Document gDYz475myNwB8K1E05zX5wZZQ

O- ^ f. /v -/ r>j VBJGoodrkh/ B.F. Goodrich Chemical Company A 0IVISI0N Of THE 8 F G000RICH COMPANY 6100 OAK TREE BOULEVARO CIEVEIANO. OHIO 44131 PHONE 216-524-0200 INTERNATIONAL DEPARTMENT March 6, 1975 VIA AIR MAIL Subject: Vinyl Chloride Included in this transmission are the following: 1) Articles related to VCM emission. 2) An Authorization to Manufacture prepared for Louisville plant for the purpose of changing recovery conditions in an effort to get PVC resin with less than 10 PPM of RVCM. 3) Report entitled "The Reaction of Potassium Permanganate with Vinyl Chloride Monomer". The Avon Lake plant is now experimenting with this procedure on a plant scale. The seal water from the recovery pumps is passed through a tank where dissolved VCM reacts with Potassium Permanganate before the water can go to sewer system. h) A meeting report on Infrared Fourier Transform System for Monitoring Taxic Gases. This is for information purposes only and serves to illustrate that B.F. Goodrich is continually looking at new VCM detection equipment. Best regards, JES/kan Attachments John E. Stroope CABLE ADORESS GOODCHEM I 0 P C . -- CODE ABC SIXTH EDITION TELEX NO. 88-04 2 7 ^ Q Q l fcS fyg 9 > . . -4 < * . 4 2 .. the couamtxotTajui, Thursday, febsuakt sa. iws i t . ii V. * -r'. * ' ' .. ' . . * Vr . "* 1A W | Industry asks ,; V stay of standards : [ on uinjZ cldoride 9- ' ..*.* -J ' i KEW YOKE -- The plastk* fcatetoy / - lux Barred to stay nr povenimest cUn* J ; tins rejutoUcj industrial wattttf fesore to vinyl chloride. The Society of the Plastic* Industry.' . Inc, said yesterjiay it weald ask the Sa* Jwesose Cosrt to rsrrietr a recent fectral appeals court decision u?boldia|t the uew . scisdardi ssA ordering Uwa ittio effect .: ApriiL ( Jbcpwsre to Thtyi chlcrtd ha been I Stoked to 21 case* of * nun, total liver .! cascer. The cbisatcVS is widely vseA in . ! the mtaafactso* ci plastics. ' = c I J?Wr stoadsrfe for exposure to the- ` [ chtedad were ordered isst year fey Sect** ` d -. I toy of I-Hhor Peter Bmmaa, and the t Occupational Safety and Health Adzotois* ~ * trstioa pbU?ld than on Oci. A - ! The standards mUouj'i in exposure l~ . Ur-^i cf rr'r 1 r,r'* r<,r trillm arerace f\ * ever sny eight-boar period and 5 part* {per mCUion creraf* over aajr l^usionto ; | pnioi *. l Workers who would be exposed to air . - , I with concentrations of vinyl chloride | treater than those limit* wnaU be ref paired to ww aspirators. % Jn Its motion before the 2nd D5. CSr* | csit Cosrt at Ar-nca'iX. the society asked 1 that the ia.eria) exposure &.aaitora ci 32' . J. part* per ralUisn he twaifflssd pending ' " { s&pes&ea of the case fey the Supreta* tCowta - -'r* vv'VV^^ !#'*?** -A*V f Jfi. A. Vittooe & D. Scott J L. Kelson E. B. Osborne K. Greene P. J. Weaver B. &. Downey B* H. G, Zvlcker C. Pov V. i. Wilcox E. W. Harrington _H. ^alternate ~B*?Kenney-A fcrtfalileid-C.3,Flynn r c I cry -ts, r* C5 / CJ ICI to expand its US UK chemical job prospects operations at Bayport encouraging Job prospects for the New Year in UK chemical manufac by Ann Taylor turing firms arc relatively en couraging. with more com [CI United Suites is studying several new chemicals manu facturing projects, following the acquisition of a 250-acrc site in the Bayport industrial a joint venture with Ccltmesc. There arc seven company divi sions. l.atest project and ICPs lar gest single investment in the Other acquisitions included Stuart Pharmaceuticals, the Chemical Manufacturing Co which produces chemicals for use in polyurethane foams, and panies nearly one in live forecasting recruitment than cutbacks, according to a survey by Manpower, the worldwide service group. development complex near US-- is the $50 million Mclinex a stake in Rubicon Chemicals, In chemical manufacturing, Houston. Tex. from an Exxon polyester film plant at Hope- find Katalco, a catalyst produ 18-6",. of companies antici subsidiary. No specific details well. Va, which is believed' to cer. pated an increase in labour arc available as none of the have capacity for about 22000 ICI America first started requirements for this quarter, projects has been approved yet. tonnes/ycar. This unit started manufacturing at Bayonne, NJ compared with 22 ) ''.', for the ICI United States is the US up at the beginning of 1972. in 1966 where operations in last quarter and 35-2". for the operating subsidiary of TCI Previously the UK market for clude the production of Cere- first quarter of 1974. America. Turnover for the last Melinex had been supplied clor chlorinated paraffin waxes, This compares with 10-1% fiscal year (I October 1973-30 from Id's Rozenburg, Nether Alloprcne chlorinated rubber, of companies expecting a de September 1974) was $300 mil lands. plant and from its Dum polyurethane speciality chemi crease for this quarter com lion. ICI United States manu fries. UK. unit. cals and PTEE. pared with 3-5and 50",", for factures a variety of chemicals including spcciati'ies. pharmaecuiic.ils. plastics, films. dyes and ' c \ 111 c chemicals, .upicuflurat Ja'ia vt!'. aeio.pace pro ducts a-al fibres the Inner via ICI made a major plunge into the US market with its acquisition of Atlas Chemical Industries in 1971 following a SIM million hid. I his com pany was merged with IC1 All the major European chemicals producers are build ing up their operations in the US. In Id's case, the likely areas for expansion include specialities, products near to the previous periods. 65-5',. of companies saw no change while 5 4', did not know. Looking at the regions, the survev says that at Darlington, Middlesbrough and Hartlepool, UK oil imports America, whose headquarters the consumer market and agro in the north-east, confidence in is now at Wilmington. Del. chemicals. ICI America has a the region's long-term pros drop by 10% in third quarter There are plants in 10 stales and corporate research labora tories in Wilmington. The group's first step in the biological research centre for agrochemicals in North Caro lina. Pharmaceuticals make a pects associated with the development of the petro chemical industries and the easing of raw material short Crude oil imports into the UK fell hy 10 dining the third quarter of 1924. continuing the trend towards cnetgy conserva tion. US came in the 1950s with the purchase of a 70` . interest in Arnold Hoffman and Co, a New England manufacturer of textile chemicals and dyestuffs. major contribution towards ICI United Slates profits, and further expansion is likely here, though probably not at Bayport. ages is tempered by cashflow problems and a continuing famine of skilled labour In creases arc forecast at Darling ton in chemicals. Imports in the third quarter totalled 25 million tons, against 28 million tons in the same VCM cancer case at BPCIperiod of 1973. Accotding to ^ Enervy Treiulx. published by the Dcpat intent of Energy, the Cutback is due to the continu ing li'gh level of stocks and lower demand for oil products, with the exception of fuel oil. The constant demand for fuel oil is a result of the use of the product by power stations due to the coal shortage. However, total energy con sumption was only 0-5'','. less in October 1974. compared to A second case of angiosarcoma has been discovered in the UK PV'C industry. The man. who was 37 years old. worked at the BP Chemicals site at Barry as an autoclave cleaner on the VCM plant, for just over 3 years, between 1906 and 1969. He died on 24 December. There is apparently no doubt that this is a case of angiosar coma. although the findings are 500 ppm. this is still consider ably below the levels of earlier years. A spokesman for BP. how ever. stressed that there were unusual medical factors in the man's medical history that were being investigated, and which could have a bearing on the case. The only previous case of angiosarcoma in a worker ex 25 ppm. It is understood that the working party was fully aware of the suspected BP case of angiosarcoma when deciding on its recommendations. Meanwhile, in the US. a federal appeals court has ordered a stay on the imple mentation of the government regulations on workers expo sure to VCM (CA, It October 1973 p 1). October 1973. due to the in creased use of natural gas. Petrol consumption rose to the year's highest level in October. although for the first 10 months of the year, still to be confirmed by a panel of government pathologists. What is different about the case, however, is the relatively short period of lime that the man was exposed to VCM. posed to VCM in the UK in volved an ICI pensioner aged 71. HP's acknowledgement of this recent case of angiosar coma came only a few days The US plastics industry has asked for a stay on the grounds that the new standards were too vague, and were not based on substantial evidence. The new standards call for workers" consumption fell by 4"... The Of the 24 cases of angiosar after the government working exposure to be reduced to con effects of recent price increases coma discovered in VCM party, looking at the angiosar centrations of VCM of 1 ppm and speed restrictions on workers throughout the world, coma/VC M question had over an eight hour shift. The demand have not yet been all except this recent case in agreed on the official exposure present maximum level is 50 reflected in petrol consumption volved workers who had been limit for the UK industry. This ppm. figures. exposed to high concentrations represents no change from the The court granted a stay on According to the Institute of over many years. voluntary limits accepted by the implementation of the new Petroleum, oil consumption in Although the level to which the UK PVC manufacturers, regulations until it had com the first nine months of 1974 the latest victim was exposed of a ceiling of 50 ppm, with a pleted its review of the situa dropped by 7-3%. over the three years was up to time weighted average of tion. CHEMICAL AGE 3 tO JANUARY 197S 3 The current goal for RVCM in Geon pearl resins is 10 ppm or lower. To attain this goal without venting VCM to the atmosphere and assuming that stripping columns will not be generally available for Geon pearl resins made in the small reactors at Louisville, the RVCM must be removed in the blowdown tank. Work at other plants has indicated that RVCM can be lowered to satisfactory levels by stripp ing in the blowdown tank to 220*F. Current stripping temperatures at Louisville vary from 170*F in Bldg. Ill to 190*F in Bldg. 1. * 10 charges then 100.000 lbs. then 250.000 lbs. then 750.000 lbs. then unlimited WHAT IS THil P.JODUC I AND HOW !S If T O BE MADE.' The products will be all pearl and G~90 series resins made in Bldg. 1, 15, and 111. Stripping to 220*F at various times to reduce RVCM in the finished resin to below 10 ppm without excessive venting to the atmosphere will be accomplished. To Re Approved By To 3e Evoluated By Production Production y y Non-Stondord Raw Materials To Be burnished By Property Of Production y A Mq chrr*en ts Manufacturing Spec. Technical Reports Dev. Development Pel Development Product Spec. REQUESTED BY DEPT 5773, 5774, and 5775 R. Baliman s. Brown ROUTINGS AND APPROVALS authority Manager Development Manufacturing Processes Offi ce -- Vi ce* Pres idem* Production Sales Manager Manufacturing Plan? -- Technical Manufacturing Plant--Production Manufacturing Plant--Mcnoger 3 P-- g - 1 5032 Field Soles Tech. Spec. DA T _________2/4/75_________ DATE 7- ? r X <0 POINTED IN US V "" L7 BFG TECHNICAL DOCUMENT . B.F.GOO&RICH CHEMICAL COMPANY TECHNICAL REPORT title The Reaction of Potassium Permanganate with Vinyl Chloride Monomer njTMon M. O'Mara, J. L. Dorsch, l DC A T IDM C. A. Daniels, R. F. Koebel n'EClTjKSTLti liv ALTC LOCA 1 J ON l)A 1 I December 30, I'HOJI ( I HO. 19 F. E. Krause SUMMARY ALTC 3690 We have previously reported that VCM in water will rapidly react with potassium permanganate (KMnO, ) to yield CC>2, HC1 and formic acid at pH - 7 and that complete oxidation to CO2, HC1 occurs at pH = 10. An extension of this work has been directed toward obtaining a material balance (chloride ion) to further our understanding of this reaction. \ VCM in pH = 7 and pH = 10 water was reacted with a solution of KMnO^ in a variable volume polyethylene reaction vessel. The results of these experiments indicate a molar stoichiometry (VCM to KMnO^) of 1.3 to 1.5 : 1. Material balance calculations (VCM-in; Cl"-out) could only account for 30 - 40% of the charged VCM. At this point we are repeating this work using an improved gas chromato graphic method of analysis for VCM and two independent methods of analysis for chloride ion in order to determine the cause of this loti? material balance. This study will be carried out on a laboratory scale reaction and a process scale reaction (treatment of seal water). Introduction The purpose of this study was to study the oxidation of vinyl chloride mon omer by potassium permanganate (KMnO^) in solution. Specifically we set the following objectives: (1) determine the rate of reaction, (2) establish the reaction stoichiometry, (3) identify the reaction products, and (4) establish a material balance (VCM-in; chloride ion-out) Since the rate of the reaction was very rapid (seconds) we decided not to spend any time on this particular objective. The reaction products at pH = 7 and pH =/0 have been established. A N.M.R. spectroscopic study has shown that at pH = 7, hydrogen chloride, formic acid, carbon dioxide, potassium ion and manganese dioxi are the reaction products. At the higher pH, formic acid is absent from the reaction products'*) due to its complete oxidation to carbon dioxide. (1) C. A. Daniels, J. L. Dorsch, B.F.G.C.C Technical Report, 12/12/74. ZOO BOO K H L V E P E NCe' .......... -- Gnou-p *j-LE ac"qT o. 001179172 ctf (4) E. A. Collins L. B. Crider R. M. Kreager F. E. Krause A. L. Schultz D. E. Witenhafer ITC G. Huddleston 8rc*1fi3l0 4/71 Brecksville Cleveland A. R. Berens W. F. Bixby C. H. Lufter-J. B. Pausch B. A. DiLiddo E. W. Harrington W. C. Holbrook G. D. Schaaf-E. R. Clayson E. G. Schwaegerle R. L. Toole H. Waltemate _.___________ B. M. G. Zwlcker __________ PRINTED IN ;. A P. E. Kr:, Page 7 IV 974 : 'f this note is to summarize our studies pertaining to the t' ung olij< ! iv.'s: stoichiometry and material balance. f. n tal A gas cliromatographic procedure was set up in order to follow the df arancc of VCM in water after reaction with KMnO^. In this method, a f ted solution of VCM in ll.^O was prepared in a polyethylene bottle. The ;l of the bottle was reduced by 50% by squeezing the sides of the vessel, .hr l'- v'then capped with a septum. At no time was a vapor space pen ' ah.' e this solution. To carry out a reaction, a certain volume of an a ; Kl1 ,(Vt solution was injected into the polyethylene bottle. This solu! 's then chromatographed and the residual vinyl chl-oride remaining after 'ion was determined (volume corrections were made). Standards Chro'- i hie standards were prepared by injecting various concen- trations of Vv ' into the chromatograph under the same conditions as used in the aqur n'.s. The p, mole VCM vs. counts calibration curve is shown in Figure this calibration curve we determined the sat- uration concentre ties- a!r at 23C. and 14 lbs./in.^ of pressure to be 0.119 .002 weigin. ' < re ns ' data^) at 30C. and 14 lbs./in. , this value is about 0.17 wei ' this may indicate an error in our g.c. procedure, I believe it u;i ore in the methods of prepar- ing a saturated solution of VCM. Wu ; 'tons' method which is the proper way of preparing a true saturated solution of a gas in a liquid. In our method we simply bubbled the gas into the solution for a period of time and assumed the solution to be near saturation. According to the above analysis, this saturation method was approximately 71% effective. Reaction at pH = 7 In this experiment, our "saturated" VCM solution was analyzed prior to reaction. The KMnO^ solution was then added to the VCM solution. Reaction was very rapid as evidenced by the immediate formation of the brown pre cipitate, MnC>2. After reaction, the solution was mgain analyzed for residual VCM. The reaction vessel was then opened and the"solution was analyzed for Chloride ion by ion potentiometry: CHC1 = CH, KMn4 _______ * h2o t M) HC1 + C09 + organics' ^ Z The results of this experiment are summarized in Table 1. (2) a. R. Berens, Inter-Organizational Correspondence, "Solubility and Diffusion of VC in Water and PVC", 2/4/74. NO . 3 *1 *2 0 O IE TZG C N G R APH PAPER 20 X 2 0 PER IN C H C tlB E N C O IC TZO C N CO. *m a d i n u . s . a . 3 F. E. Krause Page 4 December 30, 1974 Table 1 Reaction of VCM with KMnO^ in Solution at pH = 7 VCM solution: 0.117 wt. % KMnO^ solution: 0.0316 M initial VCM aliquot (75cc): 0.00141 moles KMnO^ solution added (27.5cc): 0.000868 moles final VCM in aliquot (102.5cc total): .000282 moles moles VCM consumed: .00113 moles VCM: moles KMnO^ = 1.30 Cl found (4.3 X 10 ^ M): .00044 moles chloride recovery = 38.9% Z4G 410Q 8 F. E. Krause Page 5 December 30, 1974 It is obvious that a material balance for chloride ion does not exist. At this point we do not know why this is so. We have examined the Mn02 precipitate and have found no bound chloride. The NMR experiment^) gives no evidence of a chlorinated hydrocarbon. E. Truscott has examined the aqueous solution, using atomic absorption spectroscopy, for a non-ionizing soluble manganese chloride complex. The aqueous solution contained 45 ppm of manganese which translates to 84 X 10"6 moles of Mn in the 102.5cc aliquot (Table 1). Although this is not a negligible quantity, it reflects the finite solubility of* MnC>2 and soluble and ionizing manganese chloride species that may have formed. It is our belief that once these contributions are allowed for, any residual which might account for a non-ionizing species would be negligible. We examined this reaction at a higher pH to determine" if an improvement in the material balance could be obtained. This experiment is summarized in Table 2 (duplicate). The first analysis in Table 2 gave a recovery identical to that in Table 1. The second analysis is somewhat lower. The stoichiometry of the reaction defined as moles of VCM consumed per mole of KMnO^ was found to be 1.3 (pH = 7) and 1.5 (pH = 10). The theoretical value is 1.5. Mention should be made of the high concentration, of VCM in the pH = 10 solution. The solution was attained by using a commercial buffering solution and bubbling VCM into this solution. The concentration (.298 wt. %) was appreciably above that found in experiment #1 (Table 1) and that predicted from Berens' work. It should be noted that the ionic strength of the pH = 10 solution is much higher than neutral water. The solubility of VCM in a higher ionic strength solution should increase since VCM is a polar molecule. Discussion The reaction between VCM and KMnO^ appears to be very straightforward. The NMR experiment (1) indicates that at pH = 10 only carbon dioxide, water and hydrogen chloride are formed from the VCM. Yet in our experiments we have only been able to account for only 30 - 40% of the chloride released in this reaction. Attempts at identifying another species [chlorinated hydro carbon, a manganese chloride (non-ionizing)] which could account for this lack of material balance have failed. At this point we must assume that there is a major problem in one of the methods of analysis (g.c. or ion electrode). I believe that g.c. method is adequate. This analysis can be improved with the use of an internal standard. However, our VCM data seems to check with Berens' published data although our values were l.ower. (If we used Berens' data the material balance would be worse.) At this point we must assume that the ion electrode analysis is in error, ^.though our electrode standards were made up in neutral water (for pH = 7 experiments) and buffered water (for pH = 10 experiments) this analysis should be rechecked by another method. S' Q Q CD F. G. Krause Page 6 December 30, 1974 Table 2 Reaction of VCM with KMnO^ in Solution at pH = 10 Run A VCM solution: 0.298% KMnO^ solution: 0.0316 M initial VCM aliquot (50cc): .00239 moles KMnO^ solution added (70cc): .00221 moles final VCM in aliquot (120cc): 0.0 moles moles VCM consumed: .00239 Cl" found (7.4 X 10"3 M): .00089 moles (in aliquot) chloride recovery: 37.2% Run B initial VCM aliquot (50cc): .00233 moles KMnO^ solution added (50cc): .00158 moles final VCM in aliquot (lOOcc): .000025 moles moles VCM consumed: .00231 moles VCM : Mole KMnO^: 1>46 Cl" found (6.85 X 10"3 M): .000685 chloride recovery: 29.4% 246410:10 F. E. Krause Page 7 December 30, 1974 There is another potential problem that also needs to be studied. During this work it occurred to us that some of the VCM in solution might be "disappearing" through a physical entrapment mechanism during the for mation and precipitation of manganese dioxide. In this mechanism, VCM would be trapped in the manganese dioxide precipitate and would not be accounted for in either the chromatographic analysis or the chloride ion analysis. We have briefly explored this possibility and have determined that it does take place. The following VCM vs. time data applies to a reaction at pH = 10: -> t (min.) 0 58 124 150 358 1500 VCM, Moles X 104 23.3 0.14 0.05 0.16 0.24 0.25 Percent of Original otiginal 0.60 0.21 0.69 1.03 1.07 It is seen that in the first two hours the original VCM concentration decreased by 99.8%. However as time proceeded the VCM concentration increased but not significantly. This increase must be due to VCM migration from Mn02 into the solution. This reaction was repeated at pH = 4 with the following results: t (min.) VCM, Moles X 10^ Percent of Original 0 70 95 1287 16.1 0.04 0.07 0.10 original 0.25 0.43 0.62 Again we see the same phenomenon. It should be stressed that this minor perturbation involves less than 1% of the charged VCM. We need to know if this is truly a minor effect or indicative of a much more serious problem. Future Work We are currently working with engineering to install a prototype unit in which process seal water will be treated with KMnO^. We will use improved methods of chromatography (internal standard) and two methods of chloride analysis to establish a material balance. ch T lO T W b Z i  UTO 1 - f ________ J l * *; - f 1 See Distribution rnoM L. B. Crider UOJCCT .-.i rtt i i> rot in on aknun cm r aim m t hi o> in io. *o. riCM) I'OlNT OR AKNON orPAHTMr.MI Ik HI DO. MO. Avon Lake Technical Center ciA i ( r */i#f< < i.i r i r IIAir. Mil* tCT 1 CR 1/23/75 MEETING REPORT: INFRARED FOURIER TRANSFORM SYSTEM FOR MONITORING TOXIC GASES Introduc tion In our search for new methods for monitoring toxic gases in a variety of work environments we have previously identified the Infrared Fourier Transform method as one that approaches an ideal concept in terms of being specific, rapid and having ppb detection capabilities. Applying this concept to RVCM monitoring involves the utilization of a variety of specialized technical skills, i.e., a good perception of the problem and the assemblying of the components for a system to meet a very specific need. Our several prior discussions with the technical staff of the EOCOM Corp. revealed that they had the in-house technical capabilities and were, in fact, already in the process of putting together a system for the PVC industry. It was agreed that when this system was sufficiently advanced to make a presentation based on factual data (not a purely theoretical concept) that BFG would be interested in a detailed description of their system. This presentation was made by Dr. Tom Dunn (V. P. Marketing) and Mr. George Barr (Marketing Manager) at the ALTC on January 21. The EOCOM Infrared Fourier Transform System The description of the system by Dr. Dunn was essentially the same as presented to OSHA officials in Washington on January 17. Basically, the system includes the following components: 1. Sampling system - can include multiple sample points (up to 64) in locations up to 500 feet from the analyzer. 2. Analyzer section - Fourier Multiplex system with laser source, Michelson interferometer, 40 meter gas cell, .detector and amplifier package. 3. Data System - A/D Converter, On-Line Computer (PDP-11), in-put/out-put teletype, magnetic tape storage and audio-visual alarms. 4. Software package - designed for the specific application. rO-4IIM N(7, u/n LI1HO. IN u .A. Page 2 January 23, 1975 The application of this system (as described by EOCOM) to area monitoring is sufficiently developed to allow the calculation of an 8 hour TWA based on time-motion studies of employee work practices and high frequency analysis of the AVCM level in the work environment. A "typical PVC polymerization work area" was used to describe sampling locations and sampling frequencies to develop a "universe model" used in determining TWA's (hourly and shift) and also to provide leak searching capabilities. The major advantages of the Fourier Transform infrared analyzer are the (1) high resolution (ability to discriminate among other interfering components), (2) high sensitivity ... 50 ppb for VCM, and (3) high speed ... 15 seconds/sample point. EOCOM claims less than 1% down time on the analyzer-data system. Another distinct advantage of this system is that it can be readily used to moniter other organic contaminants in air, such as acrylonitrile benzene, vinylidene chloride and others. Although OSHA was "impressed" with this concept there has been no consnitmcnt, in the form of a verbal or written assurance from OSHA, that the instructions to their compliance officer will include acceptance of this type of area monitoring in lieu of personal monitoring. Assessment and Recommendations The concept described in this presentation represents the most advanced technology for multi-component monitoring that we have identified to date. The cost of this system is $200 - 250,000. In making an analysis of how this system fits some of our current needs, the following are factors that need to be considered; 1. What specific work areas actually need (now or in the future) this type of monitoring capability, i.e., new plants, existing plants, specific buildings, or a plant envelop? 2. If the need exists, can the manufacturing location tolerate another new concept along with their present instrumental mix, i.e., does the plant have the technical where-withall to run such a system? 3. Are the potential benefits worth the cost at the present time? 4. Is there a potential cost savings, i.e., will OSHA accept this type of area monitoring in lieu of personal monitoring? Page 3 January 23, 1975 5. Does EOCOM's analysis of VCM monitoring really fit our long range needs, i.e., why dedicate a system like this to VCM when other monitoring requirements are already apparent. 6. Based on EOCOM's description we know it works in a confined area (building), but will it do equally well out-of-doors? The only recommendation that can be made at the present time is that these questions (and others I'm sure) will need to be considered and reviewed by both R & D and Manufacturing. Also, in light of some of our new monitoring requirements (other than VCM) there is a need to re-evaluate and summarize our monitoring requirements at specific plant locations. We can then begin to assess our capabilities and needs to meet these requirements and also better assess how the Fourier Transform system may fit into this total picture. ch Distribution Attendees L. B. Crider H. E. Diem M. E. Forsythe J. A. Klupar M. M. O'Mara J. W. Ryan L. W. Salzer R. D. Scott R. A. Yount P. M. Zakriski B. M. G. Zwicker L. B. Crider Others B. A. DiLiddo-E. G. Schwaegerle K. J. Kaminski F. E. Krause R. M. Kreager-A. L. Schultz C. H. Lufter J. L. Nelson-E. W. Harrington R. W. Strassburg R. L. Toole 6 10 0 QU HU BOULEVARO B.P. Goodrich Che m lea I Co sip toy I OIVISIOR OF INI I. F. (DOOIICH COMPANY CLEVELANO. OHIO 44131 P H 0 N E 2 1 8 - 3 2 4 - 0 2 0 0 INTERNATIONAL DEPARTMENT February 6, 1975 VIA AIR MAIL VINYL CHLORIDE TRANSMITTAL The court has ruled on the new OSHA Standard and upheld it in its entirety. The new effective date is April 1, 1975. Any further court action has not been decided as of this time. B.F. Goodrich has continued all preparations for implementing the new OSHA Standard during the time the court has had the case under study. Specific items in this transmittal are as follows: 1. Several newspaper and magazine articles relative to VCM exposure. 2. Results of RVCM values found in competitors' PVC resin. 3. A summary of VC1 ambient vapor concentrations being monitored in the B.F. Goodrich plants. 1+. A list of 50 raw materials used in manufacturing that could possibly come under review in the future. This data was compiled by J.A. Klupar to be used in the event any one of them might be Ques tioned. I 5- A summary of RVCM values determined in our various resin types. These will be reduced with the incorporation of new equipment being installed. 6. An article entitled "A Guide for Designing and Specifying Safe High Pressure Air Purification Systems". This is very important as the new OSHA Standard will require air line respirators which will require a good, clean source of air supply. 7. A sheet of VCM properties. * a j , f CABLE AODRESS GOOOCHEM I0PC. --- CODE ABC SIXTH EDITION TELEX NO. 93-0427 / 2 8. A good article which gives a detailed approach to be taken by PVC industry in complying with new OSHA VCM Standard. Yours very truly. JES/kan *1 '/M***h John E. Stroope \ ZOQM trH A 12 TH lOUfsyiue TIMCS. MONPAY, KMUARY 3. 1773 Federal court says new vinyl standards can be put into effect By DEXXIS POLITE LfrfnCSt TMat IK WIKW The VS. 2nd Circuit Court of Appeals la New York City say* the federal gov ernment's proposed tvgalaUos* for the vinyl-chloride jndujtry can be put Into effect April 1. It rejected a chillcnge by the Sodety for the Plastics Industry, Inc- that the rules were too stringent, and were tech nologically infeasible. "It Is our conrinsion that the chal lenged aspects of tec vinyl-chloride stan dards axe supported by substantial evi dence in the record sad the petitions tor review mast be denied.'* the court said. The rules were originally to become effective fan. 1. The plastics society went to wurt for the review, however, and the . standards were temporarily stayed, A spokesman lor the soriely said today ti. m w.. mj t|. f iw U. ta atMtVCJ., Ild3 UUV- UTTQ determined. He said the ruling was being given a legal review and the resulting course of action has not been set, A spokesman for tee federal Occupa tional Safety and Health Administration (OSHA), which issued the rule* and which will monitor the industry, said it has not yet received a copy of the coart ruling. About fit vinyl-chloride worker deaths have been attributed to the cancer. Six ot the workers were from the Louisville B. F. Goodrich Co. plant on Bells Lone. A Goodrich spokesman said today It has not seen the court ruling. But he said its production of polyvinyl chloride (pvc). a product of vinyl chloride, does not depend on the ruling. "We intend to maintain production under the new standard it all oa? PVC plants." he said. He said it would use resoirators for workers. The spokesman also said the firm has made numerous improvement* In its pro cesses and facilities since the danger of vinyl chloride became known last year, lie said'the Crus also it testing sew procedures for future use. Although the court said the nit* could become effective in 60 days, additional legal challenges by the industry could I uiua iunhtr. ) Court terms rules dear The court raid H fotmd that the OSHA rules "art clear, definite and certain, and that they are entire!}- feasible since the , goal . . . can be attained through the combination of technological means and respirators." The rules call for workers in the vinylchloride industry to be exposed to no more than one part vinyl chloride per million part* of air by Jan. 1.3 PTC. Exposure to levels higher than one part per million means the workers will nave to wear respirators, which arc op tional this year, under the proposed rules. Currently, the standard for vinyl chlo ride inside plants allow exposure up to 50 parts per million parts of air. Vinyl chloride, a chemical used in the production of many plastics. has been linked to angiosarcoma, a rare cancer r .that often affects tee liver. Xerox copies tot A. Vittone i. D. Score J. L. Kelson E. B. Osborne K. Greene P. J. Weaver R. B Downey B. M. C. Zvicker C. Pov V. J. Wilcox E. V. Herrington H. Valtemate V saoeH E^ t r i i i i Ir i i | | ir TO: MR. J.V. ELDER 'i V "V / RE: VCM LIMITS IN UK ALH JWE-7 PLS ADVISE DR. ZWICKER I HAVE TALKED WITH ROBIN RAE IN B.P. INTERNATIONAL AT DEVONSHIRE HOUSE. THE TRIPARTIT COMMITTEE DID MEET AND AGREED TO THE TEMPORARY STANDARD OF 25 PPM TWA WITH 15 MINUTE EXCURSIONS TO 50 PPM. THE COURT OF PRACTICE WILL ESTABLISH AS OFFICIAL IN MID-FEBRUARY. THE OFFICIAL RULING IS AT THE PRINTERS NOW AND RAE WILL SEE THAT I GET A COPY WHEN IT ISSUES. I WILL FORWARD COPY TO YOU UPON RECEIPT. FURTHER, THE TRIPARTITE COMMITTEE WILL RECONSIDER THIS STANDARD IN APRIL TO SEE IF FURTHER MODIFICATION IS JUSTIFIED. CONJECTURE IN UK INDUSTRY NOW IS THAT EVENTUALLY THE STANDARD WILL PE 10 PPM TWA PUT NO ONE IS PREDICTING WHEN EXACTLY. SOME SAY JANUARY 1, 1976 BUT IT IS ONLY CONJECTURE. REGARDS JJH -r&Z-'-Ui ft.;--.- ~ adeariojv : A, -.,. v .-.' the B'-- ,> - - X+A cn^a'.C;.tfc rH. * .A Xtrox copies to: A.Vlccoac ft. D. Scott J. L. Hlson ft. B. Osborn* K. Creca* P. J. Weaver I. B. Downey B. M. G. Zwlclcer G. Pov V. J. Wilcox E. V. Harrington H. tfalteoate ft. Flynn Traces outside Goodrich Bells Lane plant By UEKM5 rOLFTE iMinRlt Tn tt* wrifcr . Aftscy (SPA) also is sampltoe the sir to A npofcwrasn arid a leal review ts un gather data for a clcaa-air law on vinyl der way, ar.d to view of lie liiicsiiea ta* The state Department of Labor has chloride. vetoing the proposed stwsdsrd there bee sampling the sir outride the B. F. Bloch add the stale's survey is not do* would be bo comment -at this pcist,"* Goodrirh Co. pUr.l oa Belij Laoe and has found trsre-j of vinyl chloride to th air and si sewer outlets. Dr. 7. Bradford Block, medical coas-t!!- p&ealing the EPA's effort. There I* no standard for vinyl chloride in the catside sir. U-5. and state laws ?w allow workers inside plain* to be The firm has given $553.03) to the T?clversity of Loairrille Scowi of Medicine to study the cancer problem. : to the department. said readings of 3 exposed to sp to 50 parts <a visit chlo UL said in a ptesres* s?sSB?Rt 05 the "14 parts of viny l chloride per million ride per million parts of air for an eight- program that it has examined 790 of the parts of sir occsrionsiH" hart been fwind hoe1 period on the Average. LiK) Goodrich workers. It did not release Ja the air near toe plant. Most readings lavs been sere, he said. A regulation lowering toe txpenn level to one pert per million was to so tr.fr* J V Vtfrt wm luHM hr ft nay findings. ; Since the original Goodrich setroascev RtoatPSS st sewer outlets owsjoe me pSad bare ranged as high as 2) parts per Billion, Blocs said.. Block said the air fsmpltox. dose with lrder*l coart Reading baarnip rule. Block said the state has here? taken roesreremeste outside the plant when BICMS M A4W, M vases* v* xnfiosazeoms have beets uncovered among part or present rtoylekloridt workers. Goodrich'? couponiioD,4j to dderratee if readings have shown excessive level? in According to a. Goodrich spokesman, any other workers to Bufcbntowa SR side, The astride readies*, then, be said. there are reports of four eases discovered feeing exposed to the chctr.ic. L. reBeet the normal Inc) daring normal recently to Canada!" Vinyl chloride, a main ioeredtont for operations. Four cases were uncovered there Ust xdosI pliriics. is used fcy Goodrich in pro ducts a plastic resin. Meanwhile, Goodrich ho declined to ccuamwst about any facets, of the vtryi- year, one of than x worker who was em ployed at a plant owned by Goodrich. Vinyl chloride has also been linked to toe rare cancer angiosarcoma; six former Goodrich 'workers have died of angjowr* emu of the liver, and three ethers hare toe disease. chloride matter. It was last over a year ago that Good rich first announced the potential danger of loop-term exposure to vinyl chloride. little is known about tire most recent cases, the Goodrich spoiesrr.M said. be cause o! a Quebec law prohibiting dis closure by doctors of information con Block said the readings, which have The compsaj-'s no-comment porture cerning their patients. .feeeo taken for shout s month, will con* was disclosed in response to a reporter's A spokesman for the National T-utilete tioae in an effort to determine if s wind iatjuiry shout the status ef wetter* who for OfCi'palioaal Safety and Health said patters cornea the chemical to certain have fccce furloughed from the plant be it hid ra ir-.fcrn'AUoa on any new c-kv i areas. came of liver problems and about other It has requested raforroadua if there are j Tt B. 8. Eamswitafal Protection actions taken by the company. , - -___________ - t teases, he cold. Ni s CA) O O 4a- February 3, 1975 RESPONSE TO QUESTIONS OH YCn DECISION Tetox copla to; A. Vlttooe H. D. ScoCC B* B. Osborne H* Greene P*J, Weaver B. B. Dovney B. M. G. Zvlcker C. Pov W. J. Wilcox fA***^^ B* W. Harrington H. Waltemace -B.f.Kenney-A T ^slfiaLd-C.&.Flymi ck k'e have not seen the court's decision, and, therefore, have not had an opportunity to study the basis on which it was ~*ide. However, our plans for continued PVC production have not been contingent on a favorable ruling by the court an the petitions for review of the OHSA standard. We Intend to maintain production under the new standard at all our PVC plants with the proper use of respiratory equipment. The Company already has made n-jenerous improvements in equipment, processes and work practices, including the use of respirators as .. required. In addition, we are continuing our intensive research and develoiment programs on new and improved technology. These programs have already provided promising results which are now undergoing further evaluation and in-piant testing for possible future use. QUESTION Does this mean that your plants can now meet the 1 and 5 ppm levels set in the standard? ANSWER Hot without the use of respirators. The technology does net new exist to recch these low levels. This was confirmed In a study df technological feasibility conducted for OSKA by an independent engineering consultant firn, and our extensive work corroborates the findings of that study. QUESTION What are your exposure levels now? ANSWER Our plants are operating with average levels of 6 ppm. The frequency of excursions has been reduced to less than 2 percent of all readings at our PVC plants. (If asked) an excursion is defined as 50 ppm under the temporary standard, and will be 25 ppn under the 1975 provisions of the new standard. In cc^pllance with the standard, we have in place alarm systems which signal any levels above 25 ppm, and are installing alarms at lower levels. For the first year, wearing of respirators is optional with employes up to 25 ppm. Kc have most of the respiratory equipment required, ar.-j we have ordered additional equipment for delivery within the next 60 days. 03 O e? 1:- m-?k* 48 ECN technology \ European^Chemical News. December 13. 197 PVC processing equipment EEC sets sulphur levels for gas-oil meets new VCM regulations the EEC Economic and Social Com mittee has recently adopted in a plcnau ici Pigsties Division and T. K. Fielder Ltd. of the UK have jointly developed an aspirator system for die removal of vinyl chloride monomer from work ing areas in PVC dry blending opera tions, which is commercially available. Known as the Exorsta system, the new equipment is expected to help the plastics processing industry in meeting the OSHA I ppm standard on vinyl chloride exposure. It also substantially reduces the VCM content of processed PVC resin, from around 1 000 ppm in the uncompounded condition to be- 'tween 5-10 ppm after mixing and com pounding. In the process, VCM is removed dur ing the dry blending operation through a sophisticated system of venting and air stripping during the PVC blending and cooling cycles. Nearly all the VCM which is genera ted in the headspace of mixer and S6 000, depending on the size and com plexity of the compounding operation. In order to exploit the US and Cana dian markets, the equipment is being marketed in North America by the Wer ner and Pfleiderer Corporation from its Waldwick, New Jersey, USA Labo ratories. VCM Level Questioned Speaking during the presentation of the 1974 third quarter financial results, Mr. C. A. Cash, president and chief executive officer of the Diamond-Sham rock Corporation commented on the new OSHA standards for VCM. He said that Diamond-Shamrock will comply with the new US Labour De partment standard for VCM exposure of Ippm in the company's PVC opera tions. However, he seriously questioned the wisdom of such a rigid standard, which "creates a real and immediate, session a proposed directive concern ing the harmonization of legislation m EEC member states on the sulphur con tent of certain liquid fuels. Aim of the proposed directive is to eliminate the divergencies which exist between the legislative, regulatory, and administrative provisions of the L:I( member states concerning the maximum sulphur content of liquid fuels. Two types of gas-oil (A and Hi arc defined in the proposed directive, tor which different sulphur content targeu have been set. These are 0-5 per cen; as from October 1, 1975, and 0 3 per cent as from October 1, 1980. for the A category, and 0-8 per cent and O' per cent respectively for category li. Gas-oil for which a greater degree ot tolerance is provided is intended for use in areas where the level of atmov pheric pollution by SO. is sufficiently low. cooler vessels is exhausted away from threat to Employee's safety because of the working area throughout the cycle. the awkward and limiting equipment Monsanto UK plant The operation of the system is integra required to be worn on the job." ted into the automatic filling, mixing and discharge cycles in such a way to minimize dust carry-over and loss of production output The system is described as readily adaptable to all existing commercial dry-blending equipment and the price of the new units range from $3 000 to Additionally, Cash stated that Dia mond-Shamrock supports the US Society of Plastics Industry in its ef forts to have an impartial c&urt re view all of the evidence presented to the US Labour Department on what Diamond-Shamrock considers to be an "overly restrictive standard." receives safety award THE Ruabon plant of Monsanto I me ted has been presented with the Gold Safety Performance Citation of the Hn tish Safety Council after an evaluation of the site's safety organisation that probed 14 main areas of effort and per formance. Monsanto Ruabon, situated m ICI, Mitsubishi link on desalination Clwyd, produces industrial and specia lity chemicals and has achieved a very Mitsubishi Chemical Industries and ICI Australia have agreed to jointly de velop a new desalination process to the ment at the end of the year. ICI Australia and the Australian governmental research organization, the low accident rate in relation to the in dustrial average as a result of its con ccrtcd efforts to improve safety commercial stage using technology in Commonwealth Scientific and Indus dependently developed by both com trial Research Organization (CSIRO), EEC publishes mercury panies. The new process is intended to be used for the development of water have already jointly developed a water desalination process, ECN, November and cadmium data resources and for the recycling of water. A joint production and sales com pany is expected to be set up in Japan sometime after the middle of next year, according to Japanese reports, and it is hoped to start production of equip 15, 1974. In the joint ICI-Mitsubishi project, the ICI-CSIRO process will be com bined with Mitsubishi's ion-exchan|e resin desalination technology to evolve a low-cost water purification system. the EEC Commission has just pub lished a 700-page book containing till the papers presented at the symposium on "Problems raised by the contamina tion of man and his environment b\ mercury and cadmium," held in l.uxem bourg from July 3 to 5. earlier this year. Phillips develops aromatics extraction This publication contains detailed m formation concerning the presence of development work on aromatics ex jected because of their limited solubility. mercury and cadmium in ihc environ traction by the Phillips Petroleum Com Using this new approach, Phillips has meat, the analysis techniques used m pany has shown that extra active dis demonstrated the recovery of chemical making measurements, the ecological tillation in conventional distillation grade benzene, toluene, and xylene consequences of mercury and cadmium columns can be operated without prob from reformate and pyrolysis gasoline pollution, the significance of these two lems when two liquid phases are on aromatic concentrates. An economic pollutants for man, and their effects mi the distillation trays, according to a comparison with existing commercial public health. Phillips Petroleum statement The discovery permits highly selec tive solvents to be used for aromatics extraction which were previously re processes has shown a 15 per cent capi tal cost saving and a reduction of 8 per cent in energy requirements, the company stated to ECN. The volume, in English, is on sale at the Publications Office of the Hum pean Communities (PO Box 1003. 1 ti\ embourg). QQfr9 >Z s newsdesk European Chemical News, January 10, 1075 Norsk Hydro may soon Monsanto confident of strong 1975 first half restart PVC production Monsanto's president, John Hanley, is predicting a `reasonably strong perform Norsk hydro may be able to restart PVC production in the very near future following a relatively favourable report by the special commission investigating health risks at its PVC plants. The commission, consisting of three doctors nominated by the Government health authorities, trade unions, and the Norwegian employers' federation, stated that Hydro will be medically justified in restarting production provided it invested in more secure production methods. Specific recommendations include the installation of closed production sys tems, new polymerization vessels to re place some of the older plant on site, and the introduction of more efficient ventilation equipment. Norsk Hydro replies that alterations made before and during the shutdown ought to meet the safety requirements listed in the report, l! expects to restart production with the newer one-third of its autoclaves. Long term, the commission recommended en tirely new polymerization plants, a feature of Hydro's plans to double capacity in any case but one which will take at least 2-3 years to achieve. employed on what was then seen as a ance' for his company in the first half hazardous process. ' of 1975. A number of key Monsanto The restarting of PVC production in product areas, such as herbicides, phos the near future will come at an oppor phate products and Fisher Controls, he tune moment for Norsk Hydro. Its pointed out, arc not directly related to PVC stocks are understood to be very the industrial economy. nearly depleted after a lengthy period The group's range of products has of supplying customers without its own already meant that the slow-down in production. It admits the situation demand--shortly after mid-year in would be much worse were it not for Europe and at the end of the third the large volumes of material now quarter in the USA--did not translate available on the open market. into as significant decline in third quarter earnings as would have been Meanwhile in the UK, a former BP the case in earlier years. The continuing aetnicals employee has died of softness in automotive production, angiosarcoma of the liver, the rare form housing starts and consumer durable of cancer linked with exposure to vinyl expenditure in the final quarter had, chloride. His death, the first in the UK however, begun to affect an increasing recorded as due to angiosarcoma, brings number of products such as plastics, the number of confirmed VCM-related rubber chemicals and polybutyral sheet fatalities to 25 worldwide, although a Mr. Hanley agreed that a recovery former 1CI worker's death is also sus pected of being caused by the disease. Will begin at the mid-year, followed by a period of moderate growth. The BP case, however, involves the Monsantols capital expenditure in shortest ever exposure to VCM--the 1975 will be S500-000 million (m.) man was employed for only three years eight months in cleaning polymerization against $300m. in 1974. Overall, 1974 profits are expected to vessels. Previous cases related to ex be in the region of $323m.-$32Sm. Although production could be under posures of eleven years or more. way again within a few days, the com Government-appointed pathologists Montedison hints at pany now has to convince its workers are to examine samples of the man's that the medical risks are negligible. Meetings between the company and its employees are expected to take up the next five days or possibly up to a week. But first reactions from the workers are reported to be unfavourable and the restarting of production could prove expensive in terms of wage rises. Apart from the genuine concern on health, one of the chief reasons for the shutdown in the first place was the demand for substantially increased wages and generous time off for people liver to see if there could be any other contributory factors in view of the comparatively brief exposure period. BP Chemicals meanwhile is increasing spending on new equipment from lm. to 2m. at the Barry polymerization plants where the man was employed. The other major UK producer, ICI, is also considering the construction of new PVC facilities, partly in order to replace its ageing Hillhouse plant which is rumoured to be incapable of meeting even the 50ppm interim standard. renewed dividend signor const, managing director of Montedison, has hinted in the Italian weekly Panorama that the company should be able to pay a dividend this year--its first since 1969. Chemicals and fibres, however, were not the main causes for Montedison's improvement: Sig. Corsi pointed to large-scale borrowing of low interest rate money in 1971/2 and speculation in foreign exchange and commodity markets as the principal factors. The Montedison subsidiary, Gemina, Italian group in Occidental share deal had bought silver at $3-50/ounce, he / said, and sold it at $4.80/ounce, but unconfirmed reports from New York that it had bought Occidental shares on this speculation was not as successful maintain that Ghaith Pharaon, the Saudi the market." Such purchases would as the foreign exchange operations. The business man who acquired 1 million merely be of a trading nature and not cost of money to Montedison at present shares in Occidental Petroleum, was strategic, he indicated. Fingest is a is about 10-41 per cent and this com acting for an Italo-Saudi group who prominent operator on the world's pares with about 7-07 per cent last year. now own 4m. Occidental shares--7-5-8 money, commodity, and stock markets. per cent of the equity and the largest single shareholding. The Italian partner owning 3m. shares was strongly rumoured to be Capitalfm Investment group, owned equally by Under Securities and Exchange Com mission (SEC) regulations, the holding involved in the alleged Italo-Saudi deal would have to be notified. Quoted by the Wall Street Journal, Pharaon said German pharmaceuticals >0 continue steady progress r Germany's pharmaceutical industry con- V ENI, Banca Nazionale del Lavoro, he had bought 700-800 000 Oxy shares solidated its leading position last year in Montedison, and the two Fiat-Agnelli on behalf of himself and a European spite of increasing difficulties. (jQ holding companies. 1FI and SAL But group last April. According to the Bundcsverband der Q the company lias now denied its involve Dr Annand Hammer's statement to Pharmazeutisclien Industrie exports in (-*> ment. However, a Montedison spokesman s.iid that Fing-est lmernazionale, Monte dison's leading offshore investment the SEC that "a prominent Arab" had bought 1m. Oxy shares and its apparent conflict with Pharaon's statement will be one of the aspects of the SEC inquiry the first half of 1974 totalled DM1 800 million (m), a 23 per cent increase on 1973. Germany is tiic world's largest ex porter of pharmaceuticals, selling 36 per w group, "could not exclude the possibility into Oxy share dealings now under way. cent of production overseas. v . ~ A 14 - ,, , . . .. ; : - >/ - *. ' ' ' .` ,/ THE COtRJEH-JOUS,>U, TVE50,\V, JWtABY 21. XV73 UL gets 6300,000 f 1 to study liver cancer * Unhrraiy of Louisville trustees : wttwd yesterday the receipt of a 2309,000 /mint from tbs B. F. Goodrich Os. to be used in tuordi vnt# saiposar- *, a me liver cmcer ut bis fiabed to vinyl chloride. \ . . Tty liver cancer has killed sit workers tbe Goodrich plant on Ek-Ils Lane. 1 Tore* other local Goodrich wasters also Jarre anfjwareoma. Vioyl tbloride, a pas beroefved coder - Kwaire. is processed to prwhjte poh-- . vaod chloride, a plastic used - in vadt prodneu as pjJcncgrapSj records and * ' vipyl tops. ,,. *V XA erox copies to: ft* D. Scott J. L. Nelson ft* B. Osborne ft. Greene P* J. Veaver ft* B. Dovney B. M. G* Zvlcker G* Pov V. J* Wilcox C. W* Harrington H* Waltemate ld-C.R.Flynn yjv 52 GO O --1*4 o What the law means to you Jerome H. Heckman* Legal Exchange Readers' inquiries are solicited for this department, which is aforum for the discussion oflegal questions ofbroad interest to the plastics industry. Inquiries will be used as the basis for general comment. The comments are in no war meant to serve as a substitute for expert legal advice. Names will be withheld on request. We have been swamped with questions regarding appli cation of specific provisions in the OSHA Vinyl Chloride Standard adopted on October 4. 1974. The questions be low are among those asked most frequently. At the time of this writing, intensive appellate procedures were under way to attempt to have the entire Standard declared un lawful and invalid. Likewise, proceedings looking towards the staying of the effective date of the Standard were in process. Thus, while the responses to the questions are based on the assumption that the Standard will become ef fective January 1. 1975, it is our hope that it will not go into effect as written, that a Stay may have been granted by the time this column appears, and that the entire matter will be remanded to the Department of Labor for com plete reconsideration. An interpretation is n^eucu me euunuuiu /v/ t,x- posure to Vinyl Chioride (29 C.t.K. 19I0.9jq) promulgated by the Occupational Safety and Health Administration (OSHA) on October 4. The question relates to the needfor warning signs required by subparagraph (I) ofthe Standard. If a processor-fabricator facility is below the "permissible limit" as defined, is the facility still deemed to be a regulated area? Is it required to post the area with the sign "Cancer Suspect Agent Area--A uthorized Personnel Only"? No. "Regulated areas" are discussed in subparagraph (e) of the Standard. This subparagraph states that (1) a regulated area shall be established where: (i) vinyl chlo ride or polyvinyl chloride is manufactured, reacted, re packaged, stored, handled or used: and (ii) vinyl chloride concentrations are in excess of the permissible exposure limit (1 p.p.m.. 8 hour TWA, and 5 p.p.m. maximum for any 15-min. period). If the facility is below the permissible exposure limit, then no regulated area need be set up and consequently the signs are not required. (If monitoring shows less than 0.05 p.p.m. employee exposure to vcm, vir tually no further action is required under the Standard; this "action level" concept is not to be confused with the "permissible exposure limit" concept.) Although the question is limited to "processor-fabrica tors," the answer is equally applicable to all operations falling within the scope of this Standard. Paragraph (!) (3) requires that "containers of... other waste contaminated with vinyl chloride shall be legibly la- "Keller and Heckman. 1150 17th St. N.W.. Washington. DC. 20036. Mr. Heckman is general counsel of spi. the International Non-Woven and Dis posables Assn., and other trade groups and private companies. beled: Contaminated with Vinyl Chloride--Cancer Suspect Agent. "Are such labels required on PVC scrap within a fa cility in inventory for further processing? The purpose of the labels required by this subparagraph would be to warn employees that waste material is or may be contaminated with vinyl chloride so that a hazard might be posed to those who handle it without taking proper precautions. The provision in the Standard is aimed primarily at dealing with waste from polymer ization reactors where the possibility of entrapment of rel atively large quantities of vinyl chloride exists, or other waste generated in vc or pvc producing facilities, where contamination with vinyl chloride can be expected to oc cur. On the other hand, scrap produced in processors' or fabricators' plants by trimming of processed material poses little or no problem in this regard since such scrap can properly be considered to be a fabricated material which is outside the scope of the Standard. In other words, the type of scrap generated in the plant of a processor-fab ricator that has already been through the mass melting stage need not carry the label while it is in inventory awaiting further processing. To the contrary, compounded material which has not been through a fabrication process (for example, excess compound remaining after a run has been completed), when stored in "in-plant" containers rwniTM liHoiinn Hu* ciu-K labeling should be in ac- ccriur.cu v.-itl: subparagraph (1) (4) which applies to con tainers of polyvinyl chloride. Labeling should read: "Polyvinyl Chloride Contains Vinyl Chloride Vinyl Chloride is a Cancer-Suspect Agent" It should also be noted that we have confirmed this in terpretation of the requirements of the Standard infor mally with the appropriate OSHA officials. Shipments ofpolyvinyl chloride resin receivedfrom a manu facturer will no doubt bear the required labeling, If bulk shipments are received, are labels required on any polyvinyl chloride container within afacility? The intent of the Standard is to warn employees of the possible hazard that exists in handling polyvinyl chloride which has not previously been subjected to mass melting and which may be expected to release vinyl chloride when it is mass melted. Consequently, if bulk shipments of poly vinyl chloride resins are received, and if the PVC is placed in containers within a facility which employees are in tended to handle, those containers should carry the label ing required by subparagraph (1) (4) of the Standard. Bulk shipments contained in silos and transported within a plant by pneumatic tubes so that there is no em ployee contact with the material do not pose the same em ployee exposure as might be posed by drums or bags of the same polyvinyl chloride that would have to be opened and emptied by hand. It is in these latter cases that the contain ers require hazard labeling. Consequently, if the bulk ship ments are stored within a facility in containers that require opening and emptying by employees who might thereby be exposed to residual vc vapor, it is only these containers that will require the cautionary labeling.--END TfQ StQ frg 146 Modern Plastics, January 1975 VC1 Ambient Vapor Concentrations -/ e * DISTRIBUTION W* \ Dave Brooks ' A. W. Clements; C. B. Cooper'/:- L. B. Crider A. M. Fairlie s'>y R. J. Fawcett ' ' C. R. Flynn E. W. Harrington M. N. Johnson E. B. Katzenmeyer, Jr. R. M. Kreager P. H. Lawrence G. H. Metzger J. L. Nelson G. Pow R. N. Rylands G. D. Schaaf R. D. Scott R. W. Strassburg A. Vittone H. Waltemate A. R. Webber W. J. Wilcox C. L. Woods B. M. G. Zwicker J. a. Klupar R. A. Krueger R. L. Toole r '* ' !" ! WEEKLY SUMMARY VCl Ambient Vapor Concentrations DATE: 12/20/74 through 1/17/75 AVERAGE Z READINGS > 10 PPM Prev. 12/20 12/27 1/3 1/10 Prev. 12/20 12/27 1/3 1/10 Month 12/27 1/3 1/10 1/17 Month 12/27 1/3 1/10 1/17 AVON LAKE GEN. CHEM. 451-1 -2 -3 Avg. 6.0 9.7 7.3 7.7 461-1 -2 -3 Avg. 10.4 8.0 13.1 10.5 464-1 -2 -3 Avg. 463-1 -2 Avg. 5.0 3.2 7.1 5.1 1.0 2.1 1.6 PLANT AVG. 6.2 11 1 1 w a ca w aS3 < M< cJ < >< ` H 2O H .O 5.3 7.3 7.0 6.5 0.7 2.0 6.0 2.9 $ < 4.0 oa 2.0 1 1 12.0 J 1 6.0 1-- ___ wa<ec -- Hi -- < <> ----~ H 2C -- < a-- i-- 1-- .017 .129 .073 .033 .131 .082 -- -- 3.9 "---- 8.7 i 1 17.7 1 a a ca <MhJ c > < H 2O cu 24.0 XX 16.8 < Hi >< < H 0.7 4.7 15.3 o 6.9 5 < Hi < <> H/*> 2 <' a < 3.3 <Qs 2.7 < <c i 1 45.7 t i 1 17.2 i 0.0 0.0 \ u U 1 -'.w , 0.0 0.0 10.2 HENRY LONG BEACH Pzn-1 -2 -3 PLANT AVG. Pzn-1 -2 Roof PLANT AVG. 4.8 3.0 3.0 5.5 3.0 3.0 5.5 4.0 4.0 5.3 3.3 3.3 11 4.3 1 4.2 4.1 XH XC/3 H 4.2 5 cu I1 ii i oHB X X C/3 H a n. i i i 5.0 6.0 5.0 4.0 4.0 5.0 -- -- 4.7 5.0 -- 0.9 3.4 0.9 3.5 0.8 3.3 -- ----- 0.9 3.4 4.3 4.7 5.9 12.1 3.7 6.2. 6.3 6.9 5.8 4.7 5.7 8.7 4.6 5.2 6.0 9.2 ii ii o 1 0.3 3.0 a HX XC/3 Hx C/3 1.0 2.8 0.0 4.2 HH 5 0a. aa. 0.4 3.3 i i i ! n o g vsvz LOUISVILLE PEDRICXTOWN WEEKLY SUMMARY VC1 Ambient Vapor Concentrations Page 2 AVERAGE Z READINGS > 10 PPI Prev. 12/20 12/27 1/3 1/10 Prev. 12/20 12/27 1/3 1/10 Month 12/27 1/3 1/10 1/17 Month 12/27 1/3 1/10 1/17 1-1 -2 -3 Avg. 3.8 3.0 2.0 3.3 4.0 1.0 4.5 5.0 5.0 3.9 4.0 2.7 5.0 2.0 4.0 1.0 | 5.0 3.0 ___ 4.7 2.0 -- 7.5 1.7 6.7 3.5 8.3 11.9 7.5 5.7 10.5 8.3 11.4 10.1 3.3 0.9 4.5 2.9 15-1 -2 -3 Avg. 111-1 -2 -3 Avg. 4.0 7.0 7.0 4.3 6.0 4.0 4.5 5.0 6.0 4.3 6.0 5.7 3.5 2.0 2.0 3.5 4.0 2.0 5.0 4.0 3.0 4.0 3.3 2.3 4.0 2.0 2.0 2.0 ^ -- 3.0 2.0 ___ 3.0 2.0 -- 4.0 3.0 3.0 4.0 _ 5.0 5.0 _ _ ,, 4.0 4.0 -- 11.7 11.3 12.8 11.9 15.4 4.5 9,1 9.7 3.3 0.7 8.0 1.0 5.2 4.9 5.5 2.2 3.6 1.5 3.6 2.9 4.2 3.6 8.5 5.4 l.S 1.5 1.2 : !.5 | 3.0 ! 4.E ; 7.0 ( 4.9 115-2 12.5 17.0 24.0 15.0 9.0 57.5 50.5 59.3 21.4 Avg. i*. J 17.0 24.0 15.0 9.0 -- 57.5 50.5 59.3 91 / ! I 121-1 -2 -3 Avg. 3.0 8.0 1.0 2.8 3.0 2.0 3.3 2.0 1.0 3.0 4.3 1.3 2.0 3.0 20.0 1.8 4.2 3.6 i 3.0 2.0 8.8 4.2 8.0 3 .6 2.0 2.0 5.4 0.0 5.1 2.7 2.3 2.3 -- 11.4 2.0 5.8 3.5 PLANT AVG. 5.5 6.9 7.2 5.8 3.9 -- 18.8 14.0 16.7 6.8 512-1 -2 Avg. 513-2 -3 Avg. PLANT AVG. 5.0 4.4 4.7 3.4 2.7 5.2 6.4 5.3 5.0 8.5 2.9 -- 10.5 5.7 4.9 4.9 6.0 2.8 ------ 7.9 ii z oa 3.1 15.8 9.5 3.8 3.9 3.9 2.5 4.0 3.9 4.2 2.5 -- 9.9 3.9 3.5 5.1 6.0 -- 6.2 4.0 3.7 4.7 4.3 7.7 7.0 UC-44 7.4 3 7.3 2.1 5.8 13.6 6.6 7.9 O o 6.0 4.5 4.3 5.4 3.6 7.7 t 1 1 8.1 5.9 els a> 1 cH wco cc CD L!_ CD CALVERT CITY C o n tro l Room Chromatograph Houses C austic Scrubber Area Juench Areas /CM Column A re a s R e frig e ra tio n Machine Tank Farm Areas .oading Rack Areas : c : CLWoods GEEvens JRRender J J S c h o n a e rts R A S p u rlo c k GDSchaaf HW altemate CM bJ V<*> -.-' c.: O LlJ V0 eg CM cn CM f-4 cs NO CN *--* -4 p- CN r CM P re v . M o n th W EEKLY SUMMARY Ambient O rganic /a p o r C o n ce n tra tio n s *Z 4 & 4 g 0 i4 AVERAGE 12/301/5 1/6- 1/12 I i P re v . Month % READING > 1 0 PPM 12/301/5 1 /6 - 1/12 . .2.9_____ j 1 -1 o \ ir IT C\ o o o c O C\ r er CN o c ** c n oc oc C" c c :*wr mtwpM *S*J FIRST QUESTIONS FOR THE PURCHASER 1. WHAT SHOULD I BUY? The purchaser must determine first whether he wishes to buy an entire breath ing air process system or to buy one or more of its components. The illustration (above) provides a schematic.diagram of such a system, identify ing each of its four basic components: compressor, purification system, cascade system, and charging station. This specific system is an electricallypowered unit. It can be powered with either a gasoline or a diesel engine. It can be used cither as a stationary or a mobile unit. 2. WHERE SHOULD I LOCATE THE EQUIPMENT? After deciding what types of equipment to buy, the purchaser should decide where he is going to locate the equipment. This should be done before the specification for purchase is prepared, so that the con straints of space may be taken into con sideration. The place where the equipment is located within a fire station should be clean, dry, well ventilated, and cool. The compressor should be protected from ingesting un desirable odors and carbon monoxide from internal combustion engines, such as those which power the fire trucks. 3. WHO WILL INSTALL THE EQUIPMENT? The purchaser should then decide whether he is going to install the equipment or have it installed by the person he buys it from. If the installation is going to be performed by the dealer, determine his qualifications to perform the installation. The surest way to do this is to determine where he has made other installations, to visit the fire companies where these installations have been made, and to find out whether the people at those fire companies are satisfied w-ith the work that has been done. Once the purchaser has answered these three questions, he can then proceed to de ciding what SPECIFIC equipment to buy, SPECIFYING THE EQUIPMENT Available Electric Power I. THE COMPRESSOR When buying a compressor, the first thing to he considered is the electric power available into the building and into the area where the compressor will be located, how many volts in what phases and cycles arc available. If the compressor requires more power than is readily available, extra costs, delays in installation, and/or modifications of the compressor would occur. Such costs and delays have been known to run to as much as $5,000 and one and one-half years. Horsepower The second thing to consider is the horse power, which determines the cubic feet per minute of air the compressor can deliver. A 1 horsepower compressor will deliver 1 cubic foot per minute of air at 3000 PSIG. A 15 horsepower compressor will deliver 15 cubic feet per minute of air at 3000 PSIG. High pressure, air cooled compressors are available in 2.5. 3. 3.5. 4, 5, 6, 7. 7.5. S. 10, 15, and 20 horsepower and will deliver pressures ranging from 3000 to 5000 PSIG. Size The third thing to consider is the size of the machine you need. If yours is a paid department with a mask unit or mask service to fill bottles and repair the self-contained breathing ap paratus, this decision can be based on the anticipated air usage of the department, based on past experience and projections of future use. If yours is a volunteer department, the size of the machine should not be deter mined by the amount of air you are using but on the amount of time it takes to nil your cascade system. After a big fire, a lot of self-contained breathing apparatus must be filled from your cascade system. A typical 4 horsepower compressor will fill a large receiver that is empty in 1 hour. It will take 4 hours to fill 4 large, empty receivers. A 15 horsepower com pressor, delivering 15 cubic feet of air a minute, will fill the same four receivers in 1 hour, 15 minutes. Using the smaller compressor, a volunteer department mayhave to spend most of the night replenish ing its cascade system alter a late night fire. Whether yours is a paid or a volunteer department, it should be remembered that, if you have been buying your air or obtaining it from outside the department, you will find upon having your own air available that your use of air will double. This increase will come from the addi tional use of your self-contained breathing apparatus in training programs. CAUTION: It is not recommended that cascade bottles, or receivers, be depleted to zero PSIG. Normally, they should be depleted to no less than 300 or 400 PSIG. dcsicant, and particularly on the Hopcalitc, and to keep moist atmospheric air from saturating the Hopcalite, rendering it ineffective. Special Considerations In Preparing the Specification for the Purification System. There are several other things to keep in mind in preparing the specification for your purification system. They are: Have tne supplier spell out for you ap proximately how many cubic feet of air he expects the system to process between cartridge changes. Have him spell out the quality of air he intends to supply. In your specification, you should spell out the air quality standard you wish the system to meet. This may be the NFPA standard, the CGA standard, or the OSHA standard. Even if you do not fall under OSHA laws at the present time, it may be wise to use OSHA standards, which are increasingly influencing air-quality policies. It doesn't cost a great deal more to have the puri fication system designed to meet these standards. Refer to a specific vendor model number in your specification. If the supplier re sponds to your inquiry with that model number, you will be assured of getting the piece of equipment you want. How ever, if he offers an alternate model number, make sure that, as part of his response, he has included a statement as to how much air this alternate will proc ess between cartridge changes. Be sure he defines precisely what he is offering you if he suggests an alternate to your specification. Note on cartridge life: If you have a puri fication system rated at 3000 PSIG, the system should be operated at between 2800 and 3000 PSIG, and let the effluent or processed air flow into the cascade bottles. Do not let the pressure in the cascade bottles equalize to around 500 PSIG. Open the valves on the purifica tion system to equalize that pressure, turn the compressor on, and start pumping from that pressure to 3000 PSIG. You aren't going to fill the bottles as fast, but you arc going to substantially increase the life of the cartridges. III. THE CASCADE SYSTEM The Cascade Bottles PART NO. 119 120 DOT 3AA 2400 3GG0 NOMINAL DIMENSIONS INS. ID. 0.0. WALL 8si 9'%, .270 m 925 .375 IGTH. 55 51 PART NO. 119 120 00T 3AA 2400 3600 APPROX. WT. 137 185 MIN. CAP CU. FT. 300 360 CPR. PRESS 2400 3600 PROOF PRESS 4000 6000 The cascade bottle is also a pressure receiver. You can purchase high-pressure receivers or you can purchase highpressure bottles for a cascade system, as shown above. These bottles come in any size you may want. Most inquiries are for DOT 3AA2400 or DOT 3AA3600 bottles. The 3600 PSIG bottle costs approximately 25 percent more than the 2400 PSIG bottle, and is the more economical and frequently purchased bottle. The 3600 bottle holds 360 cubic feet of air at 3600 PSIG. The 2400 bottle holds 300 cubic feet of air at 2400 PSIG. With higher pressure self-contained breathing appa ratus coming into existence today, most systems are being designed at 3500 PSIG. They use the higher pressure bottle as the receiver. The bottles should be paint.d yellow, the CGA color indentification for "breathing air." You should specify the bottles by DOT number. It is best to purchase the bottle to Depart ment of Transportation specifications. Make sure you get a test report showing the serial number of each bottle you buy. There have been occasions when a fire department was sold used bottles without being informed that the bottles were not new ones. When receiving a bottle from a manu facturer, turn it upside down, clean the bottom surface, prime it, and paint it. Then repaint the whole bottle. Some times, the bottoms of the bottles haven't been painted; or the paint is gone by the time it is received by the fire department. Painting it upon receipt will help keep the bottle from rusting.; When receiving a bottle from a manu facturer. remove the valve, inspect the inside of the bottle for contaminants, and reinstall the valve. Then, draw a vacuum on the bottle and pressurize it with proc essed air. Cascade Racks Cascade bottles should he fastened se curely to a wall, by means of a rack, as illustrated above. If these bottles are allowed to sit loose, and should a bottle fall, breaking the valve, the bottle will act like a balloon that has just had the air released from it. It is not good practice to allow everyone in the fire department to operate the breathing air process system. Three cri teria may be used to select those who will operate the system: Demonstration of responsibility. Demonstration of an interest in the equipment. Availability for filling self-contained breathing apparatus bottles on a routine basis. The people selected should participate in the training program. The training program should consist of the following: General familarization with the equip ment and how it works. Familiarization with the hazards in volved in producing, handling, and stor ing high pressure air. Learning the step-by-step procedure. With regard this procedure, the specifi cation should contain a requirement that a written operating procedure be supplied with the equipment. Test reports on the cascade bottles should also be specified. After the equipment has been installed, a complete log should be kept on the com pressor running time and on service to the equipment. A NOTE ON OPERATING COSTS The system described should cost the fire department less than one-fifth of a cent per cubic foot of air, including costs of electricity, insurance, and amortization of the equipment over a ten-year period. This cost may be compared with the cost of purchasing air from an outside source in making a purchasing decision. It should also be remembered that when air is purchased from outside, the fire department is subject to the normal work ing day of the local air supplier. The presence in the department of a system removes this constraint. SUMMARY Three basic things should be remembered by fire department personnel in buying breathing air process systems. 1. When receiving and examining bids, look at each bid ax it pertains to every detail of the specification. If two bidders appear to meet the specification and one is considerably lower than the other in price, find out the reason. Make sure that it is understood who will install the system and what specific services will be per formed by the seller. Have these services included in the purchase contract. 2. Be sure that ai! the equipment is clean and oil-free. When a valve is opened, allowing air to flow quickly into the line, if that line is contaminated, a dieseling effect can take place due to the high heat build-up when the pressure >s released into the tubing. This can result in a dangerous explosion. 3. Put the responsibility on the supplier to give you what you want, but be sure your specification is clear enough for him to know exactly what you want. Properties 27 Chemical Names: Vinyl chloride, vinyl chloride monomer, chloroethylcnc: chlorocthcne Chemical Formula: CU.CHCI Molecular Weight: 62.5 Description: At ordinary temperatures and pres sures, vinyl chloride is a color less gas with a mild, sweet odor. But as supplied in tank cars and trucks under pressure, it is a liquid. Vinyl chloride is highly vol atile and its vapor is extremely flammable. Boiling Point, C F -13.8 +7.0 Freezing Point, C -153.7 F -245 Flash Point, open cup. C -78 F -108.4 Explosive Limits, volume % in air at 25C (77 F) 3.6 to 33 Autoignition Temperature, ' C 472 0 F 882 Critical Temperature, C 158.4 F 317 Critical Pressure, psia 775 Vapor Density, air= 1 2.15 Solubility, water in monomer at 25C (77 F), weight % 0.11 Solubility Vinyl chloride is relatively in soluble in water but soluble in most organic solvents. Reactivity Vinyl chloride polymerizes exother mically in the presence of light, air, oxygen or catalysts, ileal alone will not initiate polymerization. Vinyl chloride is thermally stable to quite high temperatures. Although perox ide formation due to air exposure is a slow reaction, certain peroxide products arc shock-sensitive. Vinyl chloride is noncorrosive to metals when dry at normal ambient temperatures, hut water at elevated temperatures accelerates corrosion. The double bond behaves as in other unsaturaled compounds. The chlorine atom is relatively inactive and is more stable than in satu rated or allylic compounds. 6 VAPOR PRESSURE LIQUID DENSITY *To convert to pound* per gallon, mntliplv grams per milliliter by 8.345. lazards ) ------- ---------- . ------------------------------------ * /-------------------------AU. I DID WAS rire and explosion Vinyl chloride vapor is extremely flammable. Its explosive limits are between 3.6 and 33% by volume in air. Sufficient ventilation and the elimination of ignition sources are mandatory in areas where vapor concentrations may reach a flammable level. 33 hen a tank car is unloaded, both the car tank and the unloading pump should be electrically ground ed An explosion hazard exists when prisons unloading a shipment draw samples or vent vapor to atmosphere. The major products of combustion include toxic and corrosive hydrogen chloride as well as carbon monoxide, and less than 10 ppm of phosgene. Only in the very near vicinity of a vinvl chloride monomer fire could detectable amounts of phosgene be present. The main sources of danger to personnel result from carbon monoxide and from the extensive formation of hydrogen chloride gas. However, the pungent odor of hydro gen chloride acts as a warning tu dear the area or to obtain the rssary breathing apparatus before ..eni|itmg any fire control measures. C arlron dioxide or dry chcmieal agents extinguish small fires ef fectively, hut no extinguisher is known for large fires. Streams of water cannot extinguish a liquid vinyl chloride fire because the mono mer does not mix with water and will float on top. 3Vater may be sprayed to cool equipment, however. If the source of the vinyl chloride monomer leak lias not been closed off, do not attempt to extinguish a large fire because hot metal can reignitc an unburned vapor cloud. No one without proper protective res piratory equipment should enter an area where there has been a fire until the area has been adequately ventilated. Chemical reactions Contamination of uninhibited vinyl chloride monomer may catalyze nnlymprizsuinn which is hiohlv exo thermic, or cause decomposition, which liberates toxic hydrogen chlo ride gas. The high purity of vinyl chloride must be maintained in shipment, transfer and storage. Exposure to oxygen, air or sun light can also catalyze polymerization. Peroxides may also form but not so readily as with many other monomers. Toxicity Uninhibited vinyl chloride 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. Most vinyl chloride monomer shipped today is unin hibited. 3Vorkmen should wear eye pro tection and protective clothing to prevent skin contact. If vinyl chlo ride gets on clothing or shoes, they should be removed immediately. If vinyl chloride contacts the skin, wash immediately with soap and water. If vinyl chloride contacts the eyes, the eyes should he washed immediately and thoroughly with water for at least 15 minutes. Cel medical attention. 3'inyl chloride vapo^ concentrations in work areas should not exceed 200 ppm as a time-weighted average atmospheric concentration for an 8-hour day to avoid adverse effects on workmen. Its odor is pleasant and the sense of smell cannot be relied upon as a warning. High vapor concentrations can cause lung irritation, dizziness and anesthesia. Chronic overexposure may injure the liver. In all cases of overexposure, immediately remove the affected individual to fresh air and obtain medical attention. More information More information on fire, ex plosion, reactivity and toxicity hazards, as well as emergency pro cedures, appears in Chemical Safety Data Sheet SD-56, "3'inyl Chloride," nuhlished in t07"> Hv thp Manu facturing Chemists Association, 1825 Connecticut Avenue. N.33'., 3Y'ashington, D.C. 20009. Living with vow How pvc Processors Can Cope It may take some effort. And expense. But you should be able to protect your workers, comply with the new OSHA regulation and stay in business. This comprehensive report is intended to help guide you through the provisions of the new rule and suggest approaches to meeting its requirements in your in dividual plant situation. By Matthew H. Naitove, Associate Editor the U.S. and Europe revealed a total of over two dozen cases of this disease among monomer and polymer produc tion and PVC fabrication workers.) Publication in the Federal Register on April 5 of an OSHA Emergency Temporary Standard limiting employee exposure in VCM and PVC production and processing plants to a 50 parts-per-million ceiling, one-tenth the prior limit. The standard also required regular workplace mon itoring of airborne VCM by no later than April 22. First public reports in June of two angiosarcoma deaths associated with PVC processing and another two such deaths of persons living a few miles from PVC proc essing operations in Connecticut. OSHA hearings in June and July which produced vol uminous testimony from representatives of industry, labor, medical science and others on possible health hazards from VCM and industry's ability to minimize these hazards. Announcement last Oct. 1 of the permanent OSHA standard on VCM, effective Jan. 1. the major thrust of which is to limit exposure to lppm averaged over 8 hrs and to maximum excursions of 5 ppm averaged over 15 min. 6nrl Tlr & Rubber Co. s this issue reaches you, the countdown will have already A begun toward the Jan. 1 deadline of the most critical challenge yet to face the plastics industry. Hardly any one involved in manufacturing or handling vinyl chloride monomer (abbreviated VC or VCM) or the PVC resin made from it is now unfamiliar with the dramatic chain of events which has led to the present crisis atmosphere. Some of the major links in that chain were: % The announcement late last January by B.F. Good rich Chemical Co. of the discovery of three deaths between 1968 and 1973 of long-time workers in a Louisville. Ky., PVC polymerization plant owing to a very rare cancer, angiosarcoma of the liver. (Subsequent intensive search in Where arc we now? OSHA's Jan. 1 deadline leaves a scant matter of weeks before the effective date of a standard that some monomer producers and most PVC makers say is impossible to meet with any known technology short of putting men into respirators--an alternative fraught with its own large difficulties. As for the PVC processor, whose only possible exposure is from the relatively small amounts of residual monomer trapped in the resin, the burden of the standard on him is assumed by its authors to be relatively light. In fact, the industry consensus seems to be that most, if not all. proc essors should be able to keep the majority of worker ex posures within allowable limits by instituting certain en gineering changes--mainly, increased ventilation--or workpractice modifications at reasonable cost. Most experts agree that the major problem for the processor under the new standard may be its ultimate effects on resin avail ability and cost. (See also p. 25.) SPI and about 10 chemical firms have gone to court in hopes of having the standard sent back to OSHA for re vision, and have appealed to OSHA for a stay in making the rule effective. Whatever the chances of some relief being granted, either bv the end of this month or later, tighter restrictions on VCM arc here to stay, and the PVC processor would be well advised to understand the new rule and know in advance what is required of him for compli ance. This is advisable both to minimize a health risk whose full extent is still only guessed at and because of the new and closer look OSHA is taking at processing operations. While the plastics industry has not until recently been considered a prime target for compliance inspections, an OSHA standards olficial in Washington says that firms manufacturing VCM and PVC "can likewise be of interest to the PVC According to Grover Wrenn, chief of plan to get to know an OSHA inspec processor because it indicates how an the Div. of Health Standards Develop tor in the near future." And the word inspector will judge compliance. Both ment, the standard is specifically not from the compliance section is ditto documents will be publicly available intended to regulate certain processes for PVC fabricators. While in one from regional and area offices. that involve only partial heating of a sense the standard may be said to be aimed mainly at monomer and poly If you want direct answers to in dividual questions about the standard fabricated material, such as thermoforming. heat-sealing, embossing, mer production, where workers are or its application to a given work situ shrink-film or blister packaging. subject to greater potential exposures, ation, a recommended starting point is Opinion in Washington seems to be OSHA also has its eye on processors, the Div. of Occupational Health Pro that scrap is exempt "fabricated prod who employ the great bulk of those potentially exposed--an estimated gramming, Washington, D.C. And for down-to-earth advice on uct"--at least until it's subjected to further melt processing. Coverage of 350,000 vs. some 6500 workers in VCM and PVC chemical operations. what to do in your own plant, your PVC resin supplier is probably your the standard in this area still looks questionable, though not if virgin is re So be prepared. best bet. Not only has he been living extruded or molded together with the Recognizing the urgent need of many of those affected for guidance with the problem longer and thus has experience in monomer detection and scrap. But even if scrap is reprocessed alone, it would be prudent to monitor and advice, this article will try to pro air analysis, but he's likely to have for VCM. though technical experience vide answers to frequent questions on his own processing facility as well and to date indicates that little or no vinyl how the standard applies to the PVC so be intimately acquainted with your chloride monomer release is likely processor, how he determines whether problem. Resin suppliers have been from this source. he has a VCM problem in his plant and what to do about it if he has. The in keeping their customers informed through letters, bulletins and other Another basic principle of the stand ard is that it aims at regulating in formation presented here has been means and; in many cases, have done dividual worker exposures, not abso gleaned from interviews with Govern actual monitoring in customer facili lute concentrations in air. That is, it is ment officials, health researchers, ma jor PVC suppliers and their custom ties. primarily concerned with amounts of VCM actually in the worker's breath ers, makers of analytical equipment First, know the law The initial state ing zone (defined, "without regard to and independent testing laboratories. In viewing what's still a fast-changing ment regarding scope of the new VCM standard (29 CFR Part 1910. Section the use of respirators") and not those in nonwork areas, such as inside a situation, this article tries to pinpoint, 1910.93q) reads in part: "This section storage silo or just adjacent to an in where possible, what's presently known applies to the manufacture, reaction, jection machine nozzle. Furthermore, and, in other cases, tries at least to packaging, repackaging, storage, han the regulation applies on an individual- warn where the question marks re dling or use of vinyl chloride or poly by-individual basis. One worker may main. vinyl chloride [homopolymer and co be exempted from its provisions while polymers!, but does not apply to the another at a different job or location The people in the know Before turn ing to specifics, here are some general handling or use of fabricated products made of polyvinyl chloride." in the' same plant may not. What's more, the standard provides remarks about two important sources of information regarding VCM-- "Fabricated product" is said to mean product "which does not require fur an extra incentive to achieve low VCM levels by promulgating the key concept OSHA itself and your resin supplier. ther processing at temperatures, and of an "action level," set at a 0.5-ppm First and most important, no PVC for times, sufficient to .cause mass time-weighted average. (TWA is a processor should be without a copy of melting of the polyvinyl chloride re measure of what levels an employee the actual standard. Reprints from the sulting in the release of vinyl chlo was exposed to for how long in vari Federal Register should be available ride." ous work stations.) "The purpose of free from your regional or area OSHA While OSHA apparently neither has the action level." according to the pre office; or else you can write to the Su closely defined "mass melting" nor in amble. "is to minimize the impact of perintendent of Documents. U.S. Gov tends to do so. it feels that the limits the standard on the employers who ernment Printing Office. Washington, of what is covered are pretty clear. have attained exposure levels well be D.C. (request Part II of the low the permissible limit. Federal Register of Oct. 4, 1974). Reprints of the OSHA Table 1---EMPLOYER REQUIREMENTS a Thus . . . employers may. in effect, be exempted from standard cost $.75 per copy. Exposure Level, ppm some provisions of the stand Two additional documents should be issued by OSHA before Jan. 1. One is the Pro gram Directive, which in structs regional and area per sonnel in how to conduct compliance inspections; it is intended to bring as much uniformity as possible to na tionwide enforcement of the Monitoring Program Meaicai Surveillance Medical Records Regulated Areas Roster of Authorized Persons Entering Regulated Areas Respirators <0.5 None No No No No No >0.5 <1.0 Quarterly Yes Yes No No No >t.O Monthly Yes Yes Yes Yes Yes ard." Or, as one industry ob server puts it, "The complex ity of life increases geometri cally above 0.5 ppm." Turning now from general principles to specific duties of employers in processing plants, the new OSHA regula tion calls for the following ac tions in specified situations: standard. The other is a Sam Warning Labels on Yes Yes Yes Monitoring is required pling Data Sheet intended to Storage Containers at least to determine initial instruct field personnel in a Training Yes Yes Yes exposure levels. (Monitoring uniform method of sampling "Data supplied by Diamond Shamrock Chemical Corp. for VCM in air. This will done before Jan. I reportedly will be accepted.) Since rnoni- Local exhaust hoods over calender rolls and other process equipment are a major means of lowering VCM exposures. toring need not be continued for any employee whose exposure is found to be at or below the action level ("unless changes have been made in production, process, control, type of resin, etc."), just what constitutes sufficient initial monitoring remains an important ques tion of interpretation, at least until the Program Directive comes out. Though this point is interpreted by some to mean only one 8-hr TWA determina tion per worker for a clean bill of health, this may not necessarily be so. Said one OSHA standards official, "Speaking as an industrial hygienist. I'm not sure I would accept a single run-through. At least the points where highest exposures might be expected should be repeated." At any rate, in cases where aboveaction-level exposures are found, moni toring must be continued at least quar terly when below the permissible limit and at least monthly when above the limit, until two successive readings no less than five working days apart con firm exposures below the action level. Regulated areas must be estab lished in processing plants wherever PVC is "stored, handled or used" and exposures exceed permissible limits. This means restricting access to "au thorized persons" and keeping daily rosters of those entering the regulated areas. Such areas, which need not be physically walled in, might consist of the work space around a piece of proc essing equipment, as long as require ments for access control and keeping of rosters are met. Respiratory protection must be supplied if exposures exceed 1- and 5ppm limits. Though the employer must provide respirators for all who are thus exposed, until Doc. 31, 1975, em ployees may choose to forego such protection as long as exposures don't exceed 25 ppm (defined as a 15-min ceiling). Anyone choosing not to wear h respirator "shall be informed at least quarterly of the hazards of vinyl chlo ride and the purpose, proper use, and limitations of respiratory devices." Provisions for employee training about the hazards of VCM apply to all PVC processors, regardless of ex posure levels at their plants. Compli ance officials offer no precise definition for any such a program; it could em ploy lectures, slides, demonstrations, pamphlets, etc. Where respirators are used, proper instruction in use and maintenance is required as per Section 1910.134 of OSHA regulations. Some review of the training program must be given annually. Medical surveillance of anyone exposed over the action level involves a specified yearly examination (or equivalent, as determined by a phy sician). provided at no cost to the worker. An OSHA-sponsored study by Foster D. Snell. Inc., Florham Park. N.J.. estimates cost of such surveil lance at SI 40-160/employee, requir ing a minimum of 1 Vi hrs of his time. It may be discontinued, as with moni toring. after exposures have been re duced below the action level. (A firm offering package medical programs specially tailored to this standard is Health Evaluation Programs, Inc., Park Ridge, III.) Containers of PVC resin--includ ing bags, boxes, loaded railcars, trucks and silos--and regulated areas must display specified signs or labels warn ing of a "cancer-suspect agent." AH records of monitoring, medi cal exams and rosters of persons enter ing regulated areas must be maintained for at least 30 years. Within a month after establishing a regulated area, reports must be sub mitted to your OSHA area director, citing plant location and number of employees in the regulated area. Each employee exposed to more than per missible levels (whether wearing a res pirator or not) must be informed in writing within 10 days of monitoring results. A simplified roster of employer du ties related to VCM levels is presented in Table I, opposite. Next, find out if you have a problem With regard to monitoring--the first step toward compliance--industry ob servers note that a large proportion of processors are already behindhand in this area. Not only have a good many PVC processors ignored the vinyl chlo ride monitoring requirement of the emergency temporary standard which has been in effect since April, but some have even indicated they will wait un til the last minute before confronting the situation. Of course, other processors have more than met their obligations. For instance, one custom molder, Ball Plas tics Div., Ball Corp.. Evansville. Ind., had been monitoring for the presence of organic vapors for several years be fore it recently began testing for VCM in particular. And several firms, par ticularly the larger ones, say they in tend to continue monitoring regularly even though they find no VCM expo sures in their plants amounting to the action level. By and large, those who have moni tored found they had little to fear. In terviews with companies in practically all areas of PVC processing--includ ing extrusion, calendering, injection, blow and rotational molding--indicate many processors will find they have been operating with virtually undetect able levels all along. This is confirmed by the experience of two independent laboratories. DeBell & Richardson Testing Institute and Gollob Analyti cal Services, which monitored for vinyl chloride in a total of about 50 PVC processing operations and found few major exposure problems that didn't seem correctable with improved venti lation. This is not to say that common prob lem areas don't exist or that you ought not anticipate such and pay special attention to these aspects of your op eration. Experience has shown what common sense would predict: that highest exposures are generally asso ciated with materials handling and storage and occur around hot-proccssing equipment, particularly in the case of intensive mixing units. Moreover, the chances of encountering unaccept able VCM levels can be related to whether one handles raw resin or com pound. powder or pellets, plasticized or unplasticizcd material as discussed below. Wherever resin is stored is a place to watch. According to Diamond Shamrock studies, area monitoring of trucks loaded with resin showed levels above 15 ppm, air space in a bulk railcar after four days' storage meas ured over 40 ppm and the inside of a silo. 1 ft above the resin surface, had more than 120 ppm. Granted that these were spot samples of areas where employees either don't work at all or for only short times, you nonetheless should be alert to possible exposures of workers unloading a truck, sampling a railcar, maintaining a silo dust filter, and opening up bags or boxes of mate rial. According to Gollob sources, poorly ventilated warehouses can contain a few ppm, with some sites going as high as 25 ppm. The contribution to a work er's TWA would depend, of course, on the amount of time he spent near the stored resin. Processing at elevated temperatures also tends to liberate residual mono mer from the resin. Most experiments show that by far the greatest amounts are released during dryblending, and that relatively little is given off during subsequent extrusion, molding, etc. For example, investigators reportedly have found insignificant VCM levels right over extruder dies. And the Dia mond Shamrock data showed expo sures to operators of extruders, injec tion and blow molding machines to be rarely above permissible or action levels, while monitoring of mixing op erations indicated the need for much greater care to avoid unacceptable levels. By this reasoning, processors han dling compounds are expected to en counter less airborne monomer by an order of magnitude, especially if the compound has been produced by highintensity mixing. Rigid pellets, accord ing to some sources, may release more VCM than powder compounds, de pending on how each was manufac tured. Finally, flexible compounds, whether powder or pellets, reportedly should give lower exposures than rigids, as the plasticizer is said to displace the monomer during compounding. Monitoring technique: no simple mat ter Probably no aspect of the VCM standard has aroused more intense dis cussion than the monitoring technology itself. Considerable research and inno vation in analytical techniques have been fostered by the attention to this issue during the past year, and new equipment offerings have greatly ex panded the choices available. However, one of the biggest ques tions remains. What will satisfy OSHA? The standard requires only that "individual employee exposure levels be determined"; in fact. OSHA officials say they mean to allow em ployers a certain amount of freedom as to exact method of compliance so long as that intent be fulfilled. (The Procram Directive should supply more information regarding criteria.) The standard's preamble expressly permits both area and personal (or "personnel") monitoring. Area moni toring of a specific plant location is said to offer the advantage of conveni ence; personnel monitoring of actual breathing zones gives more direct de termination of the time-weighted av erages, in which the regulation is ex pressed. For instance, a I-ppm TWA could result from breathing exactly 1 ppm for 8 hrs, or 2 ppm for 4 hrs, or 4 ppm for 2 hrs; or it could mean, for ex ample. breathing 1.5 ppm for 4 hrs, followed by 0.5 ppm for another 4 hrs. Some sources believe that area moni toring can give accurate determinations of TWA's without having the worker carry a personal monitoring device around with him for long periods. One way this might be done is by areamonitoring all work stations and then calculating by computer the amount of time each worker spent in each loca tion. Another approach to figuring TWA might be to combine area and personal monitoring. That is. once personal monitoring had established exposure below the action level, area monitor ing could watchdog the operation to warn if exposure changed. Besides al lowing immediate warning of highlevel excursions, as personal monitor ing does not. area monitoring has been determined by some company health determining worker exposures. (Courtesy, Aiutofe J. Sipin Co.) officers to be far more economical over the long term with regard to man power requirements. What will OSHA use? The VCM standard makes reference to only one specific monitoring and analysis meth od, described by the National Insti tute for Occupational Safety and Health in the NIOSH Manual of Analytical Methods. This method will be used by OSHA inspectors and is also the most widely employed in the industry to date. A copy of the pro cedure, "Vinyl Chloride in Air" (P&CA.M . -178), can be obtained from the NIOSH Office of Technical Publications in Cincinnati. The basic monitoring too! for this method is a personal sampling pump, a battery-powered device of the size and shape of a transistor radio, with a flexible tube attached (see photo, be low). The pump draws air in the flexi ble tube and through a glass tube con taining activated coconut-shell char coal used to adsorb any VCM present. Pumps weigh from as little as 10 oz up to about 2 lbs and may be carried in a shirt pocket or clipped to a belt. The end of the flexible tube is clipped someplace like the shirt collar to give a representative sampling of the breathing zone. To analyze monitoring results, the glass tube is removed from the pump, the charcoal emptied from the tube and shaken together with carbon disul fide solvent to desorb the VCM. Then a sample of the CS,/VCM solution is run through a gas chromatograph, which separates the VCM from other chemicals present, to a flame ioniza tion detector, which indicates how much VCM is present. From the sam ple one can calculate the total amount of VCM adsorbed by the charcoal from a known volume of air (pump flow rate having been accurately cali brated) during a measured time period --thus obtaining a TWA. Though the NIOSH charcoal-tube method is only suggested and not reauired. it has raised numerous ques tions and objections. One concerns the length of the sampling period deemed sufficient to establish an 8-hr TWA. Must one sample continuously for 8 hrs for each worker, or would several ;hortcr sampling periods suffice? Industry opinion on this point ranges Tom those who feel an 8-hr sampling ives the only definitive answer to adrocalcs of periods as short as 15 min. he latter stipulating of course that amplcs he made during times of ex acted peak exposure. The NIOSH manual recommends a pump flow rate of 50 cc/min, with total volume sampled not to exceed 5 liters for the standard charcoal tube. This recommendation is made in or der to avoid overloading the tube's ad sorbent capacity, which would result in false readings. At this flow rate, and with the normal range of sampling vol ume reportedly 1-5 liters, tubes must be changed every 20-100 min (1 liter equalling 1000 cc). Thus, for practi cality, a DeBell & Richardson con sultant recommends monitoring each worker for at least Vi hr every 2 hrs, or 4 samples/shift, even though full 8-hr monitoring might be theoretically preferable. But this same source says that inno vations in pump design now permit "a whole new philosophy of personal monitoring." Now that lower operat ing ranges of pumps have recently dropped from 50 to as low as 5 cc/ min, a worker reportedly can use a single tube throughout an entire shift. The consultant therefore recommends using a pump with a suitable operat ing range, for instance 10-50 cc/min, permitting full 8-hr monitoring with a few tubes at low flow rates; he also suggests taking a few short-time sam ples at the higher rate during periods of expected peak exposure to satisfy the 5-ppm 15-min ceiling. Here, high flow rates would be better for maxi mum accuracy since they concentrate as much VCM as possible on the char coal. Another stumbling block in inter preting the monitoring provisions has been the requirement that whatever measurement used shall have a mini mum accuracy, "with a confidence level of 95%," of 50% at 0.25-0.5 ppm, 35% at 0.5-1.0 ppm and 25% over 1 ppm. The detection method offered in the NIOSH manual currently reads, "Pre cision: Unknown." but fuller evalua tion by NIOSH is reportedly due by Jan. 1. OSHA says it will accept this method as meeting its accuracy re quirements--which the agency consid ers to be quite loose--and the unoffi cial word is that it will prove more accurate than called for. In any case, most observers agree that the NIOSH method isn't for ama teurs. Among the various sources of error, or "interferences," to which the method is reportedly subject are batchto-batch variations in charcoal, affect ing its adsorptive and desorptivc effi ciency. High humidity is also said to be particularly bad for accuracy. In exact pump calibration is another source of error, as is contamination of the carbon disulfide (itself a highly Table 2--VCM MONITORING AND ANALYSIS SERVICES* Aetna Life & Casually Co., Hartford, Conn. Airco Industrial Gases, Murray Hill, NJ. Anderson-Nichols, Boston Boehringer Laboratories, Wynnewood, Pa. Chrometrics Laboratories, Inc., Park Ridge, 111. George D. Clayton & Associates, South- field, Mich. Crobaugh Labs. Cleveland DeBell & Richardson Testing Institute, En field, Conn. Denver Research Institute, University of Denver, Denver Diamond Shamrock Corp., Environmental Laboratories, Paincsville, Ohio Gollob Analytical Service, Inc., Berkeley Heights, N.J. Gulf Research & Development Co., Pitts burgh LFE Corp., Environmental Analysis Labo ratories. Richmond, Calif. National Loss Control Service Corp., Long" Grove, 111. Pollution Control Science, Inc., Miamis- burg, Ohio Charles M. Shapiro & Son, Brooklyn, N.Y. Ten Ech Environmental Consultants, South Bend, Ind. University of Cincinnati Medical Center, Kettering Laboratory, Cincinnati U.S. Testing Co., Hoboken, N.J. *Partial listing. toxic chemical), besides numerous pos sible testing discrepancies on the part of the laboratory analyst. A number of modifications of the NIOSH method have appeared recent ly. Scientists at Western Electric's Re search Center in Princeton. N.J., de veloped a new type of sampling tube containing porous polymer adsorbent in place of charcoal. Together with thermal desorption of the VCM, in stead of carbon disulfide extraction, the method is said to be one or two orders of magnitude more sensitive and is believed to be more accurate than charcoal tubes; also, the new tubes are reusable. Western Electric also uses a mass spectrometer, report edly giving the most precise identifica tion of VCM presence of any instru ment. though it costs in the neighbor hood of $100,000. is expensive to op erate and requires highly trained per sonnel. The company is said to be planning to license the new technology and an "improved" area-monitoring method in the near future. Still another method which has at tracted considerable attention is the use of plastic bags instead of sampling tubes for personal monitoring. Now that some pumps arc available which can be operated in both a pressure and a suction mode, they can be used to fill a bag with air samples. Bags of aluminized Mylar, Tcdlar, Teflon and saran arc said to have proved acceptable. They reportedly come in 1-7 liter sizes and may be clipped to a belt or carried in a small knapsack. A 2-liter bag measures about 8 x 16 x 2 in. thick when inflated. The bags require a septum for withdrawing a sample with a gas syringe or a valve which can be directly coupled to the gas chromatograph inlet port. Bag sampling is attractive for its simplicity. Because air is merely col lected and then analyzed directly, there are fewer opportunities for error, and whatever gc reading is obtained is an actual TWA for the contents of the bag. Some knowledgeable sources vouch for bag sampling as inherently more accurate than adsorbent tube methods. Should you buy equipment? Regard less of all the above considerations, probably the main objection to the NIOSH' method, from the point of view of a great many processors, is that gas chromatographs are sophisti cated instruments, generally costing several thousand dollars and at least requiring supervision by a trained analytical chemist. Numerous smaller, simpler, less expensive versions of these and other types of instruments are being advertised. Their manufac turers claim to supply them fully cali brated for push-button operation by relatively untrained personnel. But experienced technical personnel at PVC resin companies tend to be skeptical of such claims, reasoning that analyzing for any gas in the range of V4 ppm involves considerable un certainties and that in the case of VCM, the stakes are too high to permit a casual approach. Thus resin suppliers are generally cautioning their customers against hastily jumping into large equipment purchases. They feel most processors won't be involved in monitoring over a long term. In fact, many fabricators may find that they only need perform initial, monitoring and very little there after. Most others should be able to get below the action level and stay there. Consequently, resin suppliers rec ommend that most processors begin by consulting an independent analyti cal laboratory (sec Table 2. above). Thecc groups provide various services, including complete monitoring and analysis, processing of samples taken by the customer himself and equip ment rental. A spot-check indicates that fees commonly run $IO-30/samplc, depending on number and type of samples, volume discounts being generally offered. Individual needs will of course dif fer. Smaller processors have already shown some preference for outside consultants, while larger operations, particularly those associated with a resin producer or other technical-back up source, have installed sophisticated equipment systems. General Tire & Rubber Co., for instance, has a $10,000 gas chromatograph in each of its 12 PVC processing plants (used for a variety of purposes) and a mass spec trometer at its Akron research center. A shopper's guide If you are consid ering equipment purchases, you'll quickly find there's a bewildering array of instruments now being advertised to the plastics industry--and they cov er every level of price and sophistica tion. The following brief overview of some of the basic approaches to vinyl chloride detection and measurement provides an indication of costs and representative suppliers (see also Table 3, right) : Personal monitoring pumps. These, already discussed above, are offered for $300-350 by such firms as Sipin, SKC, Bendix, Mine Safety Ap pliances and Calibrated Instruments. Charcoal tubes, at 40<5 apiece, are available from SKC and other pump suppliers as well as various distribu tors. Sampling bags may be obtained from Alltech Associates, Calibrated Instruments and other pump suppliers. They cost as much as $6 each but are reportedly reusable. e Gas chromatography. Equip ment here encompasses a wide variety of types, from laboratory analytical models for analyzing personal moni toring samples to on-line process moni tors for continuous sequential sam pling of one to 30 remote locations, as well as units that combine both capabilities. Prices also range all over the map, with large, sophisticated lab models selling for $5000-10.000 or more and simplified, portable units costing around $1000-$5000. Suppliers include Perkin-Elmer, Hewlett-Pack ard, Varian. Beckman. Bendix. GowMac, Baseline Industries. Century Sys tems. Areas. Applied Automation, and Analytical Instrument Development. Infrared absorption analysis. This technology has been attracting considerable attention as an alterna tive to gas chromatography for both personal and area monitoring. Units range from battery-powered portable types (under $3000) to computerized multipoint monitoring systems ($10,000 and over). Two firms which have shown particular interest in VCM de Table 3--VCM MONITORING and ANALYSIS EQUIPMENT SUPPLIERS* A.E.D., Inc., Chicago Environmental Compliance Corp., Pittsburgh Alltech Associates, Arlington Heights, 111. Environmental Measurement Systems, div. Analytical Instrument Development, Inc., of Western Marine Electronics, Seattle Avondale, Pa. Eocom Corp., Irvine, Calif. Applied Automation. Inc., Bartlesville, Okia. Gow-Mac Instrument Co.. Madison, N.J. Areas, Inc., Houston Hewlett-Packard, Avondale, Pa. Bacharach Instrument Co., Pittsburgh Honeywell Inc., Process Analyzer Center, Baseline Industries, Inc., Lyons, Colo. Houston. Beckman Instruments, Inc., Process Instru Ion Track Instruments, Inc., Waltham, ments Div., Fullerton, Calif. Mass. Beckman Instruments, Inc., Scientific Instru ments Div., Irvine, Calif. Matheson N.J. Gas Products, E. Rutherford, Bendix Corp., Environmental Science Div., Baltimore Bendix Corp., Process Instrument Div., Ronceverte, W. Va. E. D. Bullard Co., Sausalito, Calif. Byron Instruments, Inc., Raleigh, N.C. Microchemical Specialties Co., Berkeley, Calif. MDA Scientific, Inc., Park Ridge, 111. Mine Safety Appliances Co., Pittsburgh National Environmental Instruments, War wick, R.I. Perkin-Elmer Corp., Norwalk, Conn. Calibrated Instruments. Inc., Ardsley, N.Y. Carle Instruments, Fullerton, Calif. Anatole J. Sipin Co., N.Y.C. SKC Inc., Pittsburgh Century Systems Corp., Arkansas City, TC Systems, Inc.. Houston Kans. Devco Engineering Inc., Fairfield, N.J. Varian Associates, Palo Alto. Calif. Wilks Scientific Corp., S. Norwalk, Conn. Empire Technology Inc., Clifton Park- Elnora, N.Y. Partial listing. tection are Wilks Scientific and Eocom. Colorimetric methods. These ap pear to be another promising alterna tive. MDA Scientific has developed several models that employ a chemi cally impregnated paper tape which changes color as VCM is drawn into the sampling port. An optical sensor then measures concentration accord ing to depth of color change. System reportedly offers extremely simple op eration and sensitivity to 0.01 ppm. Continuous area-monitoring unit with paper-tape cassette costs $2900 with chart recorder, spot-sampling model is $500. MDA is also developing a personal monitor to be worn by work ers ($650 plus $950 for the tape reader); device will give both TWA and continuous profile of worker ex posure. For a simplified colorimetric approach to manual spot sampling, Bendix supplies glass tubes contain ing a reactive absorbent medium said to be highly specific to VCM. Sample from a hand pump is injected into a tube, with length of stain produced indicating concentration. Method re portedly can measure 0.5 ppm with 5-10% accuracy. (Cost is $85-90 for 10 tubes and sampling pump.) Total hydrocarbon or organic vapor analyzers. This approach to area monitoring, as the term suggests, isn't specific to VCM and so is more suitable for showing where VCM doesn't exist than where it does. Sup pliers such as Bendix, Bacharach and Century Systems provide units from portable direct-reading types to sta tionary, remote multipoint monitors. Prices range from around $600 to over $6000. Various other analytical approaches to portable and stationary area-moni toring are available. Examples include a detection system based on the differ ing physiochemical adsorptive forces of different compounds, supplied by Environmental Measurement Systems; an electron-capture detector system from Ion Track Instruments; systems from Devco Engineering based on identifying VCM by its dielectric con stant, and an electrolytic-cell gas sen sor from Bullard. (Prices vary with the unit.) But whichever way you decide to monitor, keep the OSHA inspector and the method he's using in mind. As a major PVC supplier puts it, "We want to be damn sure our results match up with his." What about respirators? Another equipment question which has been causing some confusion is that of respirators. While it's hoped and ex pected that very few workers in proc essing plants will ever need to wear one, at least one informed source doubts whether ail purchasers of uneompounded resin will be able in the short term to get below permissible VCM limits in certain plant areas, such as mixing rooms. Furthermore, a senior OSHA official says that sam pling of incoming railcars might well be classified as a "hazardous opera tion"--defined, in part, as a situa tion in which accidental overexposures might reasonably occur--and thus re quire rcspiralory protection. One major question concerns what I type of respirator is legal and practical to use. The standard lists specific types of respirators as permissible in certain maximum VCM ambient concentra tions; the equipment for the higher levels is generally more expensive. Basic types include: Air-purifying masks, which filter ambient air through cartridges or can isters containing adsorbent media. Cartridge types reportedly run $10-12, canisters about $50 and "powered" (blower-equipped) types around $200. Replacement cartridges are $3-6 and cans $10-15. Cartidge masks are per mitted for up to 10 ppm and canisters for up to 25 ppm, probably as much as would be found in a processing plant. Air-supplied masks, which are fed through a hose from an outside source. Masks themselves cost $80-85; the least expensive method of supplying air would be to connect with the plant's compressed-air system and add a low-pressure purifier (about $1000). As issued, the standard permits air-line respirators without auxiliary supply in up to 100 ppm; but the list omits what's said to be actually the most common respirator type. The list is being amended so that, for not over 1000 ppm, OSHA reportedly will per mit a Type C supplied-air, continuousflow respirator with full or half mask, helmet or hood, which costs approxi mately $60-80. Self-contained compressed-air bot tles, which, depending on type, can be used in all environments. For a 15-min supply, these units start at $350-400. Combination air-line types with selfcontained auxiliary supply would run $200. However, to refill compressedair tanks requires a high-pressure puri fier/compressor/cascade system cost ing $5000-$6000. If any respirator is used at all, clear ly the most desirable for the processor in terms of cost and convenience of use are the air-purifying types. Unfortu nately, to date no such respirators have been approved by NIOSH, as required by the standard. NIOSH reportedly only just completed testing protocols to begin evaluations and possible cer tifications of respirators this month. One important question still left hang ing is whether NIOSH will insist on end-of-servicc-life indicators (the first of which is only recently rumored to have been developed) or will go along with OSHA's acceptance of "admin istrative controls" to make sure car tridges and canisters arc replaced suffi ciently often. But even if all approvals arc made immediately, it will be impossible to Cartridge (I.) and canister [r.) type air-purifying respirators are least expensive and easiest to use, but must await NIOSH approval. supply the industry with the required number of respirators by Jan. 1, ac cording to an SPI petition for a delay of the standard. Some 25.000 respira tors are reportedly already on order for VCM and. PVC manufacturers alone, and SPI says today's supply is only 26% of current demand; with ex peditious NIOSH approvals, supply would still be only 78% of demand. But should lack of available respira tors be the only factor keeping you from compliance, OSHA sources in Washington say application for a vari ance is always a possible avenue of relief. Tips on engineering controls When asked what difficulty processors will have in lowering VCM levels in their plants, most informed sources replied that in the long run. getting rid of VCM would not properly be the proc essor's problem at all. Since his only exposure to VCM can be from unreactcd monomer in the resin (PVC does not degrade to VCM), the most evi dent solution is for the resin supplier to remove as much of it as possible. There is indeed a strong push by all resin suppliers to accomplish just that. Today's resins reportedly may contain anywhere from less than 1 ppm to over 1500 ppm of VCM, depending on method of manufacture, grade, parti cle structure and other factors. The initial goal, industry wide, seems to be to get averages below 50 ppm; some suppliers say they can achieve this consistently in certain grades or from certain production facilities. Tenneco Chemicals even claims it has been able, on a pilot-plant basis, to produce resin with "no detectable" VCM re maining. Meanwhile, the next best answer for the processor is said to be to remove as much VCM as possible, under con trolled conditions, during the com pounding process. Such an effort would leave that much less monomer to cause problems downstream. Sub stantial improvements in VCM remov al reportedly have been shown possible with a new technology developed jointly by ICI's Plastics Div. and T. K. Fielder Ltd. in England, with the tech nology now made available in the U.S. and Canada through Werner & Pfleiderer Corp., Waldwick, N.J. The system centers on the dryblend ing cycle, where most VCM is nor mally generated, and further enhances this effect while insuring that the VCM so produced is safely exhausted from the work area. In this way, it not only makes the resin more free of monomer for subsequent processing, but rcportcly also tends to yield lower VCM levels in the mixer work area. Filtered air is continuously aspirated through the mixer headspace while small amounts of low-pressure air arc also injected at or near the bottom of the mixer bowl. This air then flows through the material, stripping away additional VCM from the mix. Mono mer-laden air is drawn from the mixer through a cyclone separator, where edly can make feed lines quite hot enclosing a calendering line.) large particles are collected in a re (180-200 F) while vacuum lines are Proper ventilation is also advisable movable dust bin; it then moves on cooler (100-120 F) and thus cause less in warehouses where PVC resin is to a cloth filter to trap additional fines monomer to be released. What's more, stored. Cost and airflow requirements before passing through a turboblower and being exhausted from the work Process Control's vacuum-conveying systems feature closed-loop designs can possibly be minimized by keeping all PVC segregated in one corner, per area. (See diagram.) that both exhaust monomer outside the haps in an actual enclosure, with local With this Exorsta system, much plant and reportedly avoid particle-size exhausting provided. Alternatively, in more monomer reportedly can be re moved, at lower temperatures than classification problems said to be com mon in closed-loop pressure systems. a warehouse with relatively good over all air movement, you might scatter would otherwise be necessary. Com Process Control is working on other the PVC in smaller lots so that lesser pany data show that residual VCM in materials-handling approaches to mini local VCM concentrations could ac finished dryblend can be halved by in mize worker exposures in mixing cumulate. Amount of ventilation creasing mixing temperature from 250 areas. Here part of the problem is said needed in a warehouse will partly de F to 265 F, though even better results to be that usually only major com pend on storage temperature, more can be obtained at the lower tempera pound ingredients (such as resin and monomer being liberated at higher ture by adding headspace aspiration plasticizer) are metered automatically temperatures. How long the resin is alone. With air stripping as well, mon to the mixer while from six to 13 stored is also relevant; VCM emissions omer removal at 250 F is in from bagged resin reportedly creased more than fourfold decline rapidly to negligible again. Thus the system is said leve's after a few weeks to readily produce dryblends (though this is not necessar with only 5-10 ppm residual ily true for pelletized PVC VCM vs. more than 100 ppm materials). by conventional dry-blending Some processors are spend techniques. ing several thousand dollars Werner & Pfleiderer sup on ventilation in order to get plies complete Exorsta sys below the action level. As this tems, including engineering, is a technically complex sub training and installation serv ject in itself, you may well ices as well. The Exorsta sys want to consult a professional tem is a self-contained design engineer before making such with cyclone separator, filter an investment. and exhaust mechanisms and Dr. Maurice Oberg of LFE is said to be readily adaptable Environmental Analysis Lab to retrofitting all existing dryblend units. It costs $30006000 installed, depending on New system removes as much VCM as possible during dryblending, so less can escape downstream. (Courtesy, Werner & Pfleiderer Corp.) oratories presented some of the complexities involved at a recent SPE meeting in size and type of mixing equipment. "microingredients" (additives which to N.Y.C. For example, distance of an Considerable work is being done in gether add up to no more than 10% exhaust hood from the VCM source monomer-extraction techniques. Proc of the total) are added by hand. The is an important factor, with airflow ess Control Corp., Atlanta, reports it company recommends instead that requirements increasing proportional also has been retrofitting mixer units these microingredients be master- ly to the square of that distance. Hood with its own aspiration systems. And batched together with enough resin to configuration is likewise important, Werner & Pfleiderer is developing dilute the whole to a sizeable volume since 25% less airflow reportedly can technology for using vented twin-screw from which portions could be auto provide the same amount of control if compounding extruders to remove even matically dosed. Getting the operator the hood is flanged or if it's placed more monomer. A goal which it hopes away from the mixer as much as pos flush against a wall or other surface. to accomplish soon is to produce com sible is thus a simple answer to re One example Oberg cited was a hood pound with as little as 1 ppm residual ducing his exposure. over an extruder die, the hood flange VCM. But of all engineering controls ap contacting the die at roughly a 45 Among other techniques for mini plied to the VCM problem, ventilation angle. Such an arrangement reportedly mizing VCM exposures in processing is probably the most widespread and would provide efficient fume removal plants, automated bulk materials han versatile. Moving large volumes of air and avoid dripping condensed plasti dling is certainly a step in the right direction, as it eliminates exposure to ventilate entire work areas is the most expensive and least efficient ap cizer, for instance, on the extrudate. A flexible metal duct would permit the from opening bags or boxes or from stored material in warehouses. But re member that what happens in a pneu proach; in addition, winter weather will require that incoming air be heat ed, at considerable extra expense. hood to be moved for access to the die. The above considerations, as well as shape of hood, fan blade configuration matic feed line is reportedly something like air stripping in a mixer; that is, Locating exhaust hoods near proc essing equipment is by far the pre and duct geometry, arc only some of the factors involved in designing the there will be plenty of entrained mono ferred approach, and many processors most efficient system for your money. mer and possible leaks are a factor to consider. For this reason, Process Control Corp. engineers have been recom mending vacuum rather than pressure systems. Pressure and friction report attribute their lack of exposure prob lems to doing this. In many cases, local ventilation had already been in stalled to remove plasticizer vapors and other fumes. (One plant even went to the novel length of entirely (A professional manual on the subject is "Industrial Ventilation," published by the American Conference of Gov ernmental Industrial Hygienists Com mittee on Industrial Ventilation, Lan sing, Mich.) Reprinted from Plastics Technology, December 1974 W. M. Smith D. Y. Lewis Cleveland iii'Ui rt in r .. i /n.io.*i L; t'A:i rMimr <v m ><,. <. Avon Lake General Chemical 12/26/74 Following is the data you requested: Sample Identification American Chem ACC-102 Tulgon, Aria. RVCM (ppm) 106.07 American Chem ACC102 320-1274 Carson, Calif. 0.40 Airco Products 1230P Resin 259.35 Goodyear 278.13 Porosity 0.125 0.140 0.170 0.185 I. V. 0.902 0.921 0.866 0.876 Sonic Sifter 40 - 0.07 60 - 0.32 80 - 4.17 100 - 12.60 140 - 53.25 200 - 22.04 pan - 7.54 X - 122.0 8 - 30.6 40 _ 0.08 60 - 1.66 80 - 16.02 100 - 24.05 140 - 44.70 200 - 10.48 pan - 3.00 X - 143.5 s - 30.12 40 _ 0.33 60 - 20.90 80 - 36.16 100 - 20.75 140 - 19.42 200 - 1.85 pan - 0.60 X - 191.6 s - 32.0 40 _ 0.08 60 - 0.33 80 - 3.00 100 - 8.08 140 - 73.70 200 - 13.41 pan - 1.40 X - 124.2 -s - 19.2 8 l9`2 00 0s. fir g 4s rc-mi.1 ncv. u/?s litmo. in u.s.a. W. M. Smith Sample Identification Hooker 2 RVCM (ppm) 0.33 PVC Compound Bid. UPE-27B Bin 3507 (apparent density - .623 gms/cc) Conoco 5385 12-3-74 J M Pueblo, Colo Diamond Shamrock Car ACFX 54620 12-4-74 22.73 17.77 33.81 December 26, 1974 Porosity 0.220 I. V. 0.908 Sonic Sifter 40 - 0.09 60 - 0.19 80 - 0.71 100 - 4.36 140 - 84.97 200 - 9.07 pan - 0.61 R - 124.4 s - 14.10 Wiry .. . r. D. Y. Lewis / dl cc: F. V. Zemanek ^|comr pqr W.M. Smith Cleveland F.V. Zemanek^coPY po^NK ALGC 12/11/74 Competitive Resin Data Six (6) competitive resin samples have been sent to the M.S. Lab for RVCM, Sonic Sifter Screens, Porosity and Inherent Viscosity. The ALGC laboratory personnel ran the I.V. and RVCM analyses. Following is the identification and data: Borden Pipe Resin RVCM Porosity = I.V. S.S.- 40 = 60 = 80 = 100 = 140 = 200 = pan = 43.5 ppm 0.215 0.963* .14 .50 5.95 17.11 58.42 15.47 2.41 X = 130.35 S = 24.98 Firestone FPC9326 L-B4892 (11-27-74) RVCM Porosity = I.V. S.S.- 40 = 60 = 80 = 100 = 140 = 200 = pan = 349.35 ppm 0.180 0.963 .06 2.49 23.03 23.86 41.34 7.57 1.64 X = 149.54 S = 28.53 Air Products PVC 1230P(12-3-74) RVCM Porosity I.V. S.S.- 40 = 60 = 80 = 100 = 140 = 200 = pan = 735.99 ppm 0.130 0.884 .22 1.67 10.30 20.57 45.50 13.54 8.20 X = 136.16 S = 39.56 Hooker B-303 L-57 -4-32-13 RVCM Porosity = I.V. S.S.- 40 = 60 = 80 100 = 140 = 200 = pan = 20.25 ppm 0.180 0.909 .06 .14 .90 2.04 82.80 13.89 .16 X = 111.50 S = 12.53 (continued) Compi'i i t i vp R cs i n Data Page 2 Hooker Rucon 15-303 L-57-433-13 Hul nor Plant ACFX57135__________ RVCM = Porosity = I.V. = S .S .- 40 = 60 = SO = 100 = 140 = 200 = pan = 217.63 ppm 0.200 0.911 .04 .08 1.53 4.17 73.93 19 .92 .33 X= S 115.62 14.61 Conoco PTLX-41656 Resin Type 1843 Bulk 5385 RVCM = 265.37 Porosity = 0.215 I.V. 0.917 S.S.- 40 = .06 60 - 2.29 80 = 16.38 100 20.69 140 * 44.85 200 = 13.01 pan * 2.72 X 140.09 S = 31.30 * Note: After 24 hours of sample time preparation (heat and agitation), a good portion of the sample appeared to remain insoluble. The I.V. was run on the solution as it was. Bill, if we can be of more help give me a call. FVZ/bjs cc: J.M. Whitney l/uJ .V. Zemanek J i SUBSTANCE cetic Acid Acetone Acetonitrile Acrylamide-Skin Acrylic Acid Acrylonitrile-Skin Allyl Chloride Ammonia Aniline Benzene 1,3-Butadiene Butane Butyl Acrylate Carbon Disulfide Carbon Tetrachloride-Skin Chlorine Chloroform Cyclohexylamine-Skin 1,2-Dichloroethane Dicyclopentadiene Di-iso Butylene Diphenyl Diphe nylamine Epichlorohydrin Ethyl Acetate Ethyl Acrylate-Skin "thylene Oxide -ithylidene Norbornene Formaldehyde Hexane Isobutylene Isoprene Isopropyl Acetate Isopropyl Alcohol-Skin Mercury Methyd. Acrylate-Skin Methyl Alcohol-Skin M.B. Isocyanate (MDl) Methylene Chloride Morpholine-Sivin p-Nitroaniline-Skin Phenol-Skin Phosphoric Acid Phosphorus Trichloride Styrene Toluene Trie hloroc thylene Vinyl Acetate Vinyl Chloride Vinylidene Chloride ACGIH 1974 TLV ppm mg/rrP 10 1000 40 25 2460 70 0.3 20 1 25 5 plO 1000 p6oo 45 3 18 19 p30 2200 pl450 20 60 10 65 13 25 120 10 40 50 200 0.2 -- 5 4oo 25 50 C5 C2 plOO 1 10 19 1400 100 90 C25 C3 p36o 250 400 0.001 10 200 CO. 02 plOO 20 1 5 -- 0.5 100 100 100 10 Pending 10 950 980 0.01 35 260 CO.2 p36o 70 6 19 1 3 420 375 535 30 40 OSHA STANDARD 1910.93 TWA Acceptable Peaks ppm 1mg/m3 PPm Minutes 10 1000 40 -- 25 2400 70 0.3 20 1 50 5 10(C25) 1000 45 3 35 19 2200 50 10/8 hr. 20(C30) 10(C25) 1 C50 50(C100) 3 240 100 30/8 hr. 200 5/4 hr. 200 5/3 hr. 0.2 qs 400 25 50 3(C5) 500 1 19 1400 100 90 1800 10 30/8 hr. 250 400 10 200 CO. 02 500(C1000) 20 1 5 -- 0.5 100(C200) 200(C300) 100(C200) 1 950 980 C0.1 35 260 CO .2 70 6 19 1 3 2000 600 500 300 5 5/2 hr. 5/3 hr. 10/8 hr. 5/2 hr. 15/8 hr. Odor Threshol ppm 1 100 21 0.5 47 1 q> 0.2 100 0.3 12 0.0005 700 1 20 100 214 0.05* o.i-o.r 2-4 21 250-5000 500- 100c. ppm - Parts of vapor or gas per million parts of contaminated air by volume at 25C and 7^0 Hg. "i - Proposed for 1975* - Ceiling - Should not be exceeded, unless acceptable peak is permitted. Skin - Potential contribution branes and eye, either to by overall exposure by the cutaneous route including mucous airborne, or more particularly, by direct contact. mem C4 0 JAKrcj 1/2/7'' w PHYSICAL PROPERTIES 1 3; O SUBSTANCE MW Acetic Acid Acetone Acetonitrile Acrylamide-Skin Acrylic Acid Acrylonitrile-Skin Allyl Chloride Ammonia Aniline Benzene 1,3-Butadiene Butane Butyl Acrylate Carbon Disulfide Carbon Tetrachloride-Skin Chlorine Chloroform Cyclohexylamine-Skin 1,2-Dichloroethane Dicyclopentadiene Di-iso Butylene Diphenyl Diphenylamine Epichlorohydrin Ethyl Acetate Ethyl Acrylate-Skin Ethylene Oxide Ethylidene Norbornene Formaldehyde Hexane Isobutylene Isoprene Isopropyl Acetate Isopropyl Alcohol-Skin Mercury Methyl Acrylate-Skin Methyl Alcohol-Skin M.B. Isocyanate (MDl) Methylene Chloride Morpholine-Skin p-Nitrooniline-Skin Phenol-Skin Phosphoric Acid Phosphorus Trichloride Styrene Toluene Trichloroethylene Vinyl Acetate Vinyl Chloride Zinylidene Chloride 60.0 58.0 41.0 71.1 72.0 53.0 76.5 17.0 93-6 78.1 54.1 58.1 128.1 76.1 153.8 70.9 119.4 99.2 99.0 132.1 112.2 154.2 169.2 ' 92.5 88.1 100.0 44.0 120.2 30.0 86.2 56.1 68.1 102.0 60.0 200.6 86.0 32.0 360.3 84.9 87.2 138.1 94.1 98.0 137.4 io4.i 92.1 131.4 86.1 62.5 97.0 Formula CH3C00H CH3COCH3 CH3CN CH2=CHC0NH2 CH2=CHC00H CH2CHCN CH2=CHCH2C1 NH3 C6H5NH2 c6h6 CH2=CHCH=CJE CH3(CH2)2CH3 CH2=CHC00C4H9 CS2 cci-4 Cl-2 CHC1-3 C6H-11-NH2 CH2C1CH2C1 C-10-H-12 C8H-16 C6H5C6H5 (CoH5)2NH CHC10CHCH3 CII3C00C2H5 CH2=CHCOOC2H5 CH2-0CH2 C9H-12 HCOH CH3(CH2)4CH3 (CH3)2CCH2 CH2=C(CH3)CH=CH2 CH3COOC3H7 C3H7-OH Hr CH2=CHC00CII3 CH3-0H N2-0-2-C-15-H-10 CH2C1-2 0(CII2CH2)2NH C6H6N2-0-2 C6H5-OH H3P04 PCI-3 C6H5CH=CfE C6H5CII3 CHCl=CCl-2 CH3C00CH=CH2 CH2=CHC1 CH2=CCl-2 BP F 6l -137 -42 184 54 -117 -213 -108 21 4l -164 -211 -84 -169 -9 -150 -83 -0.4 -32 91 -150 158 127 -54 -119 -96 -163 -112 -134 -l4l -220 -233 -99 -122 -38 -103 -144 99 -143 18 295 104 108 -169 -23 -139 -99 -148 -245 -188 245 134 176 288 171 . 113 -28 364 176 23 33 - 115 171 -30 142 275 182 338 21b 492 575 243 171 212 51 298 -3 156 20 93 191 181 674 176 147 - 104 262 *v 358 - 167 295 231 188 163 7 99 Vapor Density Air=l 2.1 2.0 1.4 2.5 2.5 1.8 2.6 0.6 3.2 2.7 1.9 2.0 4.4 2.6 5.3 2.5 4.1 3.4 3.4 4.6 4.0 5-3 5.8 3-3 3.0 3.5 1.5 4.0 1.1 3.0 1.9 2.4 3-5 2.1 3.0 1.1 - 2.9 3.0 - 3-2 - 4.8 3.6 3.1 4.5 3.0 2.2 3.4 Specific Gravity H20=l 1.05 0.79 0.79 1.12 1.05 0.8l 0.94 0.77 1.02 0.88 0.62 0.60 0.89 1.26 1.58 1.47 1.49 0.87 1.26 0.93 0.72 0-99 1.16 1.18 0.90 O.92 0.87 0.90 0.82 0.66 0.60 0.68 0.87 0.79 13.6 0.95 0.79* 1.19 1.3 1.0 1.44 l.l 1.06 1.59 0.91 i!\ 0.87 ^ 1.46 ^ 0.94 ^ O.91 CAi 1,3 & JAK:cj 1/2/75 SUBSTANCE Acetic Acid Acetone Acetonitrile Acrylamide-Skin Acrylic Acid Acrylonitrile-Skin Allyl Chloride Ammonia Aniline Benzene 1,3-Butadiene Butane Butyl Acrylate Carbon Disulfide Carbon Tetrachloride-Skin Chlorine Chloroform Cyclohexylamine-Skin 1,2-Dichloroethane Dicyclopentadiene Di-iso Butylene Diphenyl Diphenylamine ^pichlorohydrin ..thyl Acetate Ethyl Acrylate-SKin Ethylene Oxide Ethylidene Norbornene Formaldehyde Hexane Isobutylene Isoprcne Isopnopyl Acetate Isopropyl Alcohol-Skin Mercury Methyl Acrylate-Skin Methyl Alcohol-Skin M.B. Isocyanate (MDl) Methylene Chloride Morpholine-Skin p-Nitroaniline-Skin Phenol-Slcin Phosphoric Acid Phosphorus Trichloride Styrene Toluene Trichloroethylene Vinyl Acetate Vinyl Chloride Vinylidene Chloride ,c - Open Cup JAKrej 1/2/15 Flash Point CC, F 109 0 42oc 130oc 32oc -25 - 158 12 < 20 -76 120oc -22 None - None 90oc 58 90oc 20 235 307 105oc 24 60oc <0 - -7 - -65 40 53 - 2700c 52 - lOOoc 390 175 - 90 40 - 18 -108 0 Ignition Temp F 869 869 975 Polym. 598 905 1204 1139 1040 788 761 559 194 --- -- 560 775 -- ioo4 1175 800 8o4 806 437 889 428 860 750 -- 725 1139 590 1319 -- -- 914 898 788 800 882 1058 Flammable Limits By Volume LEL % UEL 5-4 16.0 2.6 12.8 4.4 16.0 -- 3.0 2.9 16 1.3 1.3 2.0 1.9 1.5 1.3 None -- None -- 6.2 -- 17.0 11.1 25 -- 7.1 12.0 8.5 9-9 50.0 -- -- -- -- 16 0.6 5-8 2.2 1.8 3.6 7.0 1.1 1.8 2 1.8 2 -- 2.8 6.7 15.5 11.0 100.0 73 7.5 9.b 9 8 12 -- 25 36 66 -- -- 1.1 1.2 12.5 2.6 3.6 7.3 -- -- 6.1 7.1 90 13-4 33.0 16.0 NFPA 704M System Health Fire Reaction 22 13 23 3 32 43 33 31 32 23 24 14 22 2 ^3 30 3 .0 20 23 23 13 1 0 1 2 2 1 0 0 0 2 0 2 0 0 0 0 0 0 1 21 31 32 13 23 24 0 0 1 0 2 3 24 13 14 24 13 13 0 0 0 2 0 0 23 13 2 0 20 23 31 32 20 30 23 23 11 23 34 24 0 0 3 0 0 2 2 0 0 2 1& 2 Co o 00 o* NFPA, 704M SYSTEM: A numerical system for the identification of the Fire Hazards of Materials developed by the National Fire Protection Association. The numbers given in the three columns have been taken from NFPA publications and other sources. For full definitions of the various degrees of hazard (0 to 4 in each category), see NFPA No. 704ll-1969. Abbreviated definitions are as follovs: HEALTH 4 Can cause death or major injury despite medical treatment. 3 Can cause serious injury despite medical treatment. 2 Can cause injury. Requires prompt treatment. 1 Can cause irritation if not treated. 0 No hazard. FIRE 4 Very flammable gases or very volatile flammable liquids. 3 Can be ignited at all normal temperatures. 2 Ignites if moderately heated, 1 Ignites after considerable preheating. 0 Will not burn. REACTIVITY (Stability) 4 Readily detonates or explodes. 3 Can detonate or explode but requires strong initiating force or heating under confinement. 2 Normally unstable but will not detonate. 1 Normally stable. Unstable at high temp, and pressure. Reacts with water. 0 Normally stable. Not reactive with water. JAK:cj 1/2/75 i X i SUBSTANCE LDJO - Oral TCLo - Inhalation LCLo - Inhalation LD50 - Skin Rat - mg/Kg Human - ppm Rat - ppm Rabbit - mg/Kg Acetic Acid Acetone Acetonitrile Acrylamide-Skin Acrylic Acid Acrylonitrile-Skin Allyl Chloride Ammonia Aniline Benzene 1,3-Butadiene Butane Butyl Acrylate Carbon Disulfide Carbon Tetrachloride-Skin Chlorine Chloroform Cyclohexylamine-Skin 1,2-Dichloroethane Dic.yclo pentad iene Di-iso Butylene Diphenyl Diphenylamine Epichlorohydrin Ethyl Acetate ~'thyl Acrylate-Skin -thylcne Oxide Ethylidene Norbornene Formaldehyde Hexane Isobutyiene Isoprene Isopropyl Acetate Isopropyl Alcohol-Skin Mercviry Methyl Acrylate-Skin Methyl Alcohol-Skin M.B. Isocyanate (MDl) Methylene Chloride Morpholine-Skin p-Nitroaniline-Skin Phenol-Skin Phosphoric Acid Phusphorus Trichloride Styrene Toluene Trichloroethylene Vinyl Acetate Vinyl Chloride Vinylidcne Chloride 3310 200 170 350 93 440 3400 3730 300 710 680 4l0 2180 90 830 330 2830 800 3000 300 1050 3249 4l4 1530 4920 3000 4920 2920 OO 8000/4H 6000/5H 500/4H 2000/4H 20 2000/4H 250/4H 210 20 . 15 lO/lY 4000 6/3 OM 13-8 200 169 pg/m^ 300 0.13/30M 500/8H 100 mg/m^ 376 200 110/8H 20 4000/4H 8ooo/4h 8000/4H iooo/4h 500/4H 250/4H 2000/4H 250/4H 1000/4H 100 8000/4H 4000/4II 250/4ll/260DI 280 280 2200 820 2000 320 3890 2500 1950 2320 1 LD^O - lethal dose 50 percent kill wr.Lo - lowest published toxj.c concentration Lo - lowest published lethal concentration M - Minute H - Hour Y - Year DI - Day Intermittent JAKrcj 1/2/75 OO LSQZV3 VZ SYNONYMS SUBSTANCE Acetic Acid Acetone Acetonitrile Acrylamide-Skin Acrylic Acid Acrylonitrile-Skin Allyl Chloride Ammonia Aniline Benzene 1,3-Butadiene Butane Butyl Acrylate Carbon Disulfide Carbon Tetrachloride-Skin Chlorine Chloroform Cyclohexylamine-Skin 1,2-Dichloroethane Dicyclopentadiene Di-iso Butylene Diphenyl Diphenylamine Epichlorohydrin Ethyl Acetate Ethyl Acrylate-Skin Ethylene Oxide Ethylidene Norbornene Formaldehyde Hexane Isobutylene Isaprene Isopropyl Acetate Isopropyl Alcohol-Skin Mercury Methyl Acrylate-Skin Methyl Alcohol-Skin M.B. Isocyanate (MDl) Methylene Chloride Morpholino-Skin p-Nitronniline-Skin Phenol-Skin Phosphoric Acid Phosphorus Trichloride Styrene Toluene Trichloroethylene Vinyl Acetate Vinyl Chloride Vinylidene Chloride Ethanoic Acid Dimethyl Ketone Cyano methane Vinegar Acid 2-propanone Acrylic Amide Propenoic Acid Propene nitrile 3-Chloropropene - Aminobenzene Benzol Biethylene Bivinyl - Butylester 2-propenoic acid Carbon Bisulfide Tetrachloro methane - Trichloro methane Aminocyclohexane Ethylene Dichloride EDC 3a, 4,7,7a-Tetrahydro-4,7-Me t hanoindene 2,4,4-Trimethyl pentene-l/2,4,4-Trircethyl pentene-2 Phenyl benzene Anilino benzene l-Chloro-2,3-Epoxy Propane Acetic Acid, Ethyl Ester Chloro-1,2-Propylene Oxide Acrylic Acid, Ethyl Ester Oxirane Ethyl Propenoate 1,2-Epoxy ethane 5-Ethylidene-2-Norbornene Formalin 2-methylpropene ENB Methanal 3-methyl-l,3-butadiene Acetic Acid, Isopropyl Ester Isopropanol Quick Silver Acrylic Acid, Methyl Ester Methanol p,p'-Diphenyl methane Diisocyanate Dichloro methane Tetrahydro-2H-l,4-0xazine l-amino-4-nitro benzene Carbolic Acid Ortho-phosphoric acid Phosphorus Chloride Vinyl benzene Methyl benzene TCE Acetic Acid Vinyl Ester Chloro ethane 1,1-Dichloro ethylene 1 \ JAK:cj 1/2/75