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In keeping with its position as a lead ing producer of vinyl chloride monomer for the merchant market only, PPG In dustries expanded its Lake Charles, Louisiana, vinyl chloride plant in 1969. The Guayanilla, Puerto Rico plant, built in 1971, greatly increased PPG's capacity for making vinyl chloride monomer.
A new large tanker, the S.S. Puerto Rican, transpons refrigerated vinyl chloride monomer to a terminal at Paulsboro, New Jersey, where it is stored under refrigeration.
PPG produces vinyl chloride mono mer by the oxvhydrocblorination of ethylene and holds more than 400 do mestic and foreign patents on this pro cess.
At the PPG plant ir. GuayinHIa, Puerto Rico, the company's modem 34.000-ton chemical tanker, S.S. Puerto Rican, receives e load of vinyl chloride monomer.
At the Paulsboro, New Jersey terminal, the S.S. Puerto Rican's lead cl vinyl chloride monomer is transferred to the refrigerated storage tanks in the background.
Uninhibited VCM is quite stable and can be routinely shipped, handled and stored provided proper procedures, out lined below, are followed. To prevent polymerization in transit or storage, it is essential that the monomer be protected at all times from contact with air, oxy gen, moisture, catalytic impurities and light.
PPG normally supplies VCM unin hibited. The use of uninhibited VCM eliminates the need for subsequent pro cessing to remove the inhibitor. If re quired, suitable inhibitors will be added.
More information appears in the PPG manual, "Vinyl Chloride Monomer Han dling and Properties," form A-994-115R.
GRADES PPG Industries produces only poly
mer-grade vinyl chloride monomer.
USES Most vinyl chloride is polymerized to
polyvinyl chloride (PVC) or copoly merized with other monomers such as PPG's vinylidene chloride. Vinyl chlo ride monomer should not be used as an aerosol propellant.
TOXICITY The Occupational Safety and Health
Standard on exposure to vinyl chloride published October 4,1974, says: "Based on the demonstrated evidence of vinyl
PROPERTIES Chemical Names;
-*
Vinyl chloride; vinyl chloride monomer; chloroethylene; *
chloroethene H.
Chemical Formula: CH.CHC1; Molecular Weight: 62.5
C=C H/ NC1
Description:
At ordinary temperatures and pressures, vinyl chloride is
a colorless gas with a mild, sweet odor. But as supplied in
tank cars and trucks under pressure, it is a liquid. Vinyl
chloride is highly volatile and its vapor is extremely flam- -
able. Containers are labeled "cancer-suspect agent."
Boiling Point, *C
--13.8 Autoignition Temperature, *C 472
*F +7.0
*F 882
Freezing Point, *C
--153.7 Liquid Density at 60*F
0.9192
*F
--245
Vapor Density, air--1
2.15
Flash Point, open cup *C --78
Vapor Pressure, psia at 0*C _ 25.1
*F --108.4
20*C
49.2 *
Explosive Limits, volume %
in air at 25*C (77*F)
3.6 to 33
40*C Solubility, water in monomer, at 25*C (77*F), weight % J
87..6' - 0.11 ;
Sotubility: 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 quite high temperatures. Although peroxide formation j-
due to air exposure is a slow reaction, certain peroxide products are shock-*
sensitive. Vinyl chloride is noncorrosive to metals when dry at normal temper- -
atures, but water and elevated temperatures accelerate corrosion. The double^
bond behaves as in other unsaturated compounds. The chlorine atom is relatively '
inactive and is more stable than in saturated or allylic compounds.
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Specification and typical analysis: Specification
Typical Analysis
Appearance
Color
Acidity, as HC1, ppm Iron, as Fe, ppm (filtered sample) Nonvolatile residue, weight % Water, ppm Sulfur, as SOs, ppm Acetaldehyde, ppm Acetylene, ppm
clear, free of suspended matter
colorless, water-white 5 maximum 0.5 maximum 0.05 maximum 100 maximum 3 maximum 5 maximum 2 maximum*
clear, free of suspended matter colorless, water-white <1
0.1 0.0003 34 <1 <1 <1
This maximum i* an tadOUT Standard: however, the PPG product contain* no detectable amount of
chloride monomer's carcinogenicity in three animal species (rats, mice and hamsters), and the substantial probabil ity that vinyl chloride monomer had been the causal agent in the cases of liver angiosarcoma found in workers both here and abroad, OSHA . . . pub lished a comprehensive proposal . . . to protect employees from hazards of exposure to vinyl chloride monomer."
Stated in this OSHA standard is the following "Permissible exposure limit scheduled to become effective January
1, 1975: (1) No employee may be exposed to
vinyl chloride at concentrations greater than 1 ppm (part per million by vol ume) averaged over any 8-hour period, and
(2) No employee may be exposed to vinyl chloride at concentrations greater than 5 ppm averaged over any period not exceeding 15 minutes.
(5) No employee may be exposed to vinyl chloride by direct contact with liquid vinyl chloride."
In cases where these limits of ex posure are exceeded, the wearing of respirators will be mandatory for work ers beginning January 1, 1976. Until then, the wearing cf respirators is dis cretionary for exposures under 25 ppm.
Besides the suspected carcinogenicity, vinyl chloride monomer vapor can pro duce immediate symptoms in persons exposed to high concentrations.
The odor of vinyl chloride monomer
is sweetish and the sense of smell can not be relied upon as a warning. High vapor concentrations may cause lung irritation, can cause dizziness and anes thesia, and may do other bodily damage in ways not yet ascertained. In all cases of overexposure, immediately remove the affected individual to fresh air and obtain medical attention.
Liquid vinyl chloride monomer may cause frostbite because it evaporates so fast. If a polymerization inhibitor is included, it may cause local skin bums. However, most vinyl chloride monomer shipped today is not inhibited.
Workers should wear eye protection and protective clothing to prevent skin contact with the liquid. If vinyl chlo ride gets on clothing or shoes, they should be removed immediately. If vinyl chloride contacts the skin, wash im mediately with soap and water. If vinyl chloride contacts the eyes, the eyes should be washed immediately and thoroughly with water for at least 15 minutes. Get medical attention.
HANDLING AND STORAGE Detailed information appears in the
PPG manual, "Vinyl Chloride Monomer Handling and Properties," form A-994115R.
Fire hazard Vinyl chloride vapor is extremely
flammable. Its explosive limits are be tween 5.6 and 33% by volume in air. Sufficient ventilation and the elimina
tion of ignition sources are mandatory in areas where vapor concentrations may reach a flammable level. When a tank care is unloaded, both the car tank and the unloading pump must be elec trically grounded.
The major products of combustion include toxic and corrosive hydrogen chloride as well as carbon monoxide and carbon dioxide. Under certain con ditions, traces of phosgene may be pro duced.
Unloading tank ears If tank car valves are defective or
leaking, do not unload. Telephone the PPG Chemicals plant at Lake Charles, Louisiana, 318-882-1200. Information on unloading tank cars and trucks ap pears in the PPG manual, "Vinyl Chlo ride Monomer Handling and Proper ties," form A-994-115R.
Warning: Air should never be permit ted to enter vinyl chloride tank cars or other containers during or after unload ing. Close and seal all openings. Leave at least 10 psig of vinyl chloride vapor pressure in empty tank car being re turned.
PACKAGING AND SHIPPING PPG Industries delivers vinyl chlo
ride by ship, barge, tank car and tank truck. There are three shipping points: Lake Charles, Louisiana; Guayanilla, Puerto Rico; and Paulsboro, New Jer sey.
PPG maintains a fleet of tank cars for vinyl chloride service only. All cars are equipped for top unloading. Tank car capacity is 180,000-pounds net 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 avail
able on special request in returnable laboratory-size steel cylinders holding 5 pounds.
The technical service staff of PPG In dustries' Chemical Division is available for consulting on handling, storage and use.
=R 2M 375
^ Statements and methods proamied are
-
/ PPG INDUSTRIES, Inc. Chemical Division -
- One Gateway Center ... /
' -4-'' " information jnd practices known to PPO'dridirsTrlfts^nc. buPirt rL'u'rcsenuiiDnv or warranties of iMyrJDrmatice or ^csuii r.oi do imply, any recommendaTions IP toffinge ,'npyjpalfni an Dfler of hciTvA' under ..any "patent With fl/SpCcl. TO Its '.products PPG' Industries, Inc- warrants only that [ thoyionfprm . lo i its duality
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Read the label carefully anti
_'obserw and comply witd j>tl ihe label wam/nQs anil pr itc.autlonary ,
dirertrons ;-Althout)r> thw; materials *>re"not intended lor household-:'
thry. as all potentially ha/ardouS'rrwiieriaK, must be Kept but of-, `
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UNION CARBIDE CORPORATION P. 0. BOX 8361, SOUTH CHARLESTON, WV
Health. Safety S Environmental Affairs Department
December 16, 1981
25303
RECEIVED
DEC 2* 31
Mr. Orvle Nicholson BCM Laboratory Division
325 Thirteenth Street Dunbar, West Virginia 25064
M. G. MANETTl
Re: Vinyl Chloride and Polyvinyl Chloride Analytical Capability
Dear Mr. Nicholson:
Squire, Sanders and Dempsey, a Cleveland, Ohio law firm is seeking an independent laboratory to analyze an unsaturated
polyester fiberglass molding for contained vinyl chloride mono mer and for contained polyvinyl chloride resin. A representative formulation for the molding is as follows:
65 parts polyester resin 12 parts polyvinyl chloride copolymer 23 parts styrene monomer 200 parts hydrated alumina and calcium carbonate 1.5 parts tert butyl benzoate 10 parts carbon black
4 parts calcium stearate 0.5 part magnesium oxide
65 parts fiberglass
during molding, most of the styrene monomer reacts with the polyester yielding a cross-linked polymer.
The analysis for polyvinyl chloride content would confirm its presence in the molding and could obviate the need for re
vealing a proprietary formulation. Hopefully, this result would be to the nearest 0.1% by weight.
The analysis for vinyl chloride monomer is more difficult because it needs to be a great deal more sensitive, i.e., lOppbw,
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Mr. Orvie Nicholson Page 2 December 16, 1981
At the low concentration involved, specificity of the method becomes very important.
Attached for your consideration are the following analytical methods:
1. Union Carbide Standard Testing Method WV-294-A Determination of Polyvinyl Chloride in Resins (Equivalent to ASTM D 1303).
2. Proposed ASTM Standard Method Determining > 5ppb Residual Vinyl Chloride Content of Vinyl Chloride Homo- and co-polymers by Head Space Chromatography.
3. Union Carbide Corporation Method Determination of Law Level Residual Vinyl Chloride Monomer in Vinyl Chloride Copolymers by Automated Headspace Chromatography with an Electrolytic Conductivity Detector.
4. Dennison, et al, "Headspace Sampling and Gas-Solid Chromatographic Determination and Confirmation of > lppb Vinyl Chloride Residues in Polyvinyl Chloride Food Packaging", J. Assoc. Off. Anal. Chem. Vol. 61, No. 4, 1978.
The foregoing methods have a fault in that none have been used to analyze the material in question. Our analytical people prefer method three over methods two and four because it is more specific to vinyl chloride.
The project would involve a one time study of two polyester fiberglass molding samples, one containing polyvinyl chloride and one containing no polyvinyl chloride. The study will require a written report certified by a qualified chemist.
Currently, we would like to know if your laboratory has the facilities, equipment and personnel to do the study outlined and wishes to be considered for the work. If your answer is yes
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'"Mr. `Orvi6` Nicholson Page 3 December 16, 1981
then Mr. Robert Maynard of the law firm will contact you re garding coat, timing, etc. If you answer is no, then please return the attached material to me. I will be pleased to answer any questions you may have on the technical aspects
f the work or on the definition of the job if they are not clear in my letter.
Very truly yours,
/e.n. /*<4X-
R. N. Wheeler, Jr. Assistant Director of Product Safety RNWjr/dh Attachments *'* cc: Robert Maynard, Esq. M. G. Manetti, Esq.
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