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Chemical Safety Data Sheet SD-56 PROPERTIES AND ESSENTIAL INFORMATION FOR SAFE HANDLING AND USE OF VINYL CHLORIDE ADOPTED 1954 ChemtasU in any form ran be safely itortd, handled or wud H the physical, chemical and hazardous properties are fully under* stood and the necessary precautions, including the use of proper safeguards and personal protective equipment, are observed. MANUFACTURING CHEMISTS ASSOCIATION 1825 CONNECTICUT AVENUE. N. W. WASHINGTON. D. C 20009 BFG03' 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. (122*F.). 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. BFG03700 T 20508002 TABLE OF CONTENTS Page 1. NAME ........ ...................................................................... .... .......................................... 6 2. PROPERTIESS 2.1 Grade._______________________________________ 5 2.2 Important Physical and Chemical Properties5 2.3 Hazardous Properties_______ --_.....-- ----- 6 3. USUAL SHIPPING CONTAINERS6 3.1 Type and Size6 3.2 Label or Identification 6 8.3 Disposal and Return Precautions7 4. UNLOADING AND EMPTYING 7 4.1 Health Hazards-__________ -- 4.2 Fire and Explosion Hazards7 4.3 Cylinders__________________ 4.4 Tank Cars_____8 ---------- --------- ------- - -------- 7 7 B. STORAGE 8 B.l Hazards________________ 6.2 Conditions of Storage_____________________________ 6. HANDLING9 8 8 6.1 Health Hazards........... ... ................... ......... --........... 9 6.2 Fire, Explosion, and Polymerization Hazards9 6.3 Spills and Leakage10 6.4 Employee Education and Training________ 10 6.5 Personal Protective Equipment11 6.6 Engineering Controls _____________--... 13 6.7 Ventilation13 6.8 Tank and Equipment Cleaning and Repairs________________________________ 13 6.9 Repackaging -- - ------ ----- ------- 14 7. WASTE DISPOSAL14 8. HEALTH HAZARDS AND THEIR CONTROL....................................................... 15 8.1 Hazards----------------------------------------------------------------------------------------------------15 8.2 Prevention and Control15 8.3 Personal Protective Equipment15 8.4 First Aid and Medical Care--_______________________________________ 16 o O The information and recommendations contained in this publication have been compiled from sources believed to be reliable and to represent 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 conditions or circumstances. to (O Cft CO oo CO BFG03701 'T Chemical Safety Data Sheet Manual Sheet SD-S6 VINYL CHLORIDE Adopted February, 1954 1. NAME Chemical Names: Vinyl Chloride Chloroethylene Chloroethene Common Name: Vinyl Chloride Formula: CH,CHC1 2.1 Grade: 2. PROPERTIES Technical with inhibitor. (Purity of Bample 99.42%) 2.2 Important Physical and Chemical Properties:* Boiling Point ____ --13.8*C. (+7F.) Color_______ .........Colorless 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 Hygroscopicity___ _____No 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 20C. (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. 20508004 5 BFG03702 Manual Sheet SD-56 M*snfMturini Cbamiau' Amdelation. 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 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-106A300 and ICC105A300W. Maximum permitted Ailing 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). O 3.1 Type and Size 3.2 Label or Identification 3.1.1 Approved ICC cylinders and tank cars designed to carry liquid gases under pressure and equipped with safety relief devices. 3.2.1 Each container of vinyl chloride (in cluding tank cars) should carry an identifying label or stencil. 3.1.2 All parts of valve and safety devices 3.2.2 The Manufacturing Chemists' Asso in contact with contents of containers must be ciation recommends the following in addition to, of metal or other material, suitably treated if or in combination with, any label warnings or necessary, which will not cause formation of other statements required by statutes, regula v any acetylides. A good practice is to dismantle tions, or ordinances: VINYL CHLORIDE DANGER! EXTREMELY FLAMMABLE LIQUID AND GAS UNDER PRESSURE Keep away from heat, sparks, and open flame. Keep container closed. Use with adequate ventilation. Avoid prolonged breathing of vapor. 6 BFG03703 S0080S02 Vinyl Chloride Manufacturing Chemist*' Association, Inc. Manuat Sheet SD-36 3.2.8 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-4BS00 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. (122eF.) 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 BFG03704 20508006 T Manual Sheet SD-56 Manufacturing ChcmiiU' Association. Inc. Vinyl Chloride 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 and Their Control) 5.1.1 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. 5.1.2 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. 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 O O i 8 20508007 BFG03705 Vinyl Chloride Minufaetarinr Chraiats' AiaoeUtlon. 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 Btatic 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 REQ UIREMENTS 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 20508008 BpG03706 Manual Sheet SD-56 Minufteturinc ChemitU' Aatociatlon. 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 Are 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). In event of a fire no unauthorized person should be permitted to enter an unventilated area until the space has been thoroughly sprayed with water to remove gases such as hydrogen chloride, phosgene, carbon monoxide, etc. generated from the fire. 6.2.2 EXPLOSION HAZARDS 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 ment, and static electricity are to be avoided when handling this material. 6.2.3 POLYMERIZATION HAZARDS Vinyl chloride does not form peroxides by autoxidation as readily as many other monom ers. Aside from polymerization, vinyl chloride is chemically quite stable (See 2.2 Reactivity). Vinyl chloride can be satisfactorily stored without an inhibitor for short periods if it is kept in steel tanks under refrigeration or at normal atmospheric temperature in the absence of air and sunlight. For shipping purposes inhibitors are employed. Inhibitors, like phenol, when present have hazards of their own, being very toxic (See 7.5). 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, all 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. A6.2ll.1so).urces of ignition should be removed (See 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 should be removed to an isolated, well-ventilated area and the contents transferred to other suit able containers (See 4.3 and 5.2.2). 6.3.6 The detection of leaks in equipment of vinyl chloride can best be accomplished by the use of a flammable gas indicator, or by inspection for the presence of vapors and frost ing on the surfaces of the equipment. 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). 6.3.8 Clothing contaminated with vinyl chloride should be removed immediately and the body washed thoroughly to remove any mate rial which may have penetrated to the skin. Clothing should be washed before reuse. If necessary shoes should be replaced with new ones. Disposal of the contaminated shoes is recommended if the spilled vinyl chloride con tained a toxic inhibitor, like phenol. 6.4 Employee Education and Training 6.4.1 Safety in handling vinyl chloride and other hazardous chemicals depends upon the effectiveness of employee education, training, and the safety instructions incorporated into job instruction manuals. 10 o * t o \ 20508009 BFG03707 Vinyl Chloride M*nufturine Cb*mbU` AMoeiation. Inc. Manual Sheet SD-56 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 20508010 BFG03708 Manual Sheet SD-56 Manufacturing Cham lata' Aaaociation, 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, where 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 by 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 but harmless 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 20508011 BFG03709 Vinyl Chloride M*nufeturlne ChernUu' AMOUtion. Inc. Manual Shfet 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 20508012 BFG03710 "T Manual Shet SD-56 lLovf*eturln* ChtmliU' Association. Ine. Vinyl Chloride 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 vinyl 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 60C. (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 20508013 BFG03711 Vinyl Chloride UanufactuHnf CheinUU' AUMiation. Inc. Manual Sheet SD-56 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* suit (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 600 ppm. 8.1.2 SYSTEMIC EFFECTS In concentrations well above 600 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 water 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 20508014 BFG037I2 Manual Sheet SD-56 Manufacturing Chamlata' Aaaoelation. Ine. 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 hazardous exposure to vinyl chloride, and all personnel should be immediately evacuated from the area until the leak or spill has been located and corrected and until complete recovery from all symptoms has occurred. Because of the mildness and slew 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. In 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 20508015 BFG03713 CHEMICAL SAFETY DATA SHEETS (1W) $043 (1061) $p-41 (1067) sn.15 (1067) SnJ7 (1067) sn-7 Acrolein (1061) SO*6 , (1064) so-31 (1066) $ru>? Ammonium Dichromate Ammonia Anhydrous Ammonia Aqua (1067) Sr>46 (i06n) $njj (1047) $0-13 no60) sn.17 Antimony Trichloride (Anhydrous) Arsenic Trinxide Benzene Benzyl Chloride Benzovl Peroxide Betanaphthylamlne Boron Hvdrides (1956) SD-66 (io66) $n-6n (I960) SD-2 (1067) sn-go ___(i960) $0-81 , (1949) $[>32 (1961) SD-84 no69i oruio Butadiene (1064) sn.65 *n-Butyllithium in Hydrocarbon Solvents Butvraldehydes Calcium Carbide Carbon Disulfide ,, , (1966) SD-91 (I960) SD-78 (1948) SD-23 (1067) sn-17 Carbon Tetrachloride (1060) Rn.0 Caustic Potash Caustic Soda (1947) SD-10 (1047) $rvo Chlorine (i960) $080 Chlorosuifonic Acid Chmmic Arid Cresnl (1962) SD-89 (1949) SD-33 110671 SD-44 (1952) SIMS Diethylenetriamine (1957) $068 (1960) $n-7A Dimethyl Sulfate (1966) $019 (1066) $093 (1060) $051 Ethyl Chloride (I960) $060 Ethv! Fther ....(1965) $029 Ethvlene Oxide Forme Irtehyde Hydrochloric Acid (1947) S018 (1951) SD-38 (1960) SD-1 ... (1951) $039 (1961) $067 Hydrofluoric Acid (1957) S025 Hvdrosen Peroxide . (10551 S053 Hydrogen Peroxide (Not Exceeding 52%) (1961) SD-53--Sup. A Hydrogen Peroxide (High Strength)__ (1961) SD-53--Sup. B Hvdroeen Sulfide .... (19501 S_36 Isopropylamine (1959) $07? Maleic Anhydride (1956) $064 (1962) SD-88 Methyl Acrylate and Ethvl Acrvlate (1960) S079 (1044) SO?? Methylamines Methvl Bromide Methvl Chloride Methylene Chloride Methyl Ethyl Ketone Mixed Acid _ Naphthalene `Nitric Acid(1961) SD-5 (1955) S057 (1949) S035 (1951) SD-40 ..(1962) SD-86 (1961) SD-83 (1956) SD-65 (1956) S058 Nitrobenzene(1948) SD-21 Ortho-Oichlorobenzene_____ (1953) SD-54 Paraformaldehyde__________ (I960) SD-6 paraNitroaniline ___________ (1966) SD*94 Perchloroethylene__________ (1948) SD-24 Perchloric Acid Solution ___ (1965) SD-11 Phenol(1964) SD-4 2-67-3M (1958) SD-70 Phosphoric Anhydride______(1948) SD-28 (1947) $0-16 Phosphorus Oxychloride _____(1948) SO-26 Phosphorus Pentasulfide ___ (1958) SD-71 Phosphorus Trichloride ,,____(1948) SO-27 Phthalic Anhydride (19661 $061 (1066) Rl>$9 Sodium Chlorate (196?1 $04? Sodium Cyanide (1949) $030 Sodium. Metallic Sodium and Potassium (196?) $047 Styrene Monomer (195?) SP-46 (1961) $037 Sulfur Sulfur Chlorides Sulfur Dioxide Sulfuric Arid Tetrachloroethane (1960) $074 (I960) $077 _ ,, (1953) SP-5? (1063) $020 (1949) SD-34 (1066) On-fil Toluidine (1961) ru (I960) 0073 Vinyl Acetate (1965) $090 (1956) $014 (1969) $07$ Vinyl Chloride . Zirconium and Hafnium Powder (1964) $05$ (19661 $097 c>i<rt miaii LABORATORY SAFETY 1. Film "Safety in the Chemical Laboratory"--A 16 mm sound-color, 20-minute film. Pur chase Price $100.00. Preview charge, $5 per week--deductible from purchase cost if ordered within 30 days of preview. A Teacher's Guide accompanies die film. 2. 234 page volume--"Guide for Safety in the Chemical Laboratory"--$6J0. Order direct from D. Van Nostrand & Co., Inc., 120 Alexander St, Princeton, N. J. CASE HISTORIES OF ACCIDENTS IN THE CHEMICAL INOUSTRY Vol. One --1962 %2J0 Vol. Two--1966 $330 MANUALS L-l Guide to Precautionary Labeling of Hazardous Chemicals (Sixth Edition--1961)2.00 TC-2 Tank Cars--ICC Spec. 103B, Rub ber-Lined--Unloading when filled with Muriatic Acid, Phosphoric Acid, or other authorized liquids. .15 TC-3 Tank Cars--Unloading when filled with liquid Caustic Soda or Caus tic Potash (Revised 1946, 1950, 1952) ___ ___ _____ .20 TC-4 Tank Cars--Unloading when filled with flammable liquids (Revised, 1952) .20 TC-6Tank Cars--Unloading when filled with Phenol (Revised, 1959)____ 30 TC-7 Tank Car--Loading and Unloading Platforms 30 V,nEm*^AKU9 b Cbaitai Stfitr et* SImU Kfcid vitt Mtorltk (*| Also available for: Butyllithium Chlorine Trifluoride Diethylamine (Anhydrous) Dimethyl Ether Epichlorohydrin Ethanol Ethyl Acrylate Fluorine (Liquid) Hydrazine/UDMH Hydrogen, Liquid Isopropanol Isopropyl Ether Methyl Acrylate Methylamines (Anhydrous) Methylamines (Aqueous) Methyl Isobutyl Ketone Methyl Methacrylate Monomethyl Hydrazine Motor Fuel Antiknock Compound Nitric Acid (Red, Fuming) Nitrogen, Liquid Nitrogen Tetroxide Oleum Oxygen, Liquid Pentaborane Perchlbryl Fluoride Sulfur Trioxide Unsymmetrieaf Dimethyl Hydrazine Vinylidene Chloride Xylene CHEM-CARD MANUAL $130 CHEMICAL SAFETY GUIDES Health Factors in the Safe Handling of ChemicalsSG-1 Housekeeping in the Chemical Industry SG-2 Flammable Liquids--Storage and Handling of Drum Lots and Smaller Quantities ___SG-3 Emergency Organization for the Chemical IndustrySG-4 Plastic Foams--Storage, Handling and FabricationSG-5 Forklift OperationsSG-6 Guide for Storage and Handling of Shock and Impact Sensitive Materials SG-7 Electrical Switch Lockout Procedure. SG-8 Disposal of Hazardous WasteSG-9 Entering Tanks and Other Enclosed SpacesSG-10 Off-The-Job SafetySG-11 Public Relations in Emergencies____SG-12 Maintenance and Inspection of Fire Protection EquipmentSG-13 Safety in the Scale-up and Transfer of Chemical Processes__________ SG-14 Training of Process Operators_______SG-15 Liquid Chemicals: Sampling of Tank Car and Tank Truck Shipments____SG-16 Fire Protection in the Chemical Industry SG-17 Identification of Materials_________SG-18 Electrical Equipment in Hazardous AreasSG-19 CHEMICAL SAFETY DATA SHEETS _________________________ 30 cents each SAFETY GUIDES __________________ 20 cents each 10% discount on complete sets of chemical safety data sheets or of safety guides or total quantities of 100 or more. Future issues may be obtained, when and as issued, on a yearly subscription basis--billed at the end of the year. CHEM-CARDS5 cents each 100 to 5,000 -------------------------------------------------------------------------------20% discount Over 5,000 --------------------------------------------------------------------------------30% discount CMInmHmittsmAlunKaiiaRtMlHC. t iwmit* GirtwoMr ctt*icvZtaBAllmutuiM, i WOtMiri*tMftit,, MB. iiCn.fieMttMrli.f f) 20508016 BFG03714 03 / o( / Toxicology of Plastics and Rutter -- PLASTOMERS AND MONOMERS REX H. WILSON, M.D., F.A.C.P., anJ WILLIAM E. McCORMICK, M.S. The B. F. Goodrich Company, Akron, Ohio he popular demand for all types of articles Tmade from plastics has been so tremendous that literally there has been created an en tirely new industry in the past several years. Many plants, large and small, are devoting their entire manufacturing facilities to "plastic" items. The demand for the compounds going into the composition of the plastic materials is so great that supplies of certain of them are short. Because the industry is new and because of the ingenuity of modern research, the compounds making up the plastics are ever changing. Also, as demands for different types of articles made from plastics are increasing, this creates a de mand for different types or kinds of plastics (Table I). Naturally, the kind of material needed for a plastic automobile body is different from the material needed for an elastic garden hose or a pair of stockings. I know of no other industry which better represents the creative genius of man than the so-called plastic industry. The cre ation at less cost of better things for better liv ing is the aim of the modern business man. To achieve this, there have been brought into exist ence the wonderful modern-day research labora tories. It is important to know the chemical properties of a compound and its toxicity. It is also impor tant to know how to work with it safely. Equally important is to know the treatment for overex posure to the toxic chemical to prevent perma nent damage or death. It would be impossible to name, let alone dis cuss, the toxicological properties of all of the chemical compounds being used in the plastic in dustry. It is worth-while to discuss the properties of some of the more common resins, plasticizers, stabilizers and solvents being used.Unfortunately, the toxicological properties of all of these are not too well defined. It is to the credit of people work ing in industrial medicine and hygiene that in- Prpicntcrl at ihe Eleventh International Congress on Indus trial Medicine. Naples, Italy. September 13-19. 1951. dustry is becoming aware of the necessity for knowing the toxicity of its materials and is tak ing steps to insure that its employees are not exposed to materials that would harm them. Resins J^ehman1 in July, 1951, presented a list of resins both suitable and unsuitable for use as food packaging ingredients. He stated "that as a gen eral rule resins are so insoluble as a class that the chances of contamination by the solvent action of foods are rather slight." The types of resins he considered suitable for food use are: Polyvinyl chloride. Polyvinyl acetate. Polyvinyl chloride-acetate. Polyvinylidene chloride. Polystyrene. Polyethylene. Cellulose acetate. Regenerated cellulose. Terephthalic acid-ethylene glycol copolymer. Butadiene-acrylonitrile (Perbunan or Hycar synthetic rubber). Lehman classified as being unsuitable for use in food packages because of the lack of adequate data concerning their toxicity: Polyvinyl formal. Polyvinyl acetal. Polyvinyl butyral. Polymeric furfuryl alcohol. Coumarone-indene. Urea formaldehyde. Phenol formaldehyde. Aniline formaldehyde. A. Vinyl Type yiNYL chloride, vinylidene chloride, and vinyl acetate readily polymerize. By proper com binations of one or more of these monomers, many polymer variations can be produced. These polymers, after properly mixing with plasticizers and stabilizers, are then used in hundreds of dif- Reprinted from Industrial Medicine and Surgery, 23:11, 479-486, November, 1954 (Copyright, 1954, Industrial Medicine Publishing Company) BFG03691 N 0507001 ferent items. The tnree polymers, either indi vidually or associated with each other, are rela tively non-toxic.1 Seeler and associates studied the chronic tox icity of a copolymer of vinyl and vinylidene chlo ride.2 This work was done because the copolymer was being considered for use as a constituent of a plastic film for wrapping food products. They reported that rats fed a diet containing 5% vinyl and vinylidene chloride copolymer for two years showed no toxic effects. Two dogs were fed a diet containing 5% vinyl and vinylidene chloride copolymer without evidence of toxic effects. Some toxicological information also exists on the three monomers--vinyl chloride, vinylidene chloride, and vinyl acetate. Patty, Yant, and Waite3 investigated the acute effects of vinyl chloride on experimental animals and found this to be essentially narcosis. Carpenter and asso ciates,4 in range finding studies, observed that a vapor concentration of 32,000 ppm of vinylidene chloride resulted in a portion of deaths of the six rats exposed for four hours. The vapor toxicity is reported to be of the same order as ethylene dichloride.9 Carpenter and associates4 also re ported a level of 4,000 ppm of vinyl acetate pro duced some deaths under the same conditions. B. Acrylonitrile--Butadiene Type 'W'arious types of American made rubbers have been studied physiologically. Among those found to be acceptable for food use are Perbunan and Hycar (polymers of acrylonitrile and buta diene). However, the manufacture of these items does present some health problems. Wilson and associates9 reported on the toxicity of acrylonitrile in 1948. They stated that, in their observations, workmen handling cleaning opera tions in polymerizers with exposures varying from 16-100 ppm for 20 to 45 minutes frequently show symptoms of dull headache, fullness in the chest, irritation of all mucous membranes includ ing the eyes, nose and throat, and a feeling of ap prehension and nervous irritability. Some work men complained of intolerable itching of the skin with no demonstrable dermatitis. Direct skin contact with acrylonitrile causes irritation and erythema followed by bleb formation, desquama tion and slow healing. Wilson2 reported several cases of acrylonitrile poisoning in which there developed mild jaundice, low grade anemia and leucocytosis. Given orally the minimal fatal dose of acrylonitrile in laboratory rats is stated8 to be 150 mg/kilo body weight. Symptoms in these animals included respiratory changes, cyanosis, convulsions and death. Because the mode of action of acrylonitrile in the human system appears to be similar to that of cyanide, the treatment of overexposure to acrylonitrile was outlined by Wilson and asso ciates0 to be the same as that for overexposure to cyanide. This treatment was proved to be life saving in several instances. Vitamins I3| and C have been found to be bene ficial in preventing weight loss in laboratory ani mals exposed to acrylonitrile over long periods. Wilson and associates0 also suggested as a prophylaxis against overexposure to acrylonitrile that atmospheric concentrations should not ex ceed 20 ppm. This necessitates enclosure of pro cesses to the maximum degree possible, and the effective use of mechanical exhaust ventilation. Skin contact should be avoided, not only be cause of the compound's vesicant action, but also because of possible toxic systemic effects. In the case of skin contact with the concentrated compound, immediate washing with copious quan tities of soap and water is necessary, If spilled on clothing, the clothes should be immediately re moved and a shower taken by the individual. The effect of chronic low-grade atmospheric or skin exposures on humans is still undetermined. It is, therefore, advisable that working personnel be given periodic physical examinations, with special emphasis on hematology and liver and kidney functions. The determination of the thiocyanate level in both blood and urine has been suggested as an index of overexposure. Wilson and associates also reported on the toxicology of butadiene. They stated that buta diene is practically innocuous, aside from its nar cotizing and anesthetizing effect at very high concentrations. Human subjects who were ex posed to 8,000 ppm of butadiene complained of eye irritation, blurring of vision, coughing, nasal congestion, and drowsiness. Subsequent repeated exposures gave no indication of cumulative ac tion. A complete examination of the chest includ ing an x-ray, blood examination and urinalysis were not informative. Subsequent follow-up exam inations were also negative. In laboratory ani mals subjected to high exposures of butadiene, irritation of all of the mucous membranes and re spiratory tract occurs along with varying degrees of narcosis. Acute deaths are due to pulmonary edema. Delayed deaths are due to chemical pneu monia following pulmonary irritation. Experi mentation with butadiene in laboratory animals indicates that butadiene is not a safe general anesthetic because there is not complete muscu lar relaxation even in the fourth stage. Death ensues rapidly when the laboratory animal is kept in deep anesthesia for any length of time. Wilson and associates stated that workmen anesthetized with or suffering from exposure to butadiene should recover completely, providing they are removed from exposure while respira tion and heart action are still strong. Oxygen by inhalation should be administered until the pulse and blood pressure remain normal and the color is good. Symptomatic treatment is indicated. Special precautions need to be observed in handling the compound from a fire and explosive standpoint. These include enclosure and mechani cal exhaust ventilation and will in most cases automatically control the health hazard. There is no apparent systemic injury to humans in con centrations below 5,000 ppm. Any complaints which include eye and respiratory irritation, headache and vertigo might be considered as in dicative of excessive exposure. BFG03692 *1 / * 20507002 Common Plastics Acrylics Alkyds and Rosin Modifications Aminos (Urea and Melamine) Cellulose Plastic Materials Coumarone-Indene and Petroleum Resins Epoxies 'Fluorocarbons Nylon Phenolic and other Tar Acid Resins Polyethylene Polyester Resins Silicones Styrene Resins Vinyl Resins Uses Table I. Aircraft turrets, auto tail lights, brush backs, signs (Dynel, Acrilan, Orion textiles). Linoleum surfacings, paints for refrigerators and autos, ignition parts, magneto rotors. Buttons, dishes, laminated table tops, housings for kitchen appli ances. Display packaging, irrigation pipe, frames for eye-glasses (rayon and acetate textiles). Asphalt floor tiles, aluminum paints, waterproof coatings, print ing inks. Printed circuit backing, adhesives, surface coatings, transformer and motor laminates. Pump diaphragms, chemical tub ing, high temperature insulation. Gears, slide fasteners, combs, tumblers, tennis racket strings (nylon textile), Telephone handset, radio-TV cab inets, shell molding, dials, grind ing wheels, plywood. Squeezable bottles, semi-rigid kitch enware, packaging, coaxial cables. Reinforced plastics for auto bodies, boats, translucent panels (Dacron textiles). Insulation for generator coils, auto polishes, waterproof coatings, circuit breakers. Kitchen housewares, refrigerator parts, toys and novelties, wall tiles, lighting fixtures. Floor tile, packaging film, rain wear, toys, upholstery material, pipe and pipe fittings, valves, elec trical insulation, sponge, machine and structural parts, metal and fabric coatings. Properties Optical clarity, good weather re sistance, wide color range, shatter resistance, machinability. Fast curing, good dimensional sta bility, good electrical insulation, good heat resistance. Unlimited color range, good elec trical insulation, resistance to or ganic solvents. Toughness, high impact strength, ease of fabrication, lustrous finish, good electrical insulation. Resistance to water and caustic cleansers, compatibility with com pounding ingredients, glass. Excellent adhesion, resistance to chemicals and heat, can be cured at room temperatures. Extreme resistance to corrosive agents and solvents, wide tempera ture range, high impact strength. Good strength and toughness over wide temperature range, wear re sistance, self-lubricating. Hard and rigid, good temperature range, strong, good electrical in sulation, low water absorption. Inert to solvents, flexible and tough over wide temperature range, non toxic, odorless, tasteless. Weather resistance, can be formed with low pressure, strong, color ful, compatible with many fillers. Extreme heat resistance, low water absorption, good dielectric proper ties over wide frequency range. Lightest of commercial plastics, ex cellent moldability, unlimited color range, tasteless, odorless. Tough and strong, unlimited color range, excellent electrical insula tion, resistance to chemicals, oil and weathering. C. Miscellaneous Types COME of the newer synthetic resins which have been physiologically studied are the silicones, the polyethylene gylcols (carbowax compounds), and teflon (polytetrafluoroethylene). Rowe et al' found upon feeding guinea pigs for 50 days in amounts up to 3% of the daily diet no indication of toxicity with DC resins 003 and 2102. They also found that DC Pan Glaze possessed a very low order of oral toxicity when fed to the rat. Shaffer and Critchfield11 concluded from their study of carbowax compounds 1,000. 1,540, 4,000 and 6,000 that no significant gastrointestinal ab sorption occurred when fed to rats. They also ad ministered intravenously compounds 1,000 and 6,000 to humans and found they were readily ex creted to a high degree. Polytetrafluoroethylene (Teflon) is a synthetic resin with exceptional resistance to both heat and chemicals. It is being used for electrical in sulation, for special types of tubing, for coating molds and bread pans, and for gasket materials in jet engines. Stokinger1- has described the ill effects which may result when Teflon is heated to about 360 F as well as from exposure to the finely divided polymer itself. These effects resem ble, in the case of the polymer, those of metal fume fever; in the case of the sublimate (result ing from heating the polymer) those of hydrogen fluoride poisoning. In using Teflon, adequate ven- 20507003 BFG03693 tilation is necessary to avoid ill effects. Lehman1 reports that baking tests have shown no signi ficant increase of the fluoride level of bread bak ing: pans which have been coated with Teflon. Plasticizers T ehman in July, 1951,1 stated that plasticizers presented more serious toxicological problems than the resins because there is always the possibility that these materials may be leached out by food substances. The plasticizers which have had adequate pharmacological study demonstrating their harmlessness in the amounts now used in finished commercial films are: Ethyl Phthalyl ethyl glycollate. p-tertiary Butyl phenyl salicylate. 3- (2-Xenoxyl) -1,2-epoxypropane. 2-Ethylhexyl diphenyl phosphate. Butyl phthalyl butyl glycollate. Glycerol monooleate. Acetyl tributyl citrate. Di-iso-butyl adipate. Lehman classified as unsuitable for food use the following: Dicyclohexyl phthalate. Dibutyl phthalate. Methyl phthalyl ethyl glycollate. Di-iso-octyl phthalate. Dioctyl adipate. Dibutyl sebacate. Dioctyl sebacate. Dicapryl sebacate. Seifter in 19431* made acute toxicity, chronic toxicity and skin irritation studies on dibutyl phthalate. His summary and conclusions were: 1. Dibutyl phthalate is a mild primary skin ir ritant for animals and humans. 2. Dibutyl phthalate taken by mouth is acutely toxic. 3- Dibutyl phthalate ingested daily over long periods of time in amounts up to 2.5 gm. per kilo gram of diet, does not produce chronic poisoning. Smith14 studied dibutyl phthalate and found the acute lethal oral dose to be about 8 gm. per kilogram. When administered chronically in the diet the maximum concentration which did not significantly reduce normal growth was 0.25%. The feeding of dibutyl phthalate even in the highest dietary concentrations, did not provoke specific gross or microscopic pathologic changes. His findings also suggested that dibutyl phthalate was metabolized in the body in much the same way as the fat normally ingested in the diet. He did not feel that it was safe to incorporate dibutyl phthalate in films for wrapping foods even if the calculated safety factor was in excess of 1400. Seifter13 in studying dicapryl phthalate made the following summary and conclusions: 1. Dicapryl phthalate is not a primary skin ir ritant for animals or humans. 2. When taken by mouth dicapryl phthalate has a low acute toxicity. 3. Ingested daily over long periods of time, in amounts up to 2.5 gm. per kilogram of diet, dicapryl phthalate does not produce chronic poi soning. Seifter in 194313 came to the following conclu sions concerning triethylene didecoate: 1. It is not a primary skin irritant for animals or humans. 2. When taken by mouth, it has a low acute toxicity. 3. Ingested daily over long periods of time in amounts up to 2.5 gm. per kilogram of diet, it does not produce chronic poisoning. Smith14 found that the acute lethal oral dose of butyl stearate was greater than 32 gm. per kilogram. When butyl stearate was administered chronically in the diet, the maximum concentra tion which did not significantly reduce normal growth was more than 6.25%. Butyl stearate in the highest dietary concentration did not provoke specific gross or microscopic pathologic change and in dietary concentrations of 6.25% had no adverse effect on fertility or the number of viable young in the litter. There was in this concentra tion slight retarded growth of the young. He felt that, based on the above data, butyl stearate when incorporated in films for wrapping food* appeared to possess little, if any, potential haz ard for humans, the calculated safety factor be ing in excess of 1,400. Smith14 came to the conclusion that the acute lethal oral dose of methoxyethyl oleate was ap proximately 16 gm. per kilogram and when ad ministered chronically in the diet of rats, the maximum concentration, which did not signifi cantly reduce normal growth, was 0.01% to 0.05%. He found renal calculi in three of seven rats fed 1.25% methoxyethyl oleate for more than six months. He felt that methoxyethyl oleate was hydrolized by pancreatic lipases as rapidly as triolein. He did not feel that methoxyethyl oleate should be incorporated in films for wrapping food. Smith14 concluded that the acute lethal oral dose of dibutyl sebacate was between 16 and 32 gm. per kilogram and that when administered chronically in the diet of rats, the maximum con centration which did not significantly reduce nor mal growth was 6.25%, and that when fed in the highest dietary concentration, there were no spe cific gross or microscopic pathologic changes. Dibutyl sebacate in dietary concentrations of 6.25% had no adverse effect on fertility or the number of viable young in the litter. It did cause a slight retarded growth of the young, Smith felt that this plasticizer was metabolized in the body in much the same way as fat normally ingested in the diet, and that when it was incorporated in films for wrapping food appeared to possess little, if any. potential hazard for humans, the calcu lated safety factor being in excess of 1400. Mal- lette and Von Haami:> state that dibutyl sebacate is a non-toxic plasticizer, with no irritating or sensitizing effect on the skin, and that dibutoxy- ethyl phthalate is a non-toxic plasticizer with no irritating or sensitizing effect on the skin. Mallette and Von Haam,:i listed the following as non-toxic plasticizers: Di'2-ethylhexyl adipate. Dibutyl cellosolve azelate. 20507004 BFG03694 Cyclohexyl azelate. 2-ethylhexyl azelate. Methyl isobutyl carbinol azelate. Pentasol azelate. Diethylene glycol dicaprate. Dibutoxyethyl diglycol cavbonate. Octadecene nitrile. Dibutoxyethyl phthalate. Dicapryl phthalate. Methylacetyl ricinoleate. Dioctyl sebacate. Dibutyl sebacate. "Plasticizer 50 BM (Barrett). "Plasticizer Ellicott H." "Plasticizer SC" (Drew). "Paraplex G-25" (Rohm it Haas). "Paraplex G-40" (Rohm & Haas). "Plastolein X-55" (Emery). They stated that five of the plasticizers ex amined showed a moderately toxic effect in lab oratory animals. They were dioctyl phthalate, butylbenzyl phthalate, "santicizer 140," "santicizer 141," and "flexol 8N8." Di (2-ethyl hexyl) phthalate (commercially re ferred to as dioctyl phthalate, DOP, and 2-ethyl hexyl phthalate) was studied by Hodge14 with respect to acute oral and intraperitoneal toxicity in rats and mice. He concluded that it had a very low order of toxicity. Shaffer, Carpenter and Smyth studied it in 1945.17 Their conclusions were that it is a chemical of low toxicity and that the health hazards involved in its use as a plasticizer are slight. Such injurious action as it does exert within the body appears to be due to the alkyl part of the molecule rather than to the phthalate portion. Mallette and Von Haam19 found that dioctyl phthalate had a moderately toxic effect in labora tory animals and that the intraperitoneal injec tion of dioctyl phthalate proved fatal in doses higher than 2 gm. per kilogram of body weight. Lower doses produced weight loss, leucocytosis, severe anemia and hematuria from which the an imals recovered after a month or two. No delayed effect or permanent injury was noted in the sur viving animals. They also showed that dioctyl phthalate had a moderate skin irritating effect. Carpenter, Weil and Smyth1* reported the re sults of feeding Di (2-ethyl hexyl) phthalate for two years to rats and for one year to both dogs and guinea pigs. They obtained relatively uni form responses from all three species, with the two-year "no effect" level for rats falling between .06 and .20 gm. kilogram per day, and the oneyear "no effect" level for both dogs and guinea pigs approximating .06 gm. per kilogram per day. Lehman1 reports that food packaging films con taining this compound as a plasticizer are satis factory for wrapping foods with a high water content, but are unsatisfactory for use with foods having a high fat content, because of the ready solubility of the plasticizer in fats and oils. Halpern and Weiss1* found no irritation or induced sensitivity when 200 humans were patch tested with vinyl film containing dioctyl phthalate as the plasticizer. In 1952 Mallette and Von Haamis reported on other plasticizers, several of which they found to be moderately toxic to rats in acute exposures. These were: 1. Butylbenzyl phthalate was fatal in rats after intraperitoneal administration of doses higher than 1.8 gm. per kilogram of body weight. Oral administration of more than 4 gm. per kilogram of body weight proved equally fatal. The animals died after four to eight days, showing weight loss, apathy and leucocytosis. The histological exami nation of the organs revealed toxic splenitis and degenerative lesions of the central nervous sys tem with congestive encephalopathy, myelin de generation and glial proliferation. 2. "Santicizer 140" (monotolydiphenyl phos phate) proved fatal in intraperitoneal doses of higher than 1 gm. per kilogram of body weight. Oral doses up to 4 gm. were supported. Toxic ani mals became lethargic on the second or third day and a profuse diarrhea developed. They died with symptoms of paralysis. Autopsy showed a gen eralized capillary paralysis with severe edema and numerous hemorrhages in the brain. 3. "Santicizer 141" (2-ethyl hexyl diphenyl phosphate or mono octyl diphenyl phosphate) killed animals after intraperitoneal administra tion of doses higher than 2.4 gm., but oral ad ministration of 4 gm. per kilogram of body weight was tolerated. With the intraperitoneal administration the animals became paralyzed and lethargic. Recovery from non-fatal lesions was delayed. The histopathological examination dem onstrated a severe acute hemorrhagic encephalo pathy with cerebral edema, ganglion cell degen eration and small hemorrhages. As delayed ef fects, focal gliosis and persistent foci of myelin degeneration could be observed. Large fatal doses also proved a powerful hemolytic agent with marked vascular hemolysis, hemoglobinuria, and hemosiderosis of the spleen. 4. "Flexol 8N8" (N,N-di-beta-(2-ethyl hexyl) ethyl 2-ethyl hexylamide) proved fatal in doses higher than 4 gm. per kilogram of body weight. The animals developed convulsions followed by paralysis. The histological examination of the brain gave the picture of toxic hemorrhagic en cephalopathy with, edema, swelling of ganglion cells and small hemorrhages. Their conclusions were that these four plasti cizers proved moderately toxic in doses from 0.6 to 2.4 gm. per kilogram of body weight. The toxic reaction was displayed by the erythrocytes, the blood capillaries and the central nervous system. They also found in their studies 17 plasticizers to be slight or moderate skin irritants. Three-- "Flexol 8N8," "Paraplex G-25," and "Paraplex G-40"--proved to be severe skin irritants. A moderate sensitizing effect on the skin was found by Mallette and Von Haam1'' to exist with diethylene glycol dicaprate. methylacetyl ricino leate. "Paraplex G-25," "Paraplex G-40," and "Santicizer 140." Seeler et alin their studies on the chronic toxicity of acetyl tributyl citrate came to the fol lowing conclusions: 20507005 BFG03695 1. Rats showed no toxic effect after eating diets these compounds, however, possess a relatively containing 200 ppm, 2,000 ppm, and 20,000 ppm high degree of toxicity and they are objection of acetyl tributyl citrate for two years. able for use in items involving contact with hu 2. Dogs were given a daily oral dose of 140 mg. man food.1 There are, however, many plaatic of acetyl tributyl citrate for two years without formulas for uses in products where toxicity is evidence of toxic effect. not of particular significance and consequently, Seeler et al21 on making chronic toxicity one or more of these stabilizers can be safely studies of butyl phthalyl butyl glycollate came to used. Obviously, when these heavy metals are the following conclusions: used, adequate, safe handling procedures must 1. Rats fed diets containing 200 ppm, 2,000 be utilized in the manufacturing plant. These ppm, and 20,000 ppm of butyl phthalyl butyl involve the practice of good industrial medical glycollate for two years showed no toxic effect. and hygiene procedures. 2. Dogs were given a daily oral dose of 140 Lehman1 has also stated that zinc oxide, zinc mg. of butyl phthalyl butyl glycollate for two stearate and salts of manganese and copper are years without evidence of toxic effect. not objectionable as stabilizers in food wrapping The results of both acute and chronic oral feed material if not more than 50 ppm of the metal ing, as well as skin absorption and irritation with leaches out into the food. 2-ethylhexyl diphenyl phosphate (Santicizer 141) Some of the newer stabilizers for vinyl resins are given by Treon et al.2S These investigators are the organic tin compounds. Elemental tin has found the compound to be innocuous when ad been used for many years as a lining for food ministered orally to rabbits and rats in a single containers and is relatively harmless. The organ large dose. No effects, either irritative or system ic tin salts, however, while not known to be harm ic, were found as the result of keeping it in con ful have not thus far been shown to be sufficient tact with the abraded skin of rabbits for seven ly safe for use in food container applications. to 24 hours. Rats fed for two years on a diet con The plant manufacturing operations involving taining 1%, 0.125%, and 0.0625% by weight of the use of the organic tin stabilizers may present the compound showed no pathology, but did show some industrial health problems but again the a retarded growth rate at the 1% level. Dogs fed degree or extent of these is not known at the the compound at dietary levels of 2.5% for two present time. years showed retarded growth, but those fed a , 1.5% level grew normally. V Solvents Treon, Cappel, and Sigmon have found28 that Tn the processing of plastics into products, a a high percentage of Santicizer 141 is excreted number of chemicals are used. These include in the feces of both rabbits and humans un aromatic hydrocarbons, chlorinated hydrocar changed. Halpern and Weiss18 have shown that bons, petroleum distillates, ketones, acetates and films plasticized with Santicizer 141 are not ir alcohols. These compounds are all toxic in vary ritating and do not induce sensitivity in humans. ing degrees and present certain medical problems in their handling. Specific methods for determin Stabilizers ing the atmospheric concentrations of these ATany different materials are being used as chemicals can be found in Jacob's24 text. stabilizers for plastics. The specific type of The American Conference of Governmental Hy plastic with particular reference to its use, gov gienists35 suggested the maximum allowable con erns to a large degree the stabilizer to be selected. centrations of many of the more common solvents Obviously, uses such as that of food packaging in Table II. where there might be leaching of the stabilizer The aromatic hydrocarbons are used extensive into the food require materials that are not harm ly in the processing of plastics. Of these, benzene ful if ingested. Lehman1 states that the follow ibenzol CHc); toluene (toluol, C6HnCH3) ; and ing are not objectionable for food packaging: xylene (xylol, C0H4(CHa)2) are the principal Aluminum monostearate. ones. These compounds are of value because of Calcium acetate. the fact that they are excellent solvents. Calcium ethyl acetoacetate acetate. As pointed out by Wilson20 benzol poisoning Calcium carbonate. may result from absorption of benzene by either Calcium stearate. the respiratory tract, the alimentary tract, or Calcium glycerophosphate. probably the skin. Cases of poisoning in human Mono- di- and tricalcium phosphate. beings have been found with exposures to atmos Calcium oleate. pheric conditions as low as 25 ppm. Concentra Calcium ricinoleate. tions of 50 to 100 ppm are considered to be safe Magnesium stearate. for the average person. Individual susceptibility Magnesium glycerophosphate. varies. Acute benzol poisoning is rare. Mon-, di-, and trimagnesium phosphate. As pointed out by Wilson27 the pathologic Disodium hydrogen phosphate. manifestations of exposure to toluene are a mat- Ammonium potassium phosphate. ter of controversy. The conclusions reached by Some of the most efficient stabilizers from the various authors are in decided variance with one standpoint of performance, particularly for the another. Toluene poisoning is probably caused vinyl resins, are the heavy metal salts of barium, by absorption through the respiratory system, strontium, lithium, cadmium, and lead. All of the skin, and the alimentary tract. The absorbed BFG03696 t 20507006 r Table II. Succested Maximum Allowable Concentrations (Parts per million parts of air) Acetone ...........................................................................1000 Acrylonitrile ................................................................. 20 Amyl acetate ............................................................... 200 Amyl (iso) alcohol .................................................... 100 Benzene (benzol) ........................................................ 35 Butadiene 1,3 ................................................................1000 Butyl acetate ............................................................... 200 Butyl alcohol ............................................................... 100 Carbon tetrachloride .................................................. 25 Ethyl acetate ............................................................... 400 Ethyl alcohol ......................,...................................... 1000 Ethylene dichloride .................................................. 100 Gasoline ......................................................................... 500 Heptane .......................................................................... 500 Hexane ........................ 500 Propyl (iso) alcohol .................................................. 400 Methyl alcohol ............................................................. 200 Methyl ethyl ketone .................................................. 100 Naphtha (petroleum) ........................................... . 500 Perchlorethylene (tetrachlorethylene) ................ 200 Propyl acetate ............................................................. 200 Stoddard solvent ........................................................ 500 Tetrachlorethane ........................................................ 5 Tetrachlorethylene...................................................... 200 Toluene .......................................................................... 200 Trichlorethylene............................................................. 200 Xylene ............................ ........... .................................. 200 vapors exert a progressive depressant action on the central nervous system and the bone marrow. Toluene is also a pronounced irritant to mucous membranes. A factor to be considered whenever it is employed is individual susceptibility. Ex posure to concentrations of toluene from 200 to 500 ppm for six to eight hours will in most per sons cause tiredness and lassitude. Concentra tions over 500 ppm for one to three hours are definitely dangerous and will cause symptoms at tributable to depression of the central nervous system and the bone marrow. Xylene9 is stated to possess more severe nar cotic properties than benzene. Xylene poisoning is relatively uncommon because its volatility is lower than that of benzene or toluene. Chronic poisoning does occur. There is some evidence that xylene exerts an action on the blood forming organs similar to that of benzene. Cases of aplastic anemia have been attributed to xylene vapors. There Have been some cases reported in German literature of leukopenia and thrombocy topenia with no reduction in red cells. The commonly used chlorinated hydrocarbons in the plastic industry are: Carbon tetrachloride (tetrachlormethane) CC1. Ethylene dichloride (dichlorethane) C2H^Cl>. Tetrachlorethane (acetylene tetrachloride) C.H..CI,. Trichlorethylene (ethylene trichloride) C2HC1^. Perchlorethylene (tetrachlorethylene) C2C14. The most toxic of the group is tetrachlorethane, having, according to Matruchot,28 a comparative toxicity of G.O. Carbon tetrachtoride is listed by the same author as having a comparative toxicity of 2.6, trichlorethylene of 1.0, perchlorethylene of 1.4, and ethylene dichloride of 1.6. According to Davis20 and the U.S. Public Health Service,30 the maximum allowable concentration of carbon tetrachloride is 100 parts per million. According to Elkins31 this level is too high and should be reduced to 50 parts per million. Many of the petroleum distillates are used. Gasoline (unleaded), hexane, heptane, Stoddard solvent, varsol, and naphtha are mixtures of hydrocarbons, paraffins, olefins, cycloparaffins (naphthenes), aromatics, and other impurities including sulphur. Cracked gasoline may also carry a fairly high percentage of benzol. These substances are frequently referred to by the general name of benzine. This is to be distin guished from benzene (benzol). These distillates are narcotics, and it is possible to produce com plete anesthesia with heavy doses. However, their anesthetic properties are much less than those of the aromatic and chlorinated hydrocarbons. For this reason they may be more desirable for com mercial use. Drinker and associates, in studying the effects of gasoline vapors32 found that con centrations from 270 to 500 ppm were tolerable. Neuromuscular symptoms began at about 900 ppm; mild intoxication at 2,000 ppm. Acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone are also used. In our experience no cases of occupational disease have been attributed to the ketones. Methyl, ethyl, propyl, isopropyl, butyl and iso amyl acetate may be used. These solvents are not considered severely toxic and in most cases the allowable concentrations are based more on com fort than on toxic requirements. Methyl, ethyl, isopropyl, amyl and butyl alco hol are all used at times in plastics manufacture. Methyl alcohol is a source of grave injury to many industrial workers. It has a specific action on the optic nerve, and with long enough expo sure, blindness may result. The action is that of inflammation of the optic nerve followed by atrophy. A considerable amount of methyl alco hol poisoning was noted during prohibition days when wood alcohol was used in large amounts with subsequent optic nerve degeneration and blindness. The other alcohols, because of their volatility are not considered to be especially dangerous. Cases of narcotic poisoning have been attributed to them but not proved. The higher alcohols, like butyl and amyl, have in addition an irritant action as well as some poi sonous action on the protoplasm. Summary 'pHE advent of a great industry for the manu facture of articles of all kinds made from various chemical compounds has created many new problems for the industrial physician and the industrial hygienist. Many of the compounds used are new.and very little, if anything, is known about their toxicity. Also, since there are no set formulas or recipes, each plastic article may have a different composition. This paper attempts to discuss the toxicity of the more common compounds now being used in 20507007 BFG03697 plastics manufacture. Resins, plasticizers, stabil izers and solvents are discussed in some detail in regard to their toxic properties. The scarcity of knowledge of the properties of many of the chemicals is sufficient reason for further study. It is not enough for industry to make better things cheaper; it must also make them safely. Resume A rticles made of a variety of chemical combina tions commonly called plastics have found in creasing favor with the consuming public. Many useful products can be made stronger, better looking, longer wearing and at lower costa em ploying these versatile new materials. The imagi native creativeness of the human mind is evident in our new world of plastics. To create these man made marvels, the research chemists and develop ment engineers have not only used known chem icals but also have created new ones. Unfortunately, many of the chemicals current ly used are known to be highly toxic. Even worse, the toxicity of many of the newer chemicals is not even known. Thus, industrial medicine and hygiene face serious problems both from known and potential toxic hazards. Considerable infor mation has been published concerning some of the chemicals now being used in plastic manu facture, and at the present time many chemicals are undergoing toxicological investigation. The authors of this paper have accumulated information on many of the resins, plasticizers, stabilizers and solvents being used in the manu facture of numerous plastic articles. It will be noted that the information is meager in some instances while in others it is quite complete, but, to our knowledge, this comprehensive summary on the toxicology of plastics has not heretofore been attempted. Among the authors' conclusions is that indus try must maintain strong Departments of Indus trial Medicine and Hygiene to control toxicolo gical hazards. Many industries are diversifying manufacturing activities and entering fields of endeavor for which previous experiences may not have prepared them. Highly toxic chemicals can not be successfully handled in a haphazard man ner and it is essential to invest money for toxi cological investigation, because to be without such programs is foolhardy and more expensive in the long run. No industry can afford to endanger the health of its people by knowingly exposing them to toxic materials. It is not enough for research chemists to dis cover a chemical combination, which will create a new sales masterpiece. The industrial hygien ist must also determine the toxicity of the chem icals involved and designate wavs and means of handling them safely. If the sales potential of a new plastic does not warrant toxicological study, then the product should not bo produced. Another conclusion of the authors is that much additional toxicological study is necessary on plastics, and it is hoped that the toxicology of plastics can be added to and made more complete, year after year. References 1. Lemmas. Arnold J.: Chemical* in Food*: A Report to the Association of Food and Drug Official* on Currant Develop ment*. Accociation of Food <fr Onto Official* of CA Unitad Slatei. Vol, XV, No. 3. July. 1951. 2. Sccler. Almkt O.: Clinton, Marshall, Boggs. Joseph, Drinker, Philip: Experiment* on the Chronic Toxicity of a Copolymer of Vinyl and Vinylidn Chloride. Unpublished. 3. Patty. F. a., Yant,. W. P-. and Wait*. C. P.: Acute Response of Guinea Pin to Vapor* of New Commercial Organic Compounds. tJS- Public Health Reports, 45:1953 11930). 4. Carpenter. C. P-. Smith. H. F,. and Posxanl U. C.: The Assay of Acute Vapor Toxicity end the Grading and Interpreta tion of Results on 95 Chemical Compounds: J. Induct. Hyg. A Tot.. 31:343. 1949. 5. Reinhardt. R. C.: Handling Vinylidenc Chloride: Chem ical dt Engineering Netoe, 25:2136 (July 28) 1947. 6. Wilson, R. H., Hough, Glenn v,, and McCormick. Wit. E. : Medical Problem* Encountered in the Manufacture of American.Made Rubber. Induat. 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