles Metal or plastic rim safety spectacles with side shields may be used where continuous eye protection 8 CMA 015487 Vinyl Chloride Manufacturing Chemists Association Manual $h**t SO-56 is desirable, as in laboratories. Spectacles, however, should not be used where complete eye protection is needed such as when handling bulk quantities, when there is danger of splashing, or when the material is under pressure. 5.2.4 Face Shields Plastic shields (full length, 8" minimum) with forehead protection may be worn in addition to chemical safety goggles where complete face protec tion is desirable. Chemical safety goggles should always be worn as added protection where there is danger of material striking the eyes from underneath or around the sides oLthc face shield. 5.2.5 Respiratory Protection 5.2.5.1Severe exposure to VCM may occur in tanks during equipment cleaning and repairs, when decontaminating areas following spills, or in case of failure of piping or equipment. Employees who may be subject to such exposures should be provided with proper respiratory protection. Available types are described below: Note: Respiratory protective equipment must be carefully maintained, inspected, cleaned and sterilized at regular intervals and always before and after use by another person. (a) Self-contained Breathing Apparatus which permits the wearer to carry a supply of air compressed in the cylinder allows considerable mobil ity. The length of time a self-contained breathing apparatus provides protection varies according to the amount of air carried. Compressed oxygen must not be used where there is danger of contact with flammable liquids, vapors, or sources of ignition, especially in confined spaces such as tanks or pits because of the increased fire hazard an oxygen rich atmosphere presents. (b) Positive Pressure Hose Masks which are supplied by blowers requiring no internal lubrication may be used. The wearer must be able to use the same route for exit as for entrance and must take precautions to keep the hose line free of entangle ment. The air blower must be placed in an area free of contaminants. (c) Air-line Masks, supplied with clean ~ compressed air, are suitable for use only where con ditions will permit safe escape in case of failure of the compressed air supply. These masks are usually supplied with air piped to the area from a compres sor. It is extremely important that the air supply is taken from a safe source, and that it is not contami nated by oil decomposition from inadequate cooling at the compressor. The safer method is to use a separate compressor of the type not requiring in ternal lubrication. Pressure reducing and relief valves, as well as suitable traps and filters, must be installed at all mask stations. An alternate arrange ment frequently used is high pressure breathing air from standard (200 cu. ft.) cylinders, with a demand type valve and face piece. This arrangement may also be used with 50-100 lb. clean piped plant air, and. as an additional precaution with the demand mask, a small cylinder of compressed air may be worn for use as an emergency escape from the area. Consult a reliable safety equipment dealer for details on the proper use of U.S. Bureau of Mines approved equipment. (d) Industrial Canister-Type Gas Masks, equipped with full face pieces and approved by the U.S. Bureau of Mines, fitted with the proper canister for absorbing vapor, will afford protection against concentrations not exceeding 2 percent by volume when used in accordance with manufacturer's in structions. The oxygen content of the air must not be less than 16 percent by volume. The masks should be used for relatively short exposure periods only. They are not recommended for use in an emergency since, at that time, the actual vapor concentrations is unknown and an oxygen deficiency may exist. The wearer must be warned to leave the contaminated area immediately on detecting the odor of a chemical vapor. This may indicate that the mask is not func tioning properly, that the vapor concentration is toohigh, that the canister is exhausted or that the mask is not properly fitted. Because of the limitations out lined, use of canister masks should be restricted. Note: Where other gas having little or no odor may be encountered in addition to VCM the mask should be equipped with an "all purpose can ister" and a "timing device" as approved by the U.S. Bureau of Mines. (e) Chemical Cartridge Respirators may be used to avoid inhaling disagreeable but relatively harmless concentrations of VCM vapor. These res pirators, however, are not recommended for protec tion where toxic concentrations may be encountered or where there may be oxygen deficiency. CAUTION: Filter-type respirators do not offer protection against gases or CL deficiency and are unsuitable for use when working with VCM. 5.2.6 Head Protection "Hard" hats should be worn where there is dan ger from falling objects. "Bump caps" are satisfactory in areas where there is little or no hazard from falling objects. They will give protection from liquid leaks and splashes. 5.2.7 Foot Protection Leather or synthetic rubber safety shoes with built-in steel toe caps are recommended where there is danger of heavy objects falling on a workman's foot. Liquid vinyl chloride penetrates leather, and shoes wet with vinyl chloride should be (a) discarded 9 015488 Manual Sh** 5D-56 Manufacturing Chemists Association V'"Yl CKlcri^ if the monomer is phenol inhibited, and (b) removed and not worn until thoroughly dry when handling uninhibited monomer. 5.2.8 Body, Skin and Hand Protection 5.2.8.1 Any work gloves, clothing or wearing apparel which becomes contaminated with VCM should be removed immediately, and the body should be thoroughly washed. All contaminated work gloves, clothing or wearing apparel should be thor oughly washed, and dried before reuse. 5.2.8.2 When cleaning, inspecting, or repajr_ ing tanks, safety equipment such as sate:, i-)^' rescue harness, lifeline, clothing and respiran pro^ tective equipment should be worn as requirec ;,y the specific nature of the work and the hazards involved 5.2.8.3 Frequent inspections and necessary repairs should be made to all personal protective equipment so that it is always ready to give proper protection to the wearer. 5.2.8.4 Facilities for personal cleanliness should be provided. 6. FIRE FIGHTING 6.1 When vinyl chloride bums, the hazardous gases generated arc mostly hydrogen chloride and carbon monoxide (See 3.2.2). 6.2 Emergency Measures (See 7.5,2) 6.3 Fire involving large quantities of spilled liquid are difficult to extinguish since vinyl chloride is not miscible with water and is lighter than water (will float on top of water). Most small fires can be ex tinguished with carbon dioxide or dry chemical agents if properly applied. Adequate fire extineL.fiing equipment of carbon dioxide or dry chen al type, fixed and portable, should be provided. W.ier fog or spray is also satisfactory for cooling. Diking and/or draining should be provided for confining and disposing of the liquid in case of tank rapture or spills. Precautions should be taken to guard^against VCM entering the general sewer system. 6.4 Ho one should be permitted to enter a fire area until it has been checked and approved for safe entry unless equipped with proper protective clothing and self-contained respirator. 7. SHIPPING, LABELING, HANDLING AND STORAGE 7.1 SHIPPING 7.1.1 DOT Classification and Regulations Vinyl chloride monomer is classified by the U.S. Department of Transportation as a flammable com pressed gas. When shipped by rail, water or highway, it must be packaged in authorized containers and shippers must comply with all DOT Regulations re garding packaging, loading, handling, labeling, mark ing and placarding. 7.1.2 Usual Shipping Container-- Type and Size _ Cylinders--4B150, 4BA225, 4BW225, 3A150, 3AA150, DOT-25 and 3E-1800. Cylinders with brazed seams are not permitted. Maximum permitted fill ing density--84% Cargo Tanks--MC330 and 331. Maximum per mitted filling density--84% Tank Cars--DOT 106 500 X Maximum filling density--84% DOT 105 200 W Maximum filliru density--87% DOT112A340W Maximum filling density--86% 7.2 LABELING 7.2.1 DOT Requirements 7.2.1.1 Each container of vinyl chloride, in cluding tank cars shall carry an identifying label. 7.2.1.2 The proper shipping name Vinyl Chlo ride, as shown in the commodity list (para, 172.5) must be used and shown on the outside shipping con tainers per para 172.1(a) and 173.401(a). 7.2.1.3 Unless exempt, each individual con tainer must bear the RED LABEL for FLAM MABLE GASES as described in para. 173.408(a) (1). 7.2.1.4 DOT 177.823(b) requires that tank motor vehicles transporting VCM shall be marked on both sides and at the front and rear, with letters at least 4" high, with the words "FLAMMABLE GAS" or "FLAMMABLE COMPRESSED GAS." 10 CMA 015489 Manufacturing Chemists Association Manual Sht 5D-56 [ition, the name "VINYL CHLORIDE" must played in letters at least 2" high. The words 1ABLE GAS" must be displayed on other vehicles transporting 1000 lbs or more gross lit per para. 177.823(a). ft 7,2.1.5 Each railroad car must bear the 4GEROUS" placard per para 174.541(a)(1) 1(3). 7.2.1-6 Para. 173.402(a)(13) specifies that "EMPTY" label must be applied to containers cb have been emptied and on which the old label not been removed, obliterated, or destroyed. It must be so placed on the container as to completely cover the old label. 7.2.1.7 Para. 174.562(b) specifies that a "DANGEROUS--EMPTY" placard shall replace or cover the"Dangerous" placard on the railroad tank car which has been emptied. 7.2.2 Precautionary Labeling 7.2.2.1 The Manufacturing Chemists Associa tion recommends that all containers of VCM should bear a label as shown. The text is designed for the product as shipped for industrial use. It should be b * VINYL CHLORIDE DANGER! EXTREMELY FLAMMABLE LIQUID AND GAS UNDER PRESSURE HARMFUL IF INHALED MAY POLYMERIZE VIOLENTLY UNDER FIRE CONDITIONS OR LOSS OR REMOVAL OF INHIBITOR Keep away from heat, sparks, and open flame. Keep container closed. Use with adequate ventilation. Avoid breathing vapor. Avoid contact with skin. Keep cylinder out of sun and away from heat. Container should be grounded when being emptied. Never drop cylinder. FIRST AID: If inhaled, remove to fresh air. If not breathing give artificial respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Call a physician. In case of: Fire -- Use water spray, dry chemical, or COa. Spill or Leak--For small spills, evacuate area and permit to evaporate. For large spills or leaks, evacuate area. Dike or flush to ground and let evaporate. Do not flush to sewer because of explosion hazard. MCA Chemical Safety Data Sheet SD-56 available. 11 CMA 015490 Manual Sh#t 5D-56 Manufacturing Chemists Association Vinyl Chloride used in addition to or in combination with any spe cific wording required by law. Since individual statutes, regulations, or ordinances may require that particular information be included in a label, that certain information be displayed in a particular man ner, or that a specific label be affixed to a container, the use of this label text will not necessarily insure compliance with such laws. Such laws include the Federal Hazardous Substances Labeling Act; Federal Insecticide, Fungicide and Rodenticide Act; and similar state and municipal legislation. 7.3 CYLINDERS 7.3.1 Magnets or slings should never be used to unload cylinders. When transporting by crane or derrick a suitable platform, cradle or boot should be used. 7.3.2 Care should be exercised not to drop cylin ders or otherwise handle them roughly. 7.3.3 Cylinders may be moved by tilting and rolling them on their bottom edge. Dragging and sliding them should be avoided. 7.3.4 When cylinders are transported by hand truck, they should be held securely in position by means of a locking clamp, chain or other suitable holding device. 7.3.5 Cylinders should never be used as rollers for moving any object or material. 7.3.6 Valve protection caps should always be kept in place except when the VCM containers are connected to piping, apparatus or equipment. As soon as a cylinder is disconnected the protective cap should be replaced. 7.3.7 Avoid disturbing the fusible plug. The safety device should be tagged in order to differen tiate it from the discharge connection. 7.3.8 The area where the cylinder is connected should have adequate ventilation to prevent the build up of concentrations in the event of a leak. 7.3.9 Cylinders should be provided with pressure regulators as recommended by the supplier. 7.3.10 A water bath heated to a maximum of. 50C. (122F.) may be used to empty cylinders by' means of the vapor pressure of the vinyl chloride.' 7.3.11 Check valves must be installed in feed lines from the cylinder to prevent the reactants from entering the cylinder. 7.3.12 When the cylinder is empty, the valve should be securely closed. Air must not be allowed to enter the container. 7.3.13 Cylinders must not be filled except by or with the consent of the owner, and then only in accordance with DOT Regulations. 7.3.14 Return of Cylinders The cylinder valve protection cap or outlet car must be securely replaced. The lower portion of the DOT shipping tag, if attached to the cylinder, must be removed. In other cases, applicable to DOT Regulations, compliance is essential. Bill of lading should give the cylinder identification number (which appears on the shoulder of cylinder) for each cylin der shipped, show name of consignee and indicate that the cylinders arc empty. Full or partly emptied cylinders should not be returned without permission of the supplier. Such cylinders must be shipped as full cylinders and corre spondingly labeled and tagged. All empty cylinders should be returned promptly. 7 4 TANK CARS 7.4.1 Because of the flammable and toxic prop erties of VCM the unloading of tank cars is a hazard ous operation. The supplier should be contacted for instructions and the instructions closely followed. 7.4.2 DOT Regulations, Para. 174.560* to 174.563 inclusive, contain instructions which must be observed. 7.4.3 Cars should be unloaded only on private sidings. 7.4.4 Shipper's instructions should always be fol lowed and all caution markings on both sides of tank and dome should be read and observed. 7.4.5 No heat should be applied to the tank car. An inert gas line or compressed vinyl chloride gas line should be attached to vent connection of the tank car to provide a pressure for transfer of the liquid vinyl chloride from tank. Transfer may also be by pumping, 7.4.6 Cylinder nitrogen (inert gas) is often used as the pressuring medium in the event vinyl chloride gas is not available. Larger installations may have a suction line connected from the storage tank to a compressor which discharges compressed vinyl chlo ride gas to vent connection on tank car. The pres sure on the car should never exceed the service pres sure at which the safety valve is set to operate. 7.4.7 Return of Tank Cars As soon as a tank car is completely unloaded, ail valves must be made tight, the unloading connec tions must be removed and all closures made tight. Air must not be permitted to enter the vessel. The inert gas used for the unloading procedures should be left in the vessel at a pressure not to exceed the service pressure for which the car was designed, but sufficient to prevent forming a vacuum in cold climates. 12 CMA 015491 Vinyl Chi ride Manufacturing Chemists Association Manual 5h*t 50*56 7,4.8 The DOT DANGEROUS placards on sides and ends of tank cars must be removed, or reversed (if in metal placard holders) by the party discharging the tank car. The empty car must be offered to the receiving carrier cither without plac ards, or preferably with four (4) DANGEROUS-- EMPTY placards, 7.5 TRANSPORTATION EMERGENCIES 7.5.1 Assistance Available 7.5.1.1 CHEMTREC (CHEMical TRanspor- tation Emergency Center) This center, located in Washington, D. C. at the offices of the Manufacturing Chemists Associa tion, is manned 24 hours per day, seven days a week, and provides, by telephone, immediate response/ action information for police, fire-fighters and others concerned with the control of chemical transportation emergency situations. For assistance, dial *(800) 424-9300 in the 48 contiguous States of the USA 483-7616 in District of Columbia *(200) 483-7616 in Alaska In Canada, call Canadian Chemical Produc ers Association's TEAP (Transportation Emergency Assistance Plan). * Use long distance prefix if needed. 7.5.1.2 Company Mutual Aid A number of vinyl chloride manufacturing companies voluntarily participate in a mutual-aid or ganization under which, in the event of a transporta tion accident, the closest company VCM plant will dispatch a qualified adviser to the scene of the acci dent if requested to do so by the shipper of the commodity. 7.5.2 Emergency Control 7.5.2.1 Personnel Attending Accident Scene Shippers' representatives do not take charge of emergency operations. They are present as ad-visers only. 7.5.2.2 Recommended Emergency Kit The following are considered essential: a. Explosion meter b. Self-contained air supply c. Wood plugs and wood mallet d. Data sheet and pencil e. Camera and film f. Flashlight (Bureau of Mines approved) 13 g. Rubber gloves h. Slicker suit i. Rubber overshoes j. Safety lines (braided stainless, plastic cov ered) and harness k. Goggles l. Safety hat m. O-rings n. Strap wrench o. 10" adjustable wrench p. Screwdriver q. Ground continuity meter r. Large first aid kit and collapsible water container, approx. 50 gals. The water container should be filled at the emer gency site and be available for eye wash or treatment of chemical skin contacts. 7.5.2.3 Recommended Procedures Leaks of Vinyl Chloride I. Controllable Leaks a. Small holes: Drive wooden plugs. b. Larger holes: Neoprene patch, bonded or chained to tank. Spe cial rigs should be left to the judg ment of the man at the scene. c. Jagged holes are difficult to close. d. Potassium bicarbonate will extin guish a vinyl chloride fire but reignition often occurs. Use it around valves if it appears that a leak can be subsequently con trolled. II. Uncontrollable Leaks--No Fire a. Isolate area. b. Remove sources of ignition. c. Control spread of vapors by water spray. III. Uncontrollable Leaks--Fire a. Evacuate and isolate area. b. Keep adjacent cars cool, if possible, with water spray. c. Keep unofficial personnel away. d. Treat a non-buming tank car in vicinity of fire as if it is about to rupture. CMA 015492 Manual Sh*t SD-56 Manufacturing Cfiemijfi Association Vinyl Chloride e. If vinyl chloride gets to a sewer, evacuate area and flush sewers with fire hoses. 7.5.2.4 Spilled Vinyl Chloride Spilled vinyl chloride should not be deliber ately ignited. 7.5.2.5 Recovery or Removal of Vinyl Chloride Depending upon circumstances and extent of car damage, VCM may be recoverable, but recovery should not be the determining factor in controlling the situation. ^ a. If car condition permits, transfer contents to empty tank car using nitrogen pres sure. b. If car is ruptured, attempt to use pump with flooded suction. c. If pumping is impractical, use water or oil to float out remainder of VCM. d. Fill empty tank with water or nitrogen. e. If a vinyl-ice mixture forms, keep a water stream to the tank until it dissipates. f. Handling of vinyl chloride in a damaged car can be influenced by weather con ditions. At low temperatures, since vaporization is reduced, patch tank, if possible, so that it can be moved. 7.5.3 Marine Emergencies 7.5.3.1 U.S. Coast Guard regulations require that a cargo information card for vinyl chloride be carried aboard the tank barge mounted near a warn ing sign and in such a position as to be easily read by a man standing on the deck of the barge. The cargo information card shall also be carried on the bridge or in the pilot house of the towing vessel. Copies are available from the Manufacturing Chemists Associa tion. 7.5.3.2 Special Safety Equipment In addition to normal safety equipment pro vided at the dock, the following special items should be available: a. Self-contained breathing equipment (at least two with two spare bottles). b. Explosimeters. c. Ground continuity meter. d. Water with an appropriate number of nozzles. e. Dry chemical fire extinguisher. f. MCA Chemical Safety Data Sheet SD-s^ and Cargo Information Card CIC-,- 7.5.3.3 Recommended Emergency Procedures 7.5.3.3.1 Leaks oj Vinyl Chloride I. General--Activate Alarm II. Controllable Leaks--No Fires a. Isolate leak from source. b. Eliminate ignition source. c. Control spread of vapors by water fog. d. Attempt to repair leak using ade quate safety protection proce dures. III. Uncontrollable Leaks or Ruptures--No Fires a. Isolate area. b. Remove all sources of ignition. c. Use water spray to prevent ac cumulation of liquid and to -* dissipate vapor cloud. It is not recommended that the ship's fire water supply be hooked into the city water supply.) IV. Uncontrollable Leaks--Fire a. Isolate area. b. Evacuate area except for emer gency personnel. c. Use water fog on fire and fumes (do not extinguish fire unless leak can be controlled). d. Use copious amounts of water to keep adjacent areas cool. e. Treat adjacent tanks as if about to rupture. f. Make provisions to minimize the mixing of air with VCM vapor in confined spaces and the burning tanks or line (water, N- or inert gases). 7.5.3.3.2 Spilled Vinyl Chloride Spilled VCM should not be deliberately ignited. 7.5.3.3.3 Recovery or Removal of Vinyl Chloride Depending upon circumstances and the ex tent of the tank damage VCM may be recoverable 14 CMA 015493 Vinyl Chloride Manufacturing Chemists Association Monval Sht 50-54 but provisions must be made to keep air out of the tank. a. If tank condition permits, transfer con tents to an empty tank or back to shore. b. If tank cannot be patched and it does not have a deep well pump or the deep well pump cannot be used, sparge heated nitrogen into the bot tom of the tank to vaporize the VCM. c. Fill empty tank with water or inert gas. 7.6 STORAGE 7.6.1 VCM should always be handled with full recognition of its flammability. Precautions should be taken both to keep the material enclosed and to eliminate sources of ignition. 7.6.2 Corrosion VCM is noncorrosive at normal atmospheric temperatures when dry (moisture free). In contact with water at elevated temperatures VCM accelerates corrosion of iron or steel. 7.6.3 Volatility VCM is very volatile and is a gas at normal atmospheric conditions. Containers used for han dling VCM at ambient temperature are usually under pressure. 7.6.4 Temperature Requirements Uninhibited VCM may be stored either under refrigeration or at normal atmospheric temperature in the absence of air or sunlight. Regular checks should be made for the presence of polymers. 7.6.5 Conditions of Storage 7.6.5.1 Type of Construction All piping (including instruments leads), storage stanks, relief devices and equipment em ployed to handle VCM should be of steel and de signed to have a working pressure of at least 100-150 psi with a safety factor conforming to the A.S.M.E. code for unfired pressure vessels or any code applying to locale of planned storage. Shut-off valves and con trol valves should" be of steel or a suitable alloy not bearing copper, designed for working pressures of 150 psi or over. All-welded construction is preferred to riveted construction. It is recommended wherever possible that all liquid inlet lines enter the bottom or extend to the bottom of the vessel. This aids in guarding against the accumulation of static electric ity. All equipment should be properly grounded and bonded with resistance to ground never exceeding 25 ohms. Electrical lighting, wiring and equipment should conform to NEC. An efficient water spray system should be installed or made available. Ade quate diking and/or draining should be provided under tank area to confine and dispose of the liquid in case of vessel rupture. Cylinders used to store VCM must meet DOT Specifications. 7.6.5.2 Isolation Storage areas should be selected in accord ance with local codes or authorities having jurisdic tion. For highly volatile and flammable material, storage should be located outside of buildings. Cylin ders containing VCM should be stored always in a vertical position, outside of buildings, and in an iso lated and well ventilated area. It is preferable to store cylinders in the open, but provision should be made to shield them from the direct rays of the sun and prevent accumulation of dirt, snow, water, or icc on valves or safety devices. 7.6.5.3 Compatible and Dangerously Reactive materials Tanks in VCM service should be used only for the storage of VCM. Before VCM is placed in a ' tank, the vessel should be purged with a dry inert gas until free of oxygen. VCM is generally noncorrosive * at normal atmospheric temperatures when dry (mois ture free). However, mild to appreciable corrosion has been noted when wet, even at ordinary tempera ture. This may be due to the presence of impurities. In contact with water at elevated temperatures VCM accelerates corrosion of iron or steel. Acetylene as as impurity in VCM may form an explosive com pound (acetylide) when exposed to copper or pos sibly copper alloys. 7.7 REPACKAGING 7.7.1 Only clean, DOT Specification cylinders should be used. 7.7.2 Adequate ventilation should be provided and all sources of ignition removed from transfer area. 7.7.3 Proper personal protective equipment should be used. Transferring VCM from cylinders by the use of an uncontrolled heating method is not recommended. Temperatures of over 50C. (122F.) should not be applied to any part of a cylinder con taining compressed gas. Excessive heating weakens the structural characteristics of the metal and may seriously damage the cylinder. Low melting safety devices may reach the fusing point by the application of excessive heat to a cylinder. Never apply direct flame to a cylinder. A definite fire hazard is created. For recommended practice to transfer contents of a cylinder see 7.3. 15 CMA 015494 Manual sh*t SD*56 Manufacturing Chemists Association Vinyl Chloride ------------------------------- -------------------------------------------------------- *--------- ---------------------------------------- 8. TANK AND EQUIPMENT CLEANING AND REPAIRS (See MCA Safety Guide SG-10 "Entering Tanks and Other Enclosed Spaces") 8.1 JOB EVALUATION AND PREPLANNING 8.1.1 Because vinyl chloride monomer has phys ical and chemical properties which generate hazards of a toxic and flammable nature, tank and equipment cleaning and repairs should be conducted in such a manner as to eliminate or minimize the hazards. (See 10.1.1 Health Hazards--Note concerning Acroosteolysis.) 8,1.2 Equipment apd tank cleaning and repair should be under the direction of thoroughly trained personnel who are fully familiar with all of the haz ards and the safeguards necessary for the safe per formance of the work. All precautions pertaining to education, protective equipment, and health and fire hazards should be reviewed and understood. 8.1.3 The hazardous nature of tank inspection, cleaning, and repair requires that the foreman and crew be selected, trained, and drilled carefully. They should be fully familiar with the hazards and the safe guards necessary for the safe performance of the work. The preparation of a stepwise work procedure for the entire job, recognizing all possible hazards as they might occur, developing safe procedures and designating suitable protective equipment, has been found to be particularly effective in maintaining work safety. 8.1.4 A written work permit must be prepared before tank preparation and entry. It must describe work procedures to be used, hazards which may be encountered and procedures and equipment to be used to nullify these hazards. It must be prepared, reviewed and signed by the supervisor to whom the tank is assigned after they have satisfied themselves that tank entry and repair work can be done safely. 8.2 TANK OR EQUIPMENT CLEANING 8.2.1 Tanks and equipment, pumps, lines and valves should normally be drained and thoroughly cleaned before being repaired. Workmen should never be allowed to attempt to repair equipment while it is in operation and the lines in service unless special precautions are used such as "Hot Tap" work. 8.2.2 Smoking, use of open flames, and the pres ence of unauthorized personnel should be prohibited. 8.2.3 All lines, which may contain hazardous substances, entering or leaving the tank should be blanked. After draining, the tank should be flushed with water to remove any remaining VCM liquid. The tank should then be steamed to remove residual VCM. Water and steam lines and nozzles should be grounded to minimize hazards of static clectricitv. The tank should then be cooled by filling with water and draining. Finally, the tank should be purged with fresh air and then tested for VCM by an ap proved method. It should also be tested for oxygen sufficiency. The controls for all agitators, pumps and other electrical equipment connected to the tank should be padlocked by the worker entering the tank. 8.3 ENTERING TANK 8.3.1 No one should enter a tank or confined space until a work permit has been signed by an authorized person indicating that the vessel has been properly prepared, tested and found to be safe. 8.3.2 No workman should enter a tank or vessel that does not have a manhole opening large enough to admit a person wearing a safety harness, lifeline and emergency respiratory equipment. 8.3.3 Forced air ventilation is recommended dur ing the entire time men are cleaning, repairing or inspecting the tank. Ventilation can be accomplished by exhausting or removing vapors from the bottom of the tank either through a bottom opening or through a large flexible duct. Blowers should be sparkproof and should not be allowed to overheat and thus provide a source of ignition. All men who enter the tank should wear a safety harness and life line. 8.3.4 When a tank car or storage tank is being cleaned or repaired one man on the outside of the tank should keep the men in the tank under observa tion. This man should not leave his post or enter the tank without first obtaining a substitute. Another man should be available nearby to aid in rescue if any of the men in the tank are overcome. 8.3.5 Suitable respiratory protective equipment, together with rescue harness and lifeline, should al ways be located outside the tank for rescue purposes. 8.3.6 During the course of the work, frequent -- air samples should be taken to see that the concen trations are within safe range. 8.3.7 If repair work is interrupted, the tank atmoshere should be tested and a new work permit issued before work is resumed. 8.4 EMERGENCY RESCUE 8.4.1 A rescuer should not enter a confined space without wearing approved respiratory protec tive equipment, a safety harness and an attached lifeline. Another employee should be immediately 16 CMA 015495 lyinyl Chloride Manufacturing Chemists Association Manuol Sh**t SD-54 available to man the lifeline and to assist in the -rescue if needed. The rescuer should be in view of | the outside attendant at all times or in voice com munication with him. 8.5 EXTERIOR REPAIR WORK All outside welding, burning or spark-producing work on tanks or equipment which have contained VCM should be done after the container has been thoroughly cleaned of VCM vapors. Purging should be tested by a competent person to see if it is free of VCM. It is not recommended that air be used to purge a vessel. If the repair work is interrupted, the tank atmos phere should be checked thoroughly and a new work permit issued before resumption of work. WASTE DISPOSAL (See 7.5) 9.1 All Federal, State.`and Local regulations re garding health and pollution should be observed. Disposal of waste material, however, depends to a great extent upon surroundings, weather conditions and the emergency making disposal necessary. 9.2 When it becomes necessary to dispose of VCM as such, it is preferable to do so as a vapor, venting to an area free of any source of ignition. 9.3 When a waste disposal problem arises as a result of a major spill or equipment rupture, only properly protected and qualified personnel should remain in the area. 9.4 Waste mixtures containing VCM should not be allowed to enter drain or sewers as serious explosions in such systems may result. 10. MEDICAL MANAGEMENT 10.1 HEALTH HAZARDS 10.1.1 Vinyl chloride monomer docs not present a serious industrial health hazard provided workers are adequately supervised and observe the proper means of handling it. Under the Occupational Safety and Health Act, the U.S. Department of Labor has set a 500 ppm Ceiling Value on permitted employee exposures. Based upon animal and human observa tions, this level provides considerable margin of safety for industrial exposures. Note: A syndrome termed occupational acroosteolysis, characterized primarily by Raynaud's phenomenon and osteolytic changes in certain bones, particularly the distal phalanges of the hands, has been noted among certain workers in vinyl chloride polymerization operations. The specific cause of this disease, and particularly any role played by vinyl chloride, is unknown. _ . Recent research studies reported from Italy in dicate that repeated, long-term high level exposures of rats to vinyl chloride monomer vapor can result in the development bf malignant tumors. However, many years of industrial experience with human ex posures to concentrations frequently far above cur rent standards have not demonstrated any carcino genicity to humans. 10.1.2 Acute Toxicity Levels on the order of 6,000 ppm for five minutes exposure are required to produce minimal symptoms resembling mild alcohol intoxication in humans. Levels approximately 16,000 ppm for the same length of time will produce varying degrees of intoxication, with light-headedness, some nausea, and a dulling of visual and auditory responses in most humans. 10.1.3 Chronic Toxicity The liver is the principal target resulting from excessive chronic exposure. The currently recom mended ceiling level (OSHA) of 500 ppm is well below a level producing any signs or symptoms of toxicity. 10.2 PREVENTIVE MEASURES 10.2.1 All operations in which vinyl chloride is used should be regularly evaluated and atmospheric concentrations kept, at all times, below 500 ppm. "Sophisticated air sampling techniques are required. . , This includes gas chromatography. Processes must be closed or ventilated sufficiently to achieve a con centration control low enough so that respiratory protection devices are needed only on an emergency basis. 10.2.2 Personal Hygiene , Vinyl chloride should be kept off the skin and out of contact with the eyes. If accidental contact to the skin occurs, immediate washing with soap and water is necessary; if to the eyes, immediate irrigation 17 CMA 015496 Manual Shift SD-56 Manufacturing Chemists Association Vinyl Chloride for a minimum of 15 minutes with water is required. The pescncc of skin and eye washing equipment in the areas where vinyl chloride is used is necessary. Washing supplies and equipment should be maintained and always immediately available. 10.2.3 Physical Examinations Prcplacement examinations should be made on all workers having potential exposure to vinyl chlo ride. with particular emphasis placed upon liver and kidney functions. 10.3 SUGGESTIONS TO PHYSICIANS Treatment for vinyl chloride intoxication is symp tomatic; no special procedures arc required. It should be recognized that the principal target of chronic exposures is the liver, with secondary effects, particularly in acute exposures, to the kidney. In acute overcxposurcs the primary effect is on the central nervous system. Note to Physician: Avoid use of epinephrine or related drugs in treating acute overexposure cases since vinyl chloride may sensitize the heart to the arrhythmic action of these drugs. 10.3.1 Oxygen Administration Oxygen has been found useful in the treatment of inhalation exposures of many chemicals, especially those capable of causing either immediate or delayed harmful effects in the lungs. In most exposures, administration of lOOrioxygen at atmospheric pressures has been found i be adequate. This is best accomplished by use l ^ face mask having a reservoir bag of the non-: > breathing type. Inhalation of 100% oxygen shouid not exceed one hour of continuous treatment. After each hour, therapy may be interrupted. It may be reinstituted as the clinical condition indicates. Some believe that superior results arc obtained when exposures to lung irritants are treated with oxy gen under an exhalation pressure not exceeding 4 cm. water. Masks providing for such exhalation pressures arc obtainable. A single treatment may suffice for minor exposures to irritants. It is believed by some observers that oxygen under pressure is useful as an aid in the prevention of pulmonary edema after breathing irritants. In the event of an exposure causing symptoms, in case of a history of severe exposure, the patieru may be treated with oxygen under 4 cm. exhalation pressure for one-half hour periods out of every hour. Treatment may be continued in this way until symp toms subside or other clinical indications for inter ruption appear, CAUTION: It may not be advisable to ad*minister oxygen under positive pressure in the presence of impending or existing cardiovascular failure. The use of adrenalin is not recommended because some chlorinated hydrocarbons can increase the risk of ventricular fibrillation after adrenalin therapy. 11. FIRST AID 11.1 GENERAL PRINCIPLES First aid should be started at once in case of acute intoxication with vinyl chloride. Immediately re move the affected individual to fresh air. Refer all injured individuals to a physician and give a detailed account of the incident. washing with copious quantities of water for at least 15 minutes should be instituted immediately. It is advisable to irrigate the eyes gently with water at room temperature in order to minimize additional pain and discomfort. Prompt medical attention should be obtained. 11.2 CONTACT WITH SKIN AND MUCOUS MEMBRANES - ' Vinyl chloride, in concentrated form, is a skin irri tant. All contaminated, clothing should be removed at once; and thisxJothing, including shoes, if there is any evidence of contamination, should not be worn again until thoroughly dry. All affected skin areas should be thoroughly washed with warm water and soap. The individual should be referred to a physi cian. 11-3 CONTACT WITH EYES If vinyl chloride has entered the eyes, prompt 11.4 INHALATION Promptly remove the affected individual from ex posure. to fresh air. If breathing has ceased effective artificial respiration should be started immediately. If oxygen inhalation equipment is available oxygen should be administered, provided a person authorized for such administration by a physician is available. The patient should be comfortably warm but not hot. Stimulants will rarely be necessary where adequate oxygenation is maintained. Any such drugs for shock treatment should be given only by the attending physician. Never attempt to give anything by mouth to an unconscious patient. / 18 CMA 015497 OTHER CHEMICAL SAFETY DATA SHEETS AVAILABLE (Date of latest available edition, as of March 1972, given in parentheses) Acetaldehyde ___ _ _(1952) SD-43 Cresol______________ ....__(1952) SD-48 Acetic Acid ,_____ _______ (1951) SD-41 Cyclohexane ...... ....... (1957) SD-68 Acetic Anhydride _______ (1962) SD-15 Diethylamine_______ ____ (1971) SD-97 Acetone _____ ,,(1962) SD-87 Diethylenetriamine ... ..._ (1959) SD-76 Acetylene________(1957) SD-7 Dimethyl Sulfate ..... ._ (1966) SD-19 Acrolein _____ ______ (1961) SD-85 Dinitrotoluenes .... (1966) SD-93 Acrylonitrile __ _________ (1964) SD-31 Ethyl Acetate ......--....... (1953) SD-51 Aluminum Chloride _____ (1956) SD-62 Ethyl Chloride______ (1953) SD-50 Ammonia Anhydrous_____(1960) SD-8 Ammonia Aqua ______ (1947) SD-13 Ammonium Dichromate ....(1952) SD-45 Aniline ___ __(1963) SD-17 Antimony Trichloride (Anhydrous)___ ___ ____ (1957) SD-66 Ethyl Ether....... .......... ..(1965) SD-29 Ethylene Dichloride (1971) SD-18 Ethylene Oxide _____ ____ (1971) SD-38 Formaldehyde ......... (1960) SD-1 Hydrochloric Acid_______(1970) SD-39 Hydrocyanic Acid _______ (1961) SD-67 Arsenic Trioxide ________ (1956) SD-60 Hydrofluoric Acid .. ... (1970) SD-25 Benzenei(I960) SD-2 Hydrogen Peroxide... ____ (1969) SD-53 BBBBBBeeorueonnrttomaazznoyndinlyaiHleeCpnyPhhdeet(lo1hr_ri9or_yd6ix_ldea8i_de)sm_e((_S11i_n99D__56e-_714_(_))19__9_SS_4_DD9__)--_68(_S941_9D_5-_34_2)_(S1D96-505)SD-8HIMLMM1seyoaeeEadptltdtehrhrhooiyaycgOplnleyAoAxAnllicancdrm.rShey.y.luyis.lana.dl..tfe.t.ei.er.d..i.dea....en....._d._.....__......__...__._. ____.___..___. (1968) (1959) (1956) (1962) (1970) (1960) SD-36 SD-72 SD-64 SD-88 SD-22 SD-79 n-Butyllithium in Hydrocarbon Solvents_(1966) SD-91 Butyraldehydes (1960) SD-78 Calcium Carbide(1967) SD-23 Carbon Disulfide(1967) SD-12 Methylamines __ Methyl Bromide , Methyl Chloride .. Methylene Chloride Methyl Ethyl Ketone (1955) SD-57 (1968) SD-35 0970) SO-4Q (1962) SD-86 (1961) SD-83 Carbon Tetrachloride ,,___(1963) SD-3 Caustic Potash (1968) SD-10 Mixed Acid Naphthalene (1956) SD-65 (1956) SD-58 Caustic Soda(1968) SD-9 Nitric Acid (1961) SD-5 Chlorine(1970) SD-80 paraNitroaniline (1966) SD-94 Chloroform (1962) SD-89 Nitrobenzene (1967) SD-21 Chlorosulfonic Acid(1968) SD-33 Chromic Acid(1952) SD-44 Nitrocellulose (Wet Types) 0970) SD-96 Ortho-Dichlorobenzene ,,.(1953) SO-54 Paraformaldehyde .......... .(I960) SD4 Perchloroethylene....... ..... (1971 ;D-24 Perchloric Acid Solution (196: ;Q-U Phenol .............--....--...... (1964) SD4 Phosgene ...... .....-..... (1967) SD-95 Phosphoric Acid --- -------- (1958) SQ-7d Phosphoric Anhydride .... (1948) SD-28 Phosphorus, Elemental_(1947) SD-16 Phosphorus Oxychloride .,(1968) SO-26 Phosphorus Pentasulfide .(1958) SD-71 Phosphorus Trichloride ....(1972) SD-27 Phthalic Anhydride _____ (1956) SD-61 Propylene -------------------(1956) SD-59 Sodium Chlorate(1952) SD-42 Sodium Cyanide________ ..(1967)SO-30 Sodium, Metallic________ (1952)SD-47 Sodium and Potassium Dichromates.................. (1952) 7 46 Styrene Monomer________ (1971) ,: 37 Sulfur ___ (1959) SC-74 Sulfur Chlorides _(1960) SD-77 Sulfur Dioxide(1953) SD-S2 Sulfuric Acid(1963) SD-20 Tetrachloraethane.(1949) D-34 Toluene ,,_____________(1956) SD-63 Toluidine(1961) SD-82 Toluene Diisocyanate ___ (1971) SD-73 1,1,1-Trichloroethane___ (1965) SD-90 Trichloroethylene(1956) SD-14 Vinyl Acetate(1970) SD-75 Vinyl Chloride(1972) SD-56 Zirconium and Hafnium Powder(1966) SD-92 0472-5000 For free Publications list and prices, write or phone Publications Service MANUFACTURING CHEMISTS ASSOCIATION 1825 Connecticut Avenue, Washington, D. C. 20009 Phone: 202-483-6)26 PftINTEO IN U-S.A CMA 015498