Document 0JwqDVaxkK4eyqJJpmD53Dqxm

1 SOUTH CHARLESTON PLANT ( UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS P, O. BOX 8004. SOUTH CHARLESTON, W. VA. 25303 January 21, 1980 Mr. R. L. Hollingshead Pitney, Hardin & Kipp, Esq. 163 Madison Avenue Morristown, New Jersey 07960 (Maliko et al versus UCC) Subject: Tribukh et al "Working Conditions and Measures for their Improvement in Production and Use of Vinyl Chloride Plastics" Gigiena i Sanit. (10) 38-44, 1949 Dear Bob: The subject paper has been repeatedly cited as evidence of the early incidence of vinyl chloride and polyvinyl chloride toxicity. Other sources have stated that the author concluded that the toxic effects came from the plasticizers used. In an effort to clarify the discrepancy a copy of the original article in Russian was obtained and retranslated. The translation does not clearly attribute cause and effect to anything. The authors' conclusions are as follows: 1. Organo chlorine compounds, hydrocarbons, hydrogen chloride and carbon monoxide are given off during the fabrication of PVC plastics. 2. These cause irritation of the mucous membrance in the upper respiratory tracts. Dusts and vinyl chloride resin vapors cause dryness and atrophy of the mucous membrance and cause chronic bronchitis over a long period of exposure. 3. Changes in worker upper respiratory tracts and hepatitis indicate the need for further health research. 4. Use of sovol (diphenyl chloride) as a plasticizer causes acne type skin injury to workers. 5. Protective clothing and showers should control the skin injury from sovol. 6. For cleaner work atmosphere the decomposition of PVC must be reduced and a rational ventilation system provided. UCC 068727 Mr. R. L. Hollingshead Page 2 January 21, 1980 The authors are aware that diphenyl chloride and chlorinated naphthalenes (sovol and golowax) attack the parenchemal organs (parenchymal refers to distinguishing cells of an organ-not too clear). Severe toxic effects are acute and sub-acute yellow atrophy of the liver. They make no connection between this knowledge and the worker hepatitis. Other items of note are: 1. The specific process source of the PVC resin is not identified except that for shoe soles. Emulsion PVC is used for molding shoe soles. This type of PVC would be quite dusty and low in residual vinyl chloride monomer. Because of the widespread use of emulsion process PVC in Europe during this time it could be reasonably assumed that all the PVC used was made by this process. 2. The identification of potassium stearate as a stabilizer is in error. This is a soft soap probably used as a lubricant and non-stick agent. The stabilizer was probably some form of basic lead carbonate. No mention is made of pigments, fillers, etc. used which would contribute to dust and to toxic effects. 3. Neither diphenyl chloride (sovol) nor chlorinated naphthalenes golowax are good plasticizers for PVC. Dibutyl phthalate is the primary plasticizer. The other materials were probably added to the DBP to cheapen the cost or to get certain properties in the plastic. 4. The authors attribute the presence of organo chlorine compounds in the processing fumes to cleaved molecules of vinyl chloride (PVC-?) in different quantitative chain compound compositions. Boettner et al (Analysis of the Volatile Combustion Products of Vinyl Plastics) reports the major organic compounds given off during combustion pyrolysis of PVC are benzene and toluene with no condensible organo chlorine compounds. 5. Sampling and analytical techniques were not very sophisticated in 1949. Reactive gases such as hydrogen chloride and carbon monoxide could be accurately determined but the detection of hydrocarbon gases was based on the condensation of the material with ice or dry ice thus there could be no entrapment or measurement of very volatile hydrocarbons such as ethane, propane, butane or vinyl chloride. If organo chlorine compounds were truly collected and identified they must have resulted from the chlorine containing plasticizers in the plastic. UCC 068728 Mr. R. L. Hollingshead Page 3 January 21, 1980 My own conclusion is that this study should not be related to any vinyl chloride or polyvinyl chloride health effects. The translation was done by A. D. McCormick Company, P.0. Box 187, Dunbar, West Virginia 25064 not by Union Carbide Corporation. RNWJr:ke cc: J. W. Whittlesey Very truly yours R. N. Wheeler, Jr. UCC 068729 WORKING CONDITIONS AND MEASURES FOR THEIR IMPROVEMENT IN PRODUCTION AND USE OF VINYLCHLORIPE PLASTICS. Tribukh, S,L,, Tikhomirova, N. P., Levina, S V,, Kozlov, L. A. Gigiena i Sanit. (10):38-44(1949) The production of vinylchloride plastics and also the different goods, prepared from them gained in the last decade considerable importance. In the meanwhile from hygienical point of view, it was little studied. The basic raw material for the preparation of vinylchloride plastics is vinylchloride resin, which is prepared from vinylchloride, a colorless gas, condenses at 12 - 14 in liquid with a specific weight of 0,86 - 0,90. vinylchloride, on its turn, is prepared by the reaction of gaseous decompo sition products of petroleum vapors (vinyl) and gaseous chlorine. Sub sequently, the vinylchloride condenses by using dichloroethane and is sub jected to polymerization in autoclaves. In this way, polyvinylchloride resin is the product of vinylchloride polymerization. Due to the resist ance to alkali, diluted acids, ethers, benzin and lubricating oil.polyvinyl chloride resin is used for the preparation of acidresistant fillers, fabrics for overalls, substituents to hides, etc. At the preparation of various goods, the polyvinylchloride resin is plasticized with complex ethers of phthalic acid (dibutylphthalate), phos phoric acid (tricresylphosphate), mixture of diphenylchloride (sovol), or chlorinated naphthalenes (golowax). The selection of the plasticizer de pends on the assigned use of the plastic to be prepared. According to the data of the literature, vinylchloride belongs to weak narcotics. Its narcotic concentrations for humans are within the limits of 75 to 250 mg/l. According to the data by Petropavlovskii (1942), vola-' tile substances, liberated, when vinylchloride resin and plasticizers are heated to 13O-I650 cause in animals under the condition of one single inocculation, depending on the concentration, the following phenomena* UCC 063730 2- - irritation of the ocular mucous membrane* respiratory disorders, damage of the central nervous system, breakdown in the coordination of movements, and death, after appearance of asphyxic convulsions. Sovol and golowax, introduced into vinylchloride plastics, as plasti cizers, have general and local toxic effect. In their overall action on the organism, sovol and golowax are close to chlorinated fatty hydrocarbons. Basically they attack the parenchemal organs. Severe toxic effect takes place in form of acute, or subacute yellow atrophy of the liver. In the literature, cases with lethal outcome are described, caused by the toxic effect during the production with vinylchloride naphthalenes (golowaxj, and diphenyls (sovol). The local action of sovol and golowax causes acne-type skin eruptions and erythematous-vesicular dermatitis. We studied the working conditions at the finishing of vinyl chloride plastics under factory conditions in a vinylchloride plastic plant, using vinylchloride plastics as substituent for hides and for insulation of electric wires. Production of vinylchloride plastics>- In the vinylchloride plastics plant, the vinylchloride resin (a white powdery mass) is mixed with dibutylphthalate, or with sovol in mixing apparatus, at a temperature of 80-100. Then, the compound is transferred onto rollers, the surface of which is heated to 130-l60V. At the end of the rolling, the vinylchloride fabric is cut up in nar row tapes, which are further sorted and packaged in boxes. 31 -3- During the hygienical inspection of the vinylchloride plastic plant, the air of the working place was examined on its sovol-. organochlorine compound-, and hydrochloric acid vapor content. The obtained results are plotted in Table 1. Table 1- Organochlorine compound, sovol and hydrogenchloride content in the air of vinylchloride plastic plant 7 KQ iUtMTpJU U ft Ml, j Ha3Ba,me OTje.'.e.iMfl / Me;?} b3)ithr npclJ z x.TopopraHM- | neCK.ie coejii- j hb iiib. a tom Miic.ie coaoa * 1 U ! x.TOpacr;jS BO.topoa FT curo to biit e.i.h o e ' <? B niLijy xia noi.-rpesa 5" C.te!ue;i:ifl it Bd.lbltJtfKa To me Csep,aosoq.ioe j B ce:=xt,ie nosiswi ; Ha I ypojtti .iwxa.M.i ra.^iero \ io y si a?i{ : CMBUie.lB. KOM.IO ld.iTOi . . I .11 i' c.q;;HTe.ta so spen 1 Biarpysua ;co>tii03iia:!ii . - i12. Ha pa:oqeti xe:;i saai- j uosmiKi.................................... (j y crcai xm oauaac^ero j naacTMkira ...................... j/O y palaqsro m;ct3 ;3ep! JtoBtiiHKa ...................... ; 0,00a 4* He r>6 1,1 jiyaten 0,003 0,06--0,C8 j 0,0.3 C ,01--0,08 /s^He ooiiap; iksh 0.2--0,97 I I O.WJ 0,27 lo tie -.'OiiapyvKeii 0,005 `* * 1. Name of the departmenti 2. Place of the sample taking} 3. concentra tion in mg/lf 3a. organochlorine compounds,included sovol^; 3b. hydrogen chloride} 4. preparation} 5* mixing and rolling} 6. the same; 7. dril ling} 8, in the exhaust hood of the heated sovol} 9. in the middle of th chamber, at the respiration level of the workers} 10, at the mixer at the time when the components were mixedj 11. at the mixture, at the time when the components were discharged} 12. at the working place of rolling} 13 at the deck for the cooled plastic compound; 14, at the working place of the drill operator; 15. not detected;. In the air of the working places of the vinylchloride plastic plant, as one can see this from the data of Table 1, the concentration of organo chlorine compounds fluctuated between 0,005 to 0,27 mg/1. In the prepara tion department sovol vapors formed at its heating, discharging and trans portation, The concentrations of organochloride compounds, found in this place (0,005 mg/D can be attributed, most likely, in great part to sovol. ^ On account of the insufficiently developed method to determine separately organochlorine compounds, they were determined summarily. UCC 068732 At the mixers the organochlorine compounds were found in an amount from 0,01 to 0,08 mg/l, and in the working place of the rolling - from 0,2 to 0,97 mg/l. In the product sorting department the organichlorioe compounds, usual ly, did not exceed 0,05 mg/l. We detected hydrogenchloride only in the dif ferent samples in amounts, not exceeding thousandth part of milligram. In connection with the use of sovol, soiling the skin with ingredients, in the composition of which sovol was introduced causes serious danger. On the skin of the hands of the workers we found organochlorine compounds. To fight the contamination of the air, the plant was mounted with influent and exhaust ventilation with automatic driving. The exhaust ven tilation was constructed on the principle of local exhaust from the hood?, placed over the basic sources of gas evolution. The efficiency of the ventilation, as this was demonstrated by the sanitary-technical inspection,was insufficient, on account of the fact,that the air-feed was carried out with a rate of only 7-8 m/sec on the level of the shoulders of the workers. The unpleasant sensation, caused by si milar way of air feed, together with the infiltration and cooling of the compounds on the rollers forced the workers to overlay the damper of the sprinkling valves and already with this, the air current, escaping through the different leakages, decreased the work of the exhaust device, deviat ing the convective current, which got up from the rollers. Besides, the closing of the influx nozzle, disrupted the balance between the influx and the exhaust and attracted inorganized admission of contaminated air from the neighboring places. UCC 068733 -5- A significant defect of the ventilation system was the insufficient efficiency of the low-capacity hoods, arranged over the decks for the ready products and over the mixers. Much more effective are, according to our project executed orifices over the mixers in form of tents with open front wall (see the figure). At a productivity of 1 000 m^/hour these orifices practically completely localized the separation of noxious gas. f Scheme of the tentlike openings of the mixer. Use of vinvlchloride plastics as substituent for hides>- In the pro duction of vinylchloride footwear, the basic raw material is polyvinyl chloride resin, which is prepared by the polymerization of vinylchloride in a water-emulsion method. The temperature of the decomposition of this resin is 130 - 150. As plasticizer here dibutylphthalate and as stabiliz er potassium stearate is used. The compound for the sole is prepared by mixing textile scraps, sa turated with dibutylphthalate, and vinylchloride resin in the mixer. The obtained compound is piled on the heater to 1?0 - 200 and rubbed through, after this with Vaseline in the press mold. The, in this way filled press form is closed, it is maintained for a f w minutes, and then is placed for a short time under the hot press. -6- The composition for the upper footwear is obtained by mixing a deter mined amount of polyvinylchloride resin and dibutylphthalate in the mixer. The mass is kept there for aging 12 hours at a temperature of 70. After the aging the compound is rolled at a temperature of 120-140 with the ad dition of potassium stearate. The vinyl chloride plastic compound, obtained after the rolling is rapped in textile and pressed at a temperature of 160. The analysis of the air for noxious gas and vapor content in the plant of vinylchloride footwear production is plotted in Table 2. Table 2i- Concentration of gases and vapors in the air of working places in vinylchloride footwear manufacturing plants in mg/1 I 'X.iopopraHHie- 1 CKHe coeaHHeHHs ^ HC1 7C I (cyMMapno) MCCTO B3HTHA 4 KOHUeHipauHa a mr/.i CO npo6 /. 3 * sljsjrl a i C- iI y aaabUOB . , lb y npeccos . . \c B noyetuenHH cupoiHoit | I III 0.14 0.48 0.35 0,0-28! 0,036 0,0320,07 0.350.2 -- ` ' I I III 0,022 0.25 1,13 0,65.0.008 0,036 0.055 0,21.2.61 1.23 -- -- 0,019 j !1 0,53 1,2 0.92 0,03 0.17 0,23 0,10 0.6S 0,23 -- -- 0,01 I' 1. place of the sample takingt la. at the rollers lb. at the press; lc. at the welding place;2.organochlorine content; 3 minimum; 4. maximum; 5. average; 6, concentration in mg/1; 7, total. The organochlorine compounds, which evolve at the thermal finishing of vinylchloride resins, represent cleaved molecules of vinylchloride in dif ferent quantitative chain compound compositions. In the air of the working places at the manufacturing of vinylchloride footwear, we found these com pounds in an amount from 0,14 to 1,2 mg/1. Here we found also vapors of hydrochloric acid in concentrations from 0,008 to 0,17 mg/1, hydrocarbon vapors (determined summarily) from 0,21 to 2,6l mg/1 and carbon monoxide vapors within th limits of 0,01 to 0,022 mg/1. UCC 068735 -7- The contamination of the atmosphere by organochlorine compounds and vapors of hydrochloric acid increases in proportion with the temperature increase at the heating during the different manufacturing operations. The ventilation of the working place was carried out by means of a few exhaust devices, originally destined for local exhaustion. In spite of the comparatively . high frequency of air exchange (10 - 20), the effi ciency of the ventilation was insufficient. Its basic imperfection was the lack of local removal of the gas, evolved during the work at the pressing rolling and welding of the footwear. The hood over the welding working benches, usually used in this kind of production, was not efficient and could not be considered as a local ex haust device, because at the welding of the vinylchloride footwear, the eases evolved on the level of the knee of the seated welder, in the imme diate closeness to his face. A more radical device in the given case is a vertical exhaust channel against each working place. The removal of th air can be carried out through orifices in the platform of the working bench the upper part of which, thus, should be used as planar exhaust channel. Satisfactory effect can be observed also in case of exhaust through a horizontal box, arranged on the surface of the working bench. The rate of suction through the exhaust orifices should not be less than 6 m/sec. Use of vinylchloride plastics for the insulation of electric wiresi- In the factory, where vinylchloride plastics are used as insulating material for electric wires, the covering of the wires with vinylchloride envelope, is carried out on extruders. During the time, when the vinylchloride plastic compound is dried in th drying chambers, and also at its fusion and at the discharge of the wires from the hot envelope from the head of the extruder, in the air of the working space we found the following volatile substances (Table 3). ucc 063736 -8- Table 3 MecTO B3autsi npo6 h XaopopraHHiecKne coejrfeHa 3 ii HC1 !, C J | (cyvMapHo) ii kjJue:iTpai*H B mt/.i CO i , ' ia V--- -"x ^xU t<Afe J= Z3 11 2 =X 3X f=t ' 105PC! uX(z9 z3e*; k<i C3 10 ' ^ *2 j >* zr Z="; Ux ^J>-x*- ZZ 5X U X *t--? Z 7. y uinpHuvtauiH ibi b 3one yawxa.iHH paOoiero . . . Haj nposoJ^'i, noicpbiTbiM 6 rypqqeti n.iacTjiaccOH . . B cepciHHe no^ewenvu J| Haa cyuiH.ibHUM unca&OM 7 | Q.C03 0,1 0.00! 0,06 03 0,6 0.:4 * 0,65 He o6.u- _ - 0,017 0,05 i pyite.il `' 0.00*: 0,088' To xe j0, 0 0,14 -- 1 -- j 1 0.11 , - 0.02 0,016) 0,08 1 0.2* I - J -- !I |i 1. Place of the sample taking* 2. organochlorine compounds* 3. concentra tion in mg/1* 4. summarily* 5* at the extruder in the zone of the workers respiration* 6. over the wire* coated with hot plastics* 7. over the drying chest. 8. was not fteteeted* 9. minimum* 10. maximum 11. in the center of the place. In the composition of the volatile substances, evolved at the heating of the vinylchloride plastics, up to 120 - 140, there is an organochlo rine content of 0,003 to 0,6 mg/l, vapors of free hydrochloric acid from 0,001 to 0,06 mg/l, hydrocarbon vapors from 0,08 to 0,6 mg/l, and carbon monoxide vapors from 0,01 to 0,05 mg/l. The ventilation of the plant was accomplished by means of exhaust hoods, arranged on the telescopic downstroke over each extruder head. The gases, evolving at the drying of the plastic compound in the drying chest and at the cooling of the vinylchloride wire after discharging from the extruder head, arrived in the atmosphere of the working places,maintaining in them a considerable concentration of toxic substances. 737 -y- Results of the medical examination of the workers!- A randomly se lected group of workers in the inspected plant was subjected to medical ex amination. In the vinylchloride plant 48 men were examined, mainly roller workers. At the rhino-larynx examination, in a great number of th workers, in the upper respiratory tracts (in the nose, larynx, and thrachea! white films of dust were observed, which were formed as a result of the mixture of dust with the mucus. These films were compact at the touch and could be removed from the surface of the mucous membrane only with diffi culty. In 1? men hyperemia of the mucous membrane of the upper respiratory tract was found. Chronic bronchitis was detected in 13 men. As to the change in blood circulating organs, one must mention vascular hypotonia (90 - 100/45 - 50) in 13 men, moderate hypertonia in one, arterio-cardio- sclerosis - in 5, The condition of the gastro-intestinal tract was charac terized in 10 examined workers by chronic gastritis and in 2 by chronic colitis. In 15 workers there were alterations in the liver in form of more or less pronounced hepatitis, accompanied in 2 examined workers by cholecystitis. Regarding the blood, 29 examined workers had low hemoglobin count; on - 46$, 22 50-55$* and 6 56-6O7S, The blood picture and the ROE were with out peculiarities. One must pay attention to the skin diseases (acne, bleakheads), es pecially on the face, the neck and the chest, found in the examined group. The skin injuries were found not only on the face of those who were in contact with sovol, butalso on those, who were not in direct contact with it, but were working inthe same place. Evidently, the skin disease was caused by the action of sovol, when its vapor was sorbed. UCC 068738 10- In the chemical plant 25 female workers were examined, mainly those, working at the presses and welding with a long working record of 3 - 6 years in the said professions. In some of them, examined for ear - larynx different degree of hyperemia of the mucous membrane of the upper respira tory tract was observed, on its whole extent, or only on the organic parts. Chronic bronchitis was found in 5, mildly expressed emphysema of the lungs in 3 and remaining signs of pleurisy in 2, As to the cardio-vascular system in 14 men vascular hypotonia (R/R 90 - 110/55-65) and in 4 mildly expressed hypertonia (R/R 140 - I65/8O85) was detected. Thudding sound of the heart, its enlargement and the data of the ECG1 Low T-wave of heart, not less than by 2 basic abduction and the roundness of the S - T interval, gave foundation, in some cases, to diagnose distrophy of the myocardium. In the examined group, in 6 workers hepatitis was diagnosed. At the same time,in some persons, simultaneously liver and stomach disease was de tected. Not in one of the liver disease cases could we find in the anam nesis, or at the examination,signs of jaundice. Neither did we detect any bile pigment in the urine. In a considerable number of the examined work ers small swelling of the liver, without characteristic pain and sensitivi ty at palpation was observed. Analyzing the results of the medical examination, one must remark, that in a known part of the workers, changes in the upper and deeper res piratory tracts were detected. These findings are confirmed also by the data of the literature. One must pay attention to the high percentage of skin injuries, which is, no doubt connected ethiologically to the action of sovol. CC 68739 11- The presence of hepatitis in some workers, in contact with vinylchlo ride resin and vinylchloride plasticizers deserves serious consideration. Therefore further dynamic observations on the state of the health of the workers, who are in contact with vinylchloride resin and its plasticizers, are necessary, to prevent the development of severe liver damage* . Results , 1. - Into the composition of volatile substances, which form at the thermal finishing of vinylchloride resins and plasticizers, during the manufacturing organo-chlorine compounds, hydrocarbons, vapors of free hydrochloric acid and of carbon monoxide enter, 2. The action of these volatile substances are manifested in the ir ritation of the mucous membrane, mainly of the upper respiratory tracts* lengthy influence of finely dispersed dusts and vinylchloride resin vapors cause, besides, dryness and atrophy of the mucous membrane of the upper respiratory tracts, and is also responsible for the development of chronic bronchitis. 3. A considerable number of hepatitis among the examined workers, and also the change in the upper respiratory tracts, raise the question of the necessity for further dynamic research on the state of the health of the workers and to take a series of therapeutic-prophylactic measures, in particular by organizing heat and moisture*Inhalation of drugs for the workers, 4. At the use of vinylchloride sovol, as plasticizer, on most workers acne type skin injuries, with preferable location on the face and neck, were observed, 5 For the prophylaxis of skin diseases at the work with sovol, the following complex sanitary measures have to be taken* 1) securing for the workers work underwear and outfit* 2) construction of sanitary showers (alkaline) 12- with separate undressing for home and work cloths. At the sanitary pas sage, there must be a vapor chamber for the low temperature steaming of underwear and work outfit, at a temperature of 110-120; for one hour. The plant should be equipped with wash basins with hot and cold running water. 6, For the sanitation of the atmosphere, it is necessary to decrease, as much as possible, the degree of vinylchloride resin decomposition at its thermal finishing. This must be attained by standardizing its heat re sistance, and also by controlling the temperature when the rollers, the presses and other equipment are heated, not to exceed 120-130, Of extremely great importance is the rationally equipped ventilation system, calculated on maximum screening-off the source of gas-, vapor- and dust separation. In connection with the fact, that in some factories the inflammation of the condensate was observed, which occurred in the exhaust ventilation tubes in contact with open flame, the exhaust apparatus must be projected by observing the conditions, adopted by the construction legislation for construction , designated for the mixing of inflammable gaseous mixtures. uec 068741 TaC-inua 9. 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S \"- UCC RF.C*.P "JOURNAL TITLE Volume No.: Issue#: Pages: / -\ " UBRARY-770 Year: X If Photocopy requested is not attached, see other side of this form for report. j532 DBF v /?`/3 - /Sd -------------------------------------------------------------------------------------------------- IJCC 068750