Document 6b4YoBzQ03VNJe4K111Vy1xm

SOUTH CHARLESTON RIANT UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS 9.0. BOX 900*, SOUTH CHARLESTON! W. VA. 2S303 24. December 2, 1974 Mr. John Stender Assistant Secretary of Labor for Occupational Safety and Health U. S. Department of Labor 14th Street and Constitution Avenue Washington, D. C. 20004 Re: Dear Mr. Stender: Occupational Safety and Health Standard for Exposure to Vinvl Chloride The Occupational Safety and Health Standard for Exposure to Vinyl Chloride promulgated on October 4, 1974 applies to the transportation of vinyl chloride and polyvinyl chloride..... The broad application of this standard is such that all employees of distributive organizations must be monitored for exposure and trained in the hazards of vinyl chloride, and that records of those employees monitoring and training be maintained for thirty years. A four* ounce sample of polyvinyl chloride shipped by parcel post in a sealed can would require monitoring, training, and records for a mass of postal employees despite the'fact that no significant exposure to vinyl chloride monomer could occur. A single, fifty*pound, paper bag of resin is essentially treated the same as a rail car containing fifty tons. In the case of the large bulk container be it ship, rail car, or truck, adherence to the letter of the standard regarding monitoring, training, and record keeping is relatively easy and the tran6porta* tion company has an economic incentive to transport the product. In the case of the single bag shipment, the multi-bag shipment, or the sample shipment, the logical move on the part of the transportation company is simply to refuse shipment to spare themselves the obvious expense involved in monitoring, train ing, and record keeping. The same applies to the public warehouse man and the terminal operator. Many of these distributive companies have indicated that they plan to handle direct truck load or rail car load shipments only of poly vinyl chloride. Union Carbide Corporation owns and operates major polyvinyl chloride resin production facilities at South Charleston, West Virginia and at Texas City, Texas. Production facilities at these locations produce a variety of polyvinyl chloride res ins by four different processes - suspension polymeri zation, hulk polymerization, emulsion polymerization, and solution polymeriza tion. Only one of these polyvinyl chloride resin products, suspension resins, RNW 0276 Wr. John Stender 25. -2- December 2, 1974 ->ntains significant amounts of vinyl chloride monomer; this material is generally shipped by bulk and represents no considerable problem in distribu tion. Products from the other three processes are distributed world-wide via a network of warehouses and transportation companies. Of these resins, approximately one half or 100, 000, 000 pounds per year are ultimately delivered to about 1,500 customers in less-than-truck-load quantities. The average ship ment is estimated to be 11,000 pounds. These less-than-truck-load shipments (9,500 per year) involve 41 public warehouses and up to 200 different common carrier trucking companies in the United States alone. The value of these sales to Union Carbide Corporation is approximately $22, 000, 000 per year. A sub stantial number of trucking and warehouse companies have indicated they do not -wish to handle these shipments in the future. Union Carbide Corporation thus .finds itself with having to meet a very difficult standard in its production facilities and with being unable to supply many of its smaller customers. Other companies are faced with similar problems. Union Carbide Corporation is also concerned about the distribution problem as it is related to its customers. Many of Union Carbide's customers are formulators of lacquers, plastisols, and organosols for coating and molding applications. These liquids are normally shipped in closed steel drums by common carrier truck. As required by the Standard, monitoring, training, and record keeping are needed. `It is very hard to conceive how a vinyl resin con taining no detectable vinyl chloride monomer, formulated into a coating material, nd shipped in a sealed steel drum can be a hazard to a trucker or anyone else. This problem was discussed with Mr. Grover Wren, Chief of Health Standards Development, by Dr. R. S. Brookman of Firestone Plastics Company, Mr. Wayne T. Brooks of Organization Resources Counselors, and me on November 26, 1974. The consensus of the discussion was `that good monitoring studies of shipments correlated with type of PVC, weight of the shipment, vinyl chloride content of the PVC, the mode of shipment, and the resin container could be used to develop shipping rules, freight classifications, and resin containers to fulfill the spirit of the vinyl chloride standard without requiring all of die monitoring, et cetera burdens of the transportation company. With adequate guidelines for the shipper and the transportation company owners, application of the Standard's requirements for monitoring, training, and record keeping can be avoided without any sacrifice of employee safety. Due to the diversity of the industry interests and the broad sweep of die -vinyl chloride Standard in its safety objective, I think the Department of JLabor should take the initiative in providing clear-cut rules and procedures for vinyl resin transportation.and distribution. Certainly, a trucking company in RNW 0277 Mr. John Stender 26. 3 December 2, 1974 Dcs Moines, Iowa, hauling 2, 000 pounds of solution polymerized VYHH resin containing no detectable vinyl chloride monomer, should no; have to monitor its employee vinyl chloride exposure, train them in its hazard, and keep such records thirty years. A task force or committee, under the direction of the Assistant Secretary of Labor, should certainly be able to arrive at performance standards and rules for the distribution industry that achieve the objectives of tho Standard. Union Carbide Corporation, Firestone Plastics Company, and znany others would be willing to contribute data and alternative distribution technics to such a group. The formation of such a group could do much to clear up other questions regarding this Standard and to demonstrate that the Department of Labor considers employee safety a cooperative effort by all concerned. Very truly yours RNWJr/ra N. Wheeler, Jr. RNW 0278 Union Carbide Corporation Chemicals and Plastics Division 270 Park Avenue, New York, N. Y. 10017 27. DETERMINATION OF RESIDUAL VINYL CHLORIDE MONOMER IN VINYL RESINS Method Number WC-326-G-1 1 purpose Issue Page of 1 13 A procedure for determining small amounts of residual vinyl chloride monomer present in vinyl resins is described. The resin sample is dis Date January 20, 1975 solved in a suitable solvent and is analyzed using a gas chromatographic technique utilizing a backflush mode. The method is applicable for use with poly(vinyl chloride), vinyl chloride-vinyl acetate copolymers and other vinyl resins in which there are no volatiles which interfere in the determin ation. The method resolves vinyl chloride from major impurities found in vinyl resins and can be quantitated with proper calibrations.* 2 EQUIPMENT AND REAGENTS a) Gas chromatograph, Hewlett-Packard (F and M) Model 5753 or equivalent, equipped with a hydrogen flame ionization detector. b) Backflush valve, Bendix 8-port sliding plate valve or equivalent. c) Tetrahydrofuran, reagent grade d) Balance with accuracy to 0.10 gram e) Fritted glass 6parger, fine 3 INSTRUMENT PARAMETERS Instrument Column Backflush valve Tempera tures Column Injection port Detector Carrier gas Flows Helium carrier gas a) inject b) backflush Hydrogen Compressed air Sample size Hewlett-Packard (F and M) Model 5750 or equivalent, equipped with hydrogen flame ionization detector 20 feet x 1/8-inch stainless steel tubing packed with 20 percent TERGIT0L E-35 on Chromosorb W AW, 60/80 mesh Bendix, .8 port sliding plate valve or equivalent 70C isothermal 100C (maximum) 300C helium 40 cc/minute 40 cc/minute 20 psi at-cylinder heat 40 psi at cylinder head 40 microliters RNW 0279 Electrometer Range Attenuation Approximate elution time vinyl chloride 1 8 2.8 i minutes WC-326-G-1 Page 2 of 3 January 20, 1975 4 SCHEMATIC OFFLOW SYSTEMA schematic of the flow system utilizing the Bendix 8-port sliding plate valve is attached as Figure 1. 5 PROCEDURE Analyze the tetrahydrofuran (THF) prior to preparing any samples or calibration standards using the parameters listed in Section 3. A backflush valve has been incorporated into the system to facilitate the analysis. Four minutes after the sample injection, the column is backflushed and vented to the atmosphere thus pre* venting the solvent from reaching the detector. A backflush time of 10-15 minutes should be sufficient to elute the solvent. After the backflush period, return the valve to its original position. The base line should be allowed to equilibrate before injecting another sample. Compare the THF chromatogram with those shown below. If the scan is comparable to A, the THF will have to be sparged with nitrogen at a medium flow rate for approximately 2 hours in an attempt to remove the interfering peak. Reanalyze the sparged THF to determine if it is acceptable. If the scan is comparable to B, the THF should be acceptable for use in the analysis. i Accurately weigh one- gram of the resin to be analyzed into a 6-dram vial containing 9 grams of THF. Cap the vial and shake to _ effect solution'. Analyze the sample using the parameters listed in Section 3 and follow the above instructions for the backflush. RNW 0280 WC-326-G-1 29 Page 3 of 3 January 20, 1975 Measure the peak height of the vinyl chloride peak in millimeters. ie area can also be measured using an acceptable technique (e.g. planimeter, automatic integrator, computer, etc.). CALIBRATION Prepare solution mixtures in the THF of varying amounts of vinyl chloride to cover the expected ppm range of concentration. Obtain the gas chromatogram for each sample using the parameters listed in Section 3. Prepare a chart plotting the peak height (or area) obtained from the chromatogram of each sample versus the known concentration to establish a relative detector response. See Tigure 2 for typical calibration curve. 7 CALCULATIONS Determine the monomer content in the test solution from the cal ibration chart. Apply the peak height (or area) of the monomer obtained from the chromatographic scan of the test solution to the calibration curve and read the corresponding concentration in parts per million (ppm). The concentration value obtained from the calibration curve is total monomer in the solution. In order to convert the data to monomer concentration based on total resin, the value must be multiplied by a factor of 10. 'AS CHROMATOGRAM A gas chromatogram is attached as Figure 3 showing the response lor 1*3 ppm vinyl chloride. J RNW 0281 FIGURE 1 SCHEMATIC OF FLOW SYSTEM UTILIZING THE BENDIX 8-PORT SLIDING PLATE VALVE 30. RNW 0282 FIGURE 2 TYPICAL GAS CHROMATOGRAPHIC CALIBRATION CURVE 31 FIGURE 3 GAS CHROMATOGRAM OF VINYL RESIN WITH 1.3 PPM VINYL CHLORIDE MONOMER 32, D e te cto r response Time, minutes RNW 0284 RNW 0285 MATERIAL SAFETY DATA SHEET EFFECTIVE DATE wch 15,1981 OOU-029 PRODUCT NAME: CHEMICAL NAME: FORMULA: SYNONYMS: DEPARTMENT OF TRANSPORTATION CAS* 25085-82-9 I: ~i- r*. i <\ UCAR Solution VinySyiani^K^biaVl Hi CHEMICAL FAMILY: V V/ \ 6 / r HAZARD CLASSIFICATION SHIPPING NAME None None MOLECULAR WEIGHT: Vinyl chloride-vinyl acetate maleic acid terpolymer Mn * 8000 to 22 000 CAS NAME Acetic acid ethenyl ester, polymer with chloroethene and 2.5-furandione. 1 MELTING POINT DENSITY PER CENT VOLATILES BY VOLUME APPEARANCE AND ODOR Not applicable 1.34 1 0.005 grams per ec at 20/20 C Nil Fine, white, powdered solid: very slight, pleasant odor. MATERIAL Vinyl cftlondevinvt acetate resin - j............. Water Solvents % >97 <2 <0.5 TLV (Unite) ' Not established 1 ppm HAZARD None currently known Carcinogen Flammable. Toxic AUTOIGNITION TEMPERATURE 725 #F . ASTM D 1929 EXTINGUISHING UEDIA Use water spray, carbon dioxide, dry chemical, or alcohol-type or universal-type foams. Apply by manufacturer's recommended technique. SPECIAL FIRE FIGHTING PROCEDURES Use supplied breathing air and protective dothing. PUUNTIFF^J EXHIBIT I U>*:c\tr-23r 1 tuaniiiiMiwun 1 UNUSUAL FIRE AND EXPLOSION HAZARDS Hydrogen chloride will form under fire conditions. RNW 0286 304/744*3487 Tht number is mKibi dv, nights, and hoiidavt. Cat z* ~:*9c*a*or> asidv-- that iht aata eontamad hafatn arc taetuat and tha optntohs atofataad ara **ea o< ouaM*>ae a>aant 'gatornc ,f*t 'tsuiti o* rna ta*s eoftd.:?*: ***a :ii a*t : to da t--i aa a warranty or tayaaniatton ter wrweft Union Camtdt Corporation aaaumt togs sponsions *naaraottartdo<a-vtorvoucohaiga'aiior m` grr: .** : c* o*e ,,motthaaaoataono information must daotiprmmod t>v tha uwrtooamacco*oanc* *aonc*C'**tc*'* Stata and >oca> ana'gu:a'ton9 .V Af DURCE: None established for vinyl resin by ACGIH or OSHA. Vinyl chloride: 1 ppm. OSHA 29 CFR i 1910.1017. exemption (b) (6). :UTE EFFECTS OF OVEREXPOSURE SWALLOWING None currently known. May cause some nausea. n SKIN ABSORPTION INHALATION SKIN CONTACT EYE CONTACT None currently known. None currently known. None currently known. None currently known. riRONIC EFFECTS ' OVEREXPOSURE THER HEALTH AZAROS BMA'baaolMaed vinyl chloride as a careinogan- ACGIH has a TLV for nuisance and respirable dusts and OSHA regulates both under 29 CFR t 1910.1000, Table Z-3. Powdered vinyl resins can contribute to nuisance dusts and may contribute to respirable dusts. AND FIRST AIO PROCEDURES: SWALLOWING Give two glasses of water and induce vomiting by putting finger down throat. SKIN Flush with water. INHALATION No emergency care anticipated. EYES Flush with water. OTES TO PHYSICIAN This is a relatively innocuous substance not expected to cause harm. Any treatment that might be required for overexposure should be directed at the control of symptoms and the dinieal conditions. There is no specific antidote. RNW 0287 STABILITY UNSTABLE STABLE y/ INCOMPATIBILITY (materials to avoid) HAZARDOUS COMBUSTION OR DECOMPOSITION PRODUCTS HAZARDOUS POLYMERIZATION May Occur Will not Occur --V CONDITIONS TO AVOID None None Burning and elevated temperatures can produce hydrogen chloride. carbon monoxide, and/or carbon dioxide. CONDITIONS TO AVOID None STEPS TO BE TAKEN IF MATERIAL IS RELEASED OR SPILLED WASTE DISPOSAL METHOD Sweep up; collect in a suitable container for disposal. Bury in a landfill where permitted under appropriate Federal, State, and local regulations. RESPIRATORY protection (pccify type) VENTILATION General room ventilation should be adequate. Supplement with local exhaust equipment, should dusting conditions prevail. PROTECTIVE GLOVES OTHER PROTECTIVE EQUIPMENT Substantial leather work gloves Eye bath and safety shower SSqtcctkm j PRECAUTIONS TO BE TAKEN IN HANDUNG AND STORING Breathing dust may be harmful. Avoid breathing dust. ______________________________________________ FOR INDUSTRY USE ONLY OTHER PRECAUTIONS Limit the amount of dun available by appropriate handling and processing. Eliminate static electricity by proper procedures and by effective grounding ! i i j 1 { | 1 RNW 0288 .V AND SOURCE: ; t jv.r*. None established for vinyl resin by ACGIH or OSHA. Vinyl ppni, 00HA"3S CTTT1 WIO-TPH. exemption tbf W* ACUTE EFFECTS OF OVEREXPOSURE SWALLOWING SKIN ABSORPTION None currently known. INHALATION None currently known. SKIN CONTACT None currently known. j !i j EYE CONTACT None currently known. | CHRONIC EFFECTS OF OVEREXPOSURE OTHER HEALTH HAZARDS EMERGENCY AND FIRST AID PROCEDURES: | SWALLOWING SKIN INHALATION EYES i ACGIH has a TLV for nuisance and respirable dura and OSH A regulates both i under 29 CFR i 1910.1000, Table Z-3. Powdered vinyl resns can contribute ! to nuisance dusts and may contribute to respirable dusts Give two glasses of enter and induce vomiting by putting finger down throat. Flush with water. No emergency care anticipated. w Flush with water. NOTES TO PHYSICIAN This is a relatively innocuous substance not expected to cause harm. Any treatment that might be required for overexposure should be directed at the control of symptoms and the clinical conditions. There is no specific antidote. (f RNW 0289 MATERIAL SAFETY DATA SHEET EFFECTIVE DATE: March 15, 1881 4>002 S-3 PRODUCT NAME: CHEMICAL NAME: FORMULA: SYNONYMS: DEPARTMENT OF TRANSPORTATION ; CAS 9003-22-9 i-yz. m."' *> Vnaiv'"' i". UCAR Solution Vinyl* 1 ^ ' -V: ---- copolymers MOLECULAR WEIGHT: M. 8 000 to 35 000 HAZARD CLASSIFICATION SHIPPING NAME None N00* CAS NAME Antic add ethenyl ester, polymer with chlorethene > 1 MELTING POINT | DENSITY * PER CENT VOLATILES | BY VOLUME APPEARANCE AND ODOR Not applicable 1.35 to 1.39 grams per cc at 20/20 *C Nil Fine, white, powdered solid; very slight, pleesant odor. -- MATERIAL Vinyl chloridevinyl acetate resin aNSfMMeM* Water % >97 <2 TLV (Units) Not established A HAZARD None current!v known Carcinogen j Solvents ! AUTOIGNITION {TEMPERATURE 1 t1 i EXTINGUISHING MEDIA i <0.5 734 F . ASTM D 1929 1 >. - 1Y-. Flammable. Toxic Use water spray, carbon dioxide, dry chemical, or alcohol-type or universal-type loams. Apply by manufacturer's recommended technique. ! SPECIAL FIRE FIGHTING PROCEDURES l i Use supplied air and protective dothing. i ! UNUSUAL FIRE AND j EXPLOSION HAZARDS i I Hydrogen chloride will form under fire conditions. RNW 0290 304/744-3487 Dim numbtr it aviiliftit d*v. mffm. imkindi. and hot dtvs. wmm Carftsoa CorooraMon oautvsB mat tna oats eontatwafl nram a'a factual ano rnt ooimow* *r* * :s# ?* aua* '*ac aioant ragaromg tn rcsu o' *> tasis conouctto t*adata tnot 10 at <aa* aa a warranty or rapnaamiio* for wrngfi utmow Car&*ot Corporator aauwe aga *Dnit>"' 'iev araoHatao tott'y to* yc j so*a'ea'atio' FwinnaA aHO<aH<aiion AAviaaofi*aaaaauno*formacfonmuaroa0titrmmoaoyinBtfaoMoo<naccor0aA * appitcac1**aoarai Stata anoiocaMawsa^oragwrions UNION CARBIDE CORPORATION COATINGS MATERIALS DIVISION OLD = IDGEBURY RD. DANBURY. CT 06817 raw 0C r r stagIIUTY UNSTABLE STABLE --V INCOMPATIBILITY (materials to avoid) HAZARDOUS COMBUSTION OR DECOMPOSITION PRODUCTS i HAZARDOUS POLYMERIZATION May Occur Will not Occur -- >/ \ -\ 4 CONDITIONS TO AV0I0 None None Burning and elevated temperatures can produce hydrogen chloride, carbon monoxide, and/or carbon dioxide. CONDITIONS TO AVOID no-n--e STEPS TO BE TAKEN IF MATERIAL IS RELEASED OR SPILLED I WASTE DISPOSAL METHOD Suwp up; collect in > suitable container lor disposal. Bury in a landfill where permitted under appropriate Federal. Sate, and local regulations. , I | I VENTILATION General room ventilation should be adequate. Supplement with local exhaust equipment, should dusting conditions prevail. PROTECTIVE GLOVES OTHER PROTECTIVE EQUIPMENT Substantial leather worts gloves Eye bath and safety Fxjwer EYE PROTECTION PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING Safety glasses | Breathing dust may be harmful. Avoid breathing dust. FOR INDUSTRY USE ONLY OTHER PRECAUTIONS j Limit the amount of dust available bv appropriate handling and processing. Eliminate static electricity by proper procedures and by effective grounding. RNW 0291 V AND SOURCE: 'j,'- > iv.yr. None established for vinyl resin by ACGIH or OSH A. Vinyl elWandt I ppm, OOMA'79 CFH T TtTIO.TT3ri7. exemption (W <6H JUTE EFFECTS OF OVEREXPOSURE A/ALLOWING None currently known. May cause some nausea. SKIN ABSORPTION None currently known. INHALATION None currently known. SKIN CONTACT None currently known. j j EYE CONTACT None currently known. j HRONIC EFFECTS JF OVEREXPOSURE OTHER HEALTH HAZARDS EMERGENCY AND FIRST AID PROCEDURES: SWALLOWING SKIN INHALATION EYES Ameeem iNempewider xtmammam-- j j ACGIH has a TLV for nuisance and respirable dusts and OSH a regulates both i under 29 CFR 5 1910.1000, Table Z-3. Powdered vinyl resins can contribute ' to nuisance dusts and may contribute to respirable dusts j Give two glasses of water and induce vomiting by putting finger down throat. Flush with water. -- No emergency care anticipated. Flush with water. NOTES TO PHYSICIAN This is a relatively innocuous substance not expected to cause harm. Any treatment that might be required for overexposure should be directed at the control of symptoms and the clinical conditions. There is no specific antidote. RNW 0292