Document 2jNyjbwLD3v8LY4vGNmbYq38L

ZZL 7 PPG INDUSTRIES, INC. / ONE GATEWAY CENTER / PITTSBURGH. PENNSYLVANIA 15222 May 15, 1970 Mr. William Brydon Ethyl Corporation 451 Florida Baton Rouge, Louisiana 70801 Dear Mr. Brydons Thought you would be interested ii on Vinyl and Vinylidene Chloride. Very truly yours, .xfv // /. Fred H. Moulton product Manager V CTHYL, COR)5 R*D OEPT. BATON ROUGE MAY 201970 1IE ""'1 ~nr7RLJ ' sr.c 1 KLU MET ! 1 1 JOJ . F.VP rlK V AJH . oMO " RLH | 1 EMO "j DH oi___ ---------------------------- RLM i i,,-* 1 "OH j \ j | , n1 -- bm 7 FO 3367 Vinyl chloride monomer is the base ma terial used in the manufacture of polyvinyl chloride resins. In today's increasingly plastic world, PVC is one of the most widely used modern thermo plastics, finding applications from clear bottles to building products and clothing. Vinyl chloride monomer (VCM) is now produced by PPG Industries Chemical Division at Lake Charles, Louisiana, and will soon be produced in a new plant in Puerto Rico. When the new plant is in production, total output will exceed S00 million pounds annually. VCM from the Puerto Rico plant will be shipped to customers in the continental United States from a bulk terminal on the East coast. Uninhibited VCM is quite stable and can be routinely shipped, handled and stored provided proper procedures, outlined below, are followed. To prevent polymer ization in transit or storage, it is essential that the monomer be protected at all times from contact with air, oxygen, moisture, catalytic impurities, and light. PPG normally supplies VCM uninhibited. The use of uninhibited VCM eliminates the need for subsequent processing to remove the inhibitor. If required, suitable inhibitors will be added. PPG Industries operates two pilot reactors -- one of 500 gallons capacity, the other of 50 gallons -- for polymeri zation experiments at its Barberton, Ohio, Research Center. PPG researchers use these pilot plants to conduct poly merization studies involving VCM, vinvliudene chloride, and other monomers, as well as PPG's peroxide polymerization initiators. GRADES USES In addition to the regular polymer grade VCM, PPG Industries produces a special grade of vinyl chloride to meet more stringent specifications that may be re quired for particular end uses. Infor mation about this special grade VCM may be obtained from a PPG Chemicals sales office. PROPERTIES Most vinyl chloride is polymerized to polyvinyl chloride (PVC) or copoly merized with other monomers such as PPG's vinylidene chloride. A significant percentage goes to other uses, including aerosol propellants, pesticides and ex traction solvents. Chemical Names: Vinyl chloride; vinyl chloride monomer; chloroethylene; chloroethene Chemical Formula: CHjCHCl; Molecular Weight: 62.5 =CI! lb 'Cl Description: At ordinary temperatures and pressures, vinyl chloride is a color less gas with a mild, sweet ordor. But as supplied in tank cars under pressure, it is a liquid. Vinyl chloride is highly volatile and its vapor is extremely flammable. Boiling Point, C SF Freezing Point, C F Flash Point, open cup,C F Explosive Limits, volume % in air at 25C (77 F) -13.8 +7.0 -153.7 -245 -78 -10S.4 4 to 22 Autoignition Temperature, C F Liquid Density at 60 F Vapor Density, air=l Vapor Pressure, psia at 0C 20 C 40 C Solubility, water in monomer, weight % 472 882 0.9192 2.15 25.1 49.2 87.6 0.11 Solubility: Vinyl chloride is relatively insoluble in water but soluble in most organic solvents. Reactivity: Vinyl chloride polymerizes exothermically in the presence of light, air, oxygen or catalysts. Heat alone will not initiate polymerization. Vinyl chlo ride is thermally stable to quiLe high temperatures. Peroxide formation due to air exposure is a slow reaction and there is usually no special hazard from peroxide products. Vinyl chloride is noncorrosive to metals when dry at norma! tempera tures, but water and elevated tempera tures accelerate corrosion. The double bond behaves as in other unsaturated compounds. The chlorine atom is rela tively inactive and is more stable than in saturated or allylic compounds. if, C 3 3 3  Specification for polymer grade: nitrogen gas pressure in empty tank car Appearance \ Color Acidity, as HC!, maximum ppm Iron, as Fe, maximum ppm Nonvolatile residue, maximum weight % clear, free of suspended matter colorless, water-white 5 0.5 0.05 being returned. Use nitrogen with a maximum oxygen content of 10 ppm. More Information. The Manufacturing Chemists Association also publishes Chemical Safety Data Sheet SD-56 on the "Safe Handling and Use of Vinyl Chlo Water, maximum ppm 100 ride." More information is also available Sulfur, as S02, maximum ppm 3 from the technical service staff of PPG Acetaldehyde, maximum ppm 5 Industries Chemical Division. Acetylene, maximum* ppm 2 PACKAGING AND SHIPPING TOXICITY Uninhibited monomer is not absorbed through the skin, but the liquid may cause frostbite because it evaporates so fast. If an inhibitor is included, it may cause local skin burns. In comparison with other chlorinated hydrocarbons, vinyl chloride vapor has a relatively low toxicity. Vapor concentra tions in work areas should not exceed 500 ppm as a time-weighted average atmospheric concentration for an S-hour day to avoid adverse effects on workmen. High vapor concentrations can cause diz ziness and anesthesia. More information appears in "Industrial Hygiene and Toxi cology," second revised edition, volume II, edited by Irish and Fassett, Inter science Publishers, New York, N.Y., 1967, pages 1303-1305. Fire hazard Vinyl chloride vapor is extremely flam mable. Its explosive limits are between 4 and 265o by volume in air. Proper ventila tion and the elimination of ignition sources are mandatory in areas where vapor con centrations may reach a flammable level. When a tank car is unloaded, both the car tank and the unloading pump should be electrically grounded. The products of combustion include toxic and corrosive hydrogen chloride as a major product, and the possibility of very small quantities of phosgene being produced cannot be ruled out. Carbon dioxide or dry chemical agents extinguish fires effectively. Streams of water cannot extinguish a liquid vinyl chloride fire because the monomer does not mix with water and will float on top. Water may be PPG Industries delivers vinyl chloride byship, barge, tank car and tank truck. There are 3 shipping points: Lake Charles, Louisiana, Guayanilla, Puerto Rico, and an East coast terminal. PPG maintains a fleet of tank cars for vinyl chloride service. All cars are equip ped for top unloading. There are two car sizes: 180,000-pound net weight; and 220,000-pound not weight. Tank trucks hold up to 40,000 pounds. Ships and barges hold up to several million pounds. SAMPLES AND SERVICE Samples of vinyl chloride are available on special request in returnable laboratorysize steel cylinders holding 5 pounds or in cylinders holding 200 pounds. The technical service staff of PPG In dustries Chemical Division is available for consulting on handling, storage and use. HANDLING AND STORAGE Aluminum and its alloys must not be used in equipment to store or handle sprayed to cool equipment. No one with out proper protective respiratory equip ment should enter an area where there has been a fire until the area has been This maximum is an industry standard; however, the PPG product contains no detectable amount of acetylene. vinyl chloride because explosive alumi adequately ventilated. num chioroalkyls can be formed. PPG's vinyl chloride is made from ethylene and Unloading tank cars contains no detectable amount of acety If tank car valves are defective or leaky, lene. Vinyl chloride made from acetylene do not unload. Telephone the PPG Chem by an older process contains traces of icals plant at Lake Charles, Louisiana,- acetylene that could react explosively 318-882-1200. Information on unloading with copper or its alloys to form copper appears in Manual Sheet TC-4 on "Un acetylides. It is not safe to use such vinyl loading Flammable Liquids From Tank chloride in processing equipment con Cars," published by the Manufacturing taining copper or brass. Chemists Association, 1S25 Connecticut Exposure of vinyl chloride to oxygen and Avenue, N.W., Washington D.C. 20009. air results, after a time, in polymer formation. This can cause problems in Warning: Air should never be permitted equipment used for storage and transfer to enter vinyl chloride tank cars or other of monomer. Vinyl chloride should be containers during or after unloading. stored under a blanket of nitrogen with a Close and seal all openings. Leave approx maximum oxygen content of 10 ppm. imately 10 psig of vinyl chloride or -1000 2.5; 470 fc 3369 Pr-nted in U.S.A. Vinylidenc chloride monomer (VDC) is a versatile product used with other mo nomers to make a wide variety of copoly mer resins and latiees. Properly inhibited and protected from exposure to air, oxygen, water and light, VDC is stable in shipment and storage at ambient temperatures. Correct handling practices, outlined below, must be fol lowed at all times. VDC supplied by PPG from its Lake Charles, Louisiana, plant is inhibited with hydroquinone monomethyl ether (HQMME or MEHQ) to prevent polymeri zation during shipment and storage. It is shipped under a nitrogen blanket to avoid contact with air and to prevent the formation of a peroxide that can act as a polymerization initiator. For most applications, the MEHQ inhi bitor in PPG vinylidenc chloride need not be removed. If uninhibited monomer is required, however, the MEHQ can be removed by distillation or alkali extrac tion. PPG Industries operates two pilot reactors -- one of 500 gallons capacity, the other of 50 gallons -- for polymeri zation experiments at its Barberton, Ohio, Research Center, PPG researchers use these pilot plants to conduct poly merization studies involving VDC, vinyl chloride, and other monomers as well as PPG's peroxide polymerization initiators. GRADES The standard grade of VDC manufactured by PPG is inhibited with hydroquinone imonomethyl ether at approximately 200 R>arls per million. FPG can also supply, on request, a special grade inhibited with phenol at 0.6% to 0.S%. USES Vinylidene chloride monomer has been used for many years, primarily as a copolymer with such monomers as vinyl chloride, vinyl acetate, acrylonitrile, and acrylic acid esters. The copolymer resins and latiees are formed into films, fibers, coatings and linings. VDC imparts to finished products quali ties of flame rotardance, chemical resis- tance, and impermeability to water vapor and gases. Data on reactivity ratios of VDC copoly merizations with 36 monomers are presen ted in a booklet, "Vinylidene Chloride (Inhibited), handling, properties and reac tivity rates" Form A967, available on request from PPG Industries, Chemical Division. PROPERTIES Chemical Names: Vinylidene chloride; vinylidene chloride monomer; 1,1-dichloroethylene Chemical Formula; CIIjCCL; hP_<Xc! Molecular Weight: Description: 96.95. Contains 73.14% chlorine. At ordinary handling temperatures, below its boiling point of 88.9F (31.6r'C), vinylidene chloride is a liquid. It is clear and colorless and has a sweet odor. Vinylidene chloride is highly volatile and its vapor is toxic and extremely flammable. Boiling Point, C aF +31.6 +88,9 Freezing Point, C F -122.5 -188.5 Explosive Limits, volume % in air 7 to 16 Flash Point, Cleveland open cup, C -15 F +5 Autoignition Temperature, C F 570.0 1058 Critical Pressure, atmospheres 51.3 Critical Temperature, C F 222 432 Absolute Viscosity at 20C, cps 0.330 Specific Gravity, 20S/203C 1.213 Density at 205C, pounds/gallon 10.1 Refractive Index, nD at 20SC 1.-1247 Vapor Pressure, mm Ilg, at 20C 475.1 Solubility, water in monomer, weight % 0.035 Solubility: Reactivity: Vinylidene chloride is practically insoluble in water but soluble In most organic solvents. Uninhibited, or inhibitor-depleted, vinylidene chloride may pc-lymerizc very slowly even in the absence of oxygen. To further retard polymerization, the uninhibited monomer should be main tained in darkness below 14F (-10C) Uninhibited, or inhibitor-depleted, vinylidene chloride reacts readily with oxygen or air to form a peroxide at temperatures as low as -40 F or C. EC O Specification for regular grade: Appearance Color, maximum A PI IA Vinylidcnc Chloride, minimum weight % (excluding inhibitor) ^Acetylene, Acetylidcs, as C^Hj, maximum ppm Other Chlorinated Hydrocarbons, no one to exceed this maximum weight % Acidity, as HC1, maximum ppm Peroxide, as H20j , maximum ppm Water, maximum ppm Inhibitor, HQMME*, ppm Hydroquinone monomethyl ether is sometimes referred to as MEHQ tmonomethyl ether of hydroquinone). . clear, free of suspended matter 25 99.6 TOXICITY Inhibited vinylidene chloride is irritating to the eyes and skin. Upon evaporating, the inhibitor can cause local skin irrita tions or burns unless washed off thoroughly. Vinylidene chloride is highly volatile and its vapor is heavy. Its odor-warning pro perties are not adequate. Overexposure to vapor can lead to anesthesia, irrational behavior and-if eontinued-lo unconscious ness. In all cases of overexposure, medical attention should be obtained. Prolonged or repeated exposures can cause damage to liver and kidneys. jhe toxicity of vinylidene chloride vapor 1 considered to be greater than that of Tthylene dichloride but less than that of carbon tetrachloride. Vapor concentra tions in work areas should not exceed 25 ppm as a time-weighted average atmo spheric concentration for an 8-hour day to avoid adverse effects on workmen. Above a level of 200 ppm, respiratory protection is recommended. Workmen cleaning up spills or stopping leaks should have self-contained or air-supplied breathing apparatus. More information appears in "Industrial Hygiene and Toxicology," second revised edition, volume II, edited by Irish and Fassett, Interscience Publishers, New York, N.Y., 1967, pages 1305-1307. HANDLING AND STORAGE If tank car valves are defective or leaky, do not unload. Telephone the PPG Chem icals plant at Lake Charles, Louisiana, 31S-SS2-1200. Nitrogen used with vinylidene chloride should have a maximum oxygen content of 10 ppm. Information on unloading tank cars and drums, handling spills and leaks, construc tion materials, storage tanks and transfer lines is presented in a booklet on "Vinyli dene Chloride (inhibited), "Form A967 available on request from PPG Industries Chemical Division. Fire hazard Vinylidene chloride vapor is extremely flammable and burns vigorously at con centrations between 7 and 16% by vol ume in air. Proper ventilation and the elimination of ignition sources are manda tory in areas where vapor concentrations may reach a flammable level due to spills or leaks. Firemen should be warned that the pro ducts of combustion include toxic hydrogen chloride and that vinylidene chloride vapors in high concentrations are toxic. Carbon dioxide or dry chemical agents can extinguish fires effectively, also, water spray or foam may be used. Water may also be sprayed to cool equip ment. No one without proper protective respiratory equipment should enter an area where there has been a fire until the area has been adequately ventilated. Explosion hazard The peroxide compound that forms when uninhibited vinvlidene chloride has been exposed to atmospheric oxygen' is poten tially dangerous. This peroxide can also form if the inhibitor content lias been depleted. Depletion can result from any of several causes including distillation or exposure to oxygen due to improper storage. The presence of peroxide can be detected by sharp, acrid odors or by the precipitation of a white flocculant poly mer. Dried polymer residues may contain ad sorbed peroxide which can be exploded by a slight mechanical shock or by heat. These residues should be handled with extreme caution. Adding water that is at room temperature to polymer residues containing peroxide renders them inactive. However, the hazard may return if the water evaporates. The peroxide can be destroyed by several washes with fresh 5% sodium bisulfite solution or with 10To sodium hydroxide solution that is at room temperature. Vinylidene chloride monomer that contains peroxide may be purified by washing in the same manner. Separation and handling of precipitated polymer, and its potentially dangerous adsorbed peroxide, must be done with extreme caution. Equipment not used continually should be filled with water when shut down. PACKAGING AND SKIPPING PPG Industries ships vinylidene chloride (inhibited) in tank cars of 10,000-galIon (105,000-pound) capacity from Lake Charles, Louisiana, and in 55-gallon (500-pound) drums from Bayonne, New Jersey. SAMPLES AND SERVICE Samples of Vinylidene Chloride are avail able, on request in 1 pint and 5 gallon containers. The technical service staff of PPG Industries Chemical Division is avail able for consulting on handling, storage and use. A-IOCH 2.5V 470 EC 3371. *rinisd m U.5.A,