Document 0J98B9Omq9xNEQ4eOXKgdJnBO

Ol'lS/e* 10:33 tJ02 S8 8770 VT. RECORDS CTR. Mor.utkl of Ha.as.rdi to Health from Chaaiaola Ul*d kt Th* Plants and Laboratories Of Carbide and Carbon Chaaioula Corp. aioos hIc i*1 A\r>. 5-h*.^ f^A<+ .b,.. copy flunber CtypTijhtad jS-w Carbide i Carbon Cbaniwili Cofjj. Cooperatively prepared by the Medical Department, C S C C C Industrial Toxlcoloey Department, U.C.C. . WorHfl Laboratory, C & c c C, South Charleston '" Chemical Hygiene ?8llawBhlp, Mellon Institute, Pittsburgh* Pa, first Edition May 1, 1949 iiiieiiiii UCC100487-1 Page 001 uCC manual.max luce,100487 UCC 100487 0J/15'fl9 10:23 T7S02 aas 3T7o VT. RECORDS CTR. (3ooe * 3-a^I-i 5-1-49 K" 1 ^ 430 V/!:;'-: ' - * J ' : r r! /, v;4K .i . . - i <r-i: worrit This, manual- la inwndsd fortho us* of: ernployeea. ofiths^Carbide' St Carbon Chemicals Corporation, who -have responsibilities fnr.nsmiTuetinTirig, engineering and research operations. Tha Judgements expressotl herein refer to health hazards, in' chemical manufacturing procedures', which-nra conducted with reasonable caro. They stress accidental single exposures^ opposed to repeated or substantially continuous exposures. tlo tabular summary can predict the safety-of. technical applications - of chanicals, particularly where human contact or exposure is inevitable, oft-repeated)or-jprolongodThis manual is net intended for such predictions. Each application must be judged on its owv meritst with full Knowledge of all the.'particulars. The estimates In this manual are based upon experiments with small animals and the-experience of industrial, physicians.;;:; In"*'large nmber of Instances analogy in chemical structure has been rolled upon to allow predictions where no observations have been recorded. The judgements expressed arc necessarily tentative and subject to revision an experience . accuBulutes. Despite care used Is cheeking the tables there undoubtedly : exist inconsistencies and omissions, hi^i-jsR * flhsn crude mixtures are being handled the hazards may be . somewhat greater than for the partially purified or substantially purs chemicals considered herein. .joco/i '* ' . The undersigned expects to serve os a clearing house for the . collection of new observations end correctiona in preparation for subsequent editions. .. r Henry F. anyth, Jr. Mellon Institute Pittsburgh 13, Penna. UCC100487-2 Page 002 uCC manual.max luCC, 100488'" UCC 100488 OS-'H/flS 10-24 tt902 B88 3770 VT. RECORDS CTR. Soot Syobola used to describe relative hemrd \ 1. No residual injury is to be expected froa as 1 exposure svn if no treatment is applied. *b Minot- residual - injury may result fron eomo-aaeideutol .{.jepo'eureB'`if 'no-troatnent is applied..; 'i' 0 ' ...- i * --U'j'i* . i,tj;( I.'; 'V J . r:JU ^.Vi .... J,i.. I t vt*J Major'-reeiduftl' injury nay result if no treatawntf ie- : i; o-.` O? b.i.yj [ -applied.'1-- 1- . Ti.v.r >! * *! iiji'.7 'u : 'li.iJ.n'... U,'. - ; . | -tLT 4..^fiajor residual-in jury may result in -spit** of .ptbapt . i^F.iu'-.vitreataient.-, r * ' J ,2,.` iijt* it :-j t,\ ti-jiri';" ' ' . !> ipjsysioal properties of chemical make. the .particular ! .-.uj-j. ija exposure almost impossible. .... u. --* .. .... . _i:` I .-see gqiplenontal notes on loft side - ofjpage j i {* ui OJiiO'.iV1;1*.^ y. i-*y ^ . J i ' ;.! . * : iv-:''' ',J \ .i.i i !'." V;L-:!'J .'.` tUu-Uii'l ..Ta;tv; v.-,.'1C.. : WO-iiis i .r ' ; ,.u.o=>.; :! . .'...^si.iVi -Lin^/auii * Acetaldehyde . * '..I I " t,..; i* j: .t^iXU May sensitize the slcin r:i vur r.!Ami..' : -------------..! r.-j.-; J.:.>-.i =.. .. .; 1 * Aoetoaootacetyl othylcnediamine , Mey sensitise the skin tJTK't .*!:; .. ; * ^otony2jh3 etor.e ... .Jf< .r..5 f '.,l L.*`. .*' J V. , I l.f f* i LCi! . ..iuztt ir.i Stains the skin browi UCC100487-3 Page 003 uCC manual.max UCC 100489 OJ/ia/98 10:28 tJSO! 888 8^70 VT. RECORDS CTR. '3)008 rage 31 4Ca' Chemical Jlnlatlve Hazard ol ; Swallow fSKB dlcin Ureath Fluid, " j in* - Pene Irrita ing ' ' Puat, ; i i ! tra 1 tion tion '' ' Vapor or Oust. Vapor in Bye Vanadium (metal) 1' I "Varsol" , r i- j i 2 1 :1 1 .3. .. "l ^ .2 ' 1 3 ' victoria blue B base dye . . . . . * 12fIfi 3 ; Vinyl acetate ` - 11 1 . Vinylo c atylene .... * . f! a j! _ ,`Wli " i . i Vinylbutyl CAUBIXOL j i 2 . 1------------3 1* ! 2 . . :i-- I. r \' i .. is ' i- "3 3 2. 3 1 1 3' w I Vinyl butyl ether ' \\ 2 i! -a-- i *3 1 j Vinyl butyrate .................................. i 2 12 | i r\ *. 3 1 ! Vinyl chloride Vinyl chloroethyl ether !2 i :. 3 1 | 2 1i 2 i1 1 3 4 2 .. X 2-Vinylcrotomildehyd8 !*. 3 .j 4 ^ .frry M 4 Vinyl etiyl ether 1 viny.l 2-ethylhexyl ether - - -.... - . J ' 2 2 1 2 i i;' 3 l i*--..... 1l 2 i 2 l1 1 2 ! vinyl texyl ether 2 !2 ? 2 ,2 2 Vinyl ieobutyl irther j Vinyl isopropyl ether j "Vinylite" re3ins | "Vinylite'1 adh;=i'vss .... ! Vinyl ?-methoyethyl ether 1 Vinyl raethyl ether 1 2 2 1 ...... J 1 2 .2 ! j2 | 1 i i2 1 ii i |1 | i !i 1 i j2 l ii !^ *i> 3 !2 12 S4 1 1 1 1 3 : 1 w H ---------- } 1 J See additional notes on laft aide of thia page. 5 rini'ii ii! alii it 1111lllfl iiHI UCC100487-4 Page 004 uCC manual.max UCC 100490 SiorAin 0tries Manufacturing Chemists A (RWOU Iff)) 246 Woceeju Butzotxo --15th and H 3*k, N. . Vaxksmctqh 5. D. C t October 2, 1953 To Heabers of; General Safety Ccoolttee . Medical Advisory Caaaittee To Chairmen of; - IAPI Conmittee Metal Packages Committee Miscellaneous Packages Committee Tank Car Ccmlttae Water Pollution* Abatement Consaittee Subject: Chemical Safety Data Sheet vrmX CHLCRXDg - SD-5^ _________ Gentlemen: - Appended hereto ia the FINAL draft for the above referred to Chemical Safety Data Sheet. The text contains a number of revisions suggested by meeker* of the Committee and producers and users of vinyl chloride. In order to comply vitb wr publication schedule It is earnestly requested that all consents and corrections be placed at our disposal not later than October 23. O -LI Copies of the draft are being sent to those producers and users who have re ceived copies of the previous draft in the hope that those paragraphs on vhlch they had consented might .he re-examined, and if necessary, deleted or corrected. The producers and users ars The Dev Chemical Company, The Flrestooe Plasties Company, B. F. Goodrich Chemical Caspany, Goodyear Tire A Rubber Company, Inc. and Naugatuck Chemical Division, United States Rubber Company. The writer appreciates very much the cooperation of all concerned in completing the present draft. AJW:mba Attachment 011-1953-00003883 iHunifiiiiiiiiiiiniiiiiiniiiiiiijiiiiiiiNBHMiiiiUf 10/2/53 I CC 004192 - lo -I CC 004215 iMgitvl Pn-ct*. [nn.iiI2-,HSip ucc 004192 uCC manual.max 11/0IMPMMkllOMMfMtVM. Tt i'P t- > y< ****** ***.************ * * * * ** * CHEMICAL SAFETT DATA SHEET SL-5^ a * l* * Properties And Essential Information a * * * For * # *. Safe yTLAHng And Use # * *' Of * *. ** * VHtYL CHLORITE *' * * * *4 * * * * *, Adopted 1953 - * # * * * * * * * *"* ***#*******# * # * # Chemicals in "ny fora, can he safely stored, handled or used if the physical, chemical and hazardous properties are fully understood and the necessary precautions. Including the use of proper safeguards and personal protective equipment, are observed. . SEAL Manufacturing Chemists* Association, Inc. 2U6 Woodward Bldg., 15th` & E Sts., S. W., Washington 5, D. C. IIIIIIHIU 011-1953-00003886 Page 001 uCC manual.max /D INrMMMlOH *trn*L 1(1* Che illcal Saf^t" *' VINYL i i' moIW - SUMMARY vinyl chloride 1 highly volatile extremely FLAMMABLE compressed gas vhlch is ordinarily ."bandied In liquefied form under pressure. It has a mild anesthetic action t in concentrations above 500 ppm.and the vapors are Irritating to the eyes. Precautions necessary In hendHwg the material are detailed In the body of the Safety Data Sheet. Key points to consider for safe handling include: 1. Keep avay from heat, sparks and open flame. 2. Provide adequate ventilation. .* 3. Ground equipment and containers before discharging to reduce danger of ignition from static sparks. '' 4. In discharging do not heat containers above 50C. (I22y.). Ho beat should he applied to tank cars. 5* All equipment etc. should be of steel and have a designed working pressure of at least 100-150 psi. 6. In the event of accidental leaks, spills or vbenever excessive vapor concentrations may be encountered only personnel equipped vlth approved respiratory protection should be permitted In the contaminated area. - 7. Chemical safety goggles should ha worn vhen* discharging containers or tank cars . or whenever there is a danger of the' liquid or saturated vapor cooing In contact vlth the eyes. 8. Waste disposal should be avay from any source of Ignition. Dilute phenolic residues before discharging to sfver. . _ In case of fire use carbon dioxide or dry chemical extinguishing equipment. In the event of contact vlth the liquid remove contaminated clothing Immediately, for eyes flush Immediately.vlth large quantities of vater for at least 15 minutes while seeking medical attention. Is 011-1953-00003887 Page 002 ucc 004212 uCC manual.max ft/o iMronMAHOM mrniivAt. (!'# 1. HAKE 2. PROPERTIES. ........................................ ^. 2.1 Grade ....................................................................... J 2.2 luyorta'-v Physical sad Chemical Properties 2.3 Hazardous Properties ............................................ 3. USUAL aBTrPTHS CURTAInur................... . . .. . . 3 1 Type and Size...................................... .... 3.2 Label or Identification ...................................... 3-3 Disposal sad Return Precautions. ...... 1*. UNLOADING AND EMPTYING.................................. "... 4.1 Health Hazards ....................................................... 4.2 Fire and Explosion Hazards 4.3 Cylinders................................................................... 4.4 Tarir Cars............................................................... .... 5 STORAGE................................................................................ 5-1 Hazards. ........................................................... : . 5-2 Ccaditions of Storage........................................... 6. HAHDLIHQ............................................................................ 6.1 Health Hazards........................................................... 6.2 Fire, Explosion, and Polymerization Hazards 6.3 Spills and Leakage ............................................... 6.4 Eaployee Education and Training..................... 6.5 Personal Protective Equipment.......................... 6.6 Engineering Controls............................................... 6.7 Ventilation ........................................... 6.8 Tank and Equipment Cleaning and Repairs . . 6.9 Repackaging............................................................... ' 7- WASTE DISPOSAL . i , 8. HEALTH HAZARDS AHD THEIR CONTROL . '..................... 3.1 Hazards.................................. '.................................... 8.2 Prevention and Control.............................. .... . 8.3 Personal Protective Equipment.......................... 8.4 First Aid and Medical Care.............................. (WARRANTY CLAUSE) Page iiiiiiiiiiiiiimiiunll ttEiRnNIInMII 011-1953-00003888 Page 003 uCC manual.max ucc 004213 Mr* Brlntoa Sermon -Tbs Dev Chemical Company . :.'h. > VINYL CHLORIDE V. Chemical Names: Adopted October,. 1953 1. NAME Vinyl Chloride * ChlOrOctbyleae Chloroetheoe l Ccnsoa Name: ' Vinyl Chloride Tnrwfiil a: CHgCBCl '. 2.1 Grade 2. . PROPERTIES ' Technical with inhibitor. (Purity of sample 99*^2jl) 2.2 Important Physical and Chemical Properties r* Bolling Point................................................... Color...................................................................... -13.8C. Colorless or water white Corroslrlty ....................................................... '' Noncorroslve at normal atmospheric tempera* tures when dry (moisture free). In contact with water at elevated temperatures vinyl chloride accelerates corrosion of Iron or steel. Critical Pressure . . . . .......................... 4- '. Critical Temperature.............................* . 52-7 atmospheres 158.tC. (318.8P.) Deliquescence .............. No Explosive Limits (Percent by Volume In*. Lower Air) Upper 22 Plash Point.................................................................. 78C. (-180.4?.), Open Cup Nygroscoplcity................................................. No' *Many of the data recorded under this paragraph were determined In the research labora tory of one of the large producers of vinyl chloride end are based oo a technical grade material having a purity of 99.h2jt. Materials fren other sources may vary In accordance with the nature of the Impurities or the character of the Inhibitor present. IBffilSffi 011-1953-00003889 Page 004 ucc 004214 * 'D uCC manual.max m to IM P O ilM A fiO M Ignition Temperature, Autogenous .Light Sensitivity......................... 472.22C. (8air''. Hot a factor <n >. " ) ' chloride Jfeltlng Point .................................. (Freezing Point) . Molecular Weight Odor..................... ... Pfcyilcal State ............... ... -153*71C. (-245?.) 62.50 ' Sweet awlllng gas. Gas at ordinary temperature and pressure. Liquid under pressure In cylinders or pressure vessels at rooa temperature. Reactivity ........................................................... . Polymerises readily In presence of air, sunlight, oxygen dr heat. This behavior Is due to the presence of a double bond. Otherwise vinyl cHloride Is quite stable. Specific Gravity....................................................... 9121 20/20C. (water* 1.00) Vapor Density..................................................... 2.15 (Airs 1.00) . Vapor Pressure..........................*...................... 25^0 m- of mercury 20C. (66?.) 2.3 Hazardous Properties 2.3.1 Bealth Hazards (See 6. Health Hazards and Their Control) Vinyl chloride presents no very serious problem In general hand!Ing aside from the risk of fire and exploaioa. The presently accepted upper Halt of safety aa a health hazard Is 500 ppm. 2.3.2 Fire Hazard . .. ` Vinyl chloride vapors fora flamable mixtures with air at all temperatures shove 7SC. (-108.4?.). 3. USUAL SHIPPING CQOTAIHERS 3 .1 Type and Size 3*1.1 Approved IOC cy.linders, tank cars and tank trucks designed to carry` liquid gases under pressure and provided vlth safety relief. apparatus. 3*1.2 All parts of valve and safety devices in contact vlth contents of containers must be of metal or other material, suitably treated if necessary, which will not cause 1* formation of any acetylldes. A good practice Is to dismantle all valves for Inspection before each loading. Approved cylinders Include ICC - 4B300 and ICC - 4BA300, ICC - lilllllffigDIIIIWIllBIBIilllinillll 011-1953-00003890 Page 005 ucc 004215 uCC manual.max AA 1001- THE DOW CHEMICAL COMPANY Abbott Road Buildings, Midland IRSS,168022 TECHNICAL SERVICE AND DEVELOPMENT Schober, A. E. AA-1001 11-28-58 EVALUATION OF VINYL CHLORIDE AS A PROPELLANT FOR AEROSOL PAINTS A propellant system comprised of 8076 vinyl chloride and 20% pro pane performs satisfactorily in aerosol paints. Flammability of *si- a paint system containing this system is very similar to current commercial formulations. Polymerization of vinyl chloride did nolj^ occur under severe test conditions in the presence of known poly merization catalysts FeCl 3' AlCl^ and air. A savings of 5*4 cents per 16 ounce unit can be realized by aerosol paint fillers if this propellant system is used rather than dichlorodlfluoromethane (Freon 12, Genetron 12, Isotron 12). Based on 1957 production figures, 11.9 million pounds of dichloro dlfluoromethane were consumed in aerosol paints and thus a 5 to 10 million pound potential exists for vinyl chloride based on 50 to 100% replacement. ctrv.. rry 'ciOvju -ft.-:.:' *1 ii';l 7i\] A" CC^T:r.L EESEARC! `i'dA IK__i. (9 220 00 - Halocarbons, Miscellaneous New Applications)! S,W`` SEP 24 '59 TYPE OF REPORT1 Laboratory .PACES:. 7 RESEARCH CLASS)FICATIO+I: MATERIAL . USE. QttrutUTtOH ( * COMPL ETE REPORT) 0LANDCfil(3Capi..) EXECUTIVE RESEARCH *J . C. Van Horn *A. J. Pastor *E. W. Larabee, ARB *W. U. Seiler, ARB *R. L. Brown, 433 *R. K. Treichler, Fpt., A-2421 E. B. Barnes, Fot., B-1210 *A. E. Schober *W. C. Bauman, 687 *Problem No. 9 220 00 TS&D Files -TYPE STAGE- -DISTRIBUTION . ^pibo in midland cm HAY 2 5 1993 *J. D. Kerr *D. K. Ballman, 47 *T. J. Christiansen, ARB *N. R. Peterson, 433 W. A. Henson. 433 R. H. Smith, Fpt., B-121 *M. E. Pruitt, Fpt., B-1215 *M. J. Stoesser, Sarnia R. A. Lindsay 0. C. Cessna r~0 A" V FOR USE OF DO* EMPLOYEES ONLY ff iiiii iiiiiiiniiiiiniiiiii R&S168022-1 Page 001 B&S168022 uCC manual.max mi iiiiBiiiiiiiiiin R&S168022-2 Page 002 INTRODUCTION: An investigation was conducted to determine which Dow products could be used as low cost propellants for aerosol paints. The aerosol industry currently utilizes dlchlorodlfluoromethane, (Freon 12, Genetron 12, Isotron 12) hereafter called Propellant 12, as the propellant. Any replacement for Propellant 12 should be a low cost, liquifiable gas, low in toxicity, compatible with paint systems and have a boiling point such that substantial pressure will be exerted by the gas at room temperature. Knowing these requirements it was decided that vinyl chloride should perform satisfactorily as a propellant. The limitations of vinyl chloride as a propellant were determined. The limitations considered were; vapor pressure, possible polymeri zation of vinyl chloride containing formulations, flammability of finished formulations and market potential. The flammability of vinyl chloride would be its primary drawback. However, this should not be a detering factor as present aerosol paints are very flammable. _ EXPERIMENTAL WORK: Vapor Pressure . Propellant 12, the pressurizing agent presently employed, exerts a pressure of 70 psig at 7CfF. A typical aerosol paint consists of 60$ paint concentrate and 4o$ Propellant 12. This combination exerts a pressure of about 38 psig at 7Cf F. Vinyl chloride boils at -13.27C. and at 7(fF. exerts 50 psig. Because paint concentrates are formulated to give a satisfactory spray pattern with Propellant 12 it was, therefore, necessary to Increase the pressure of vinyl chloride to give a spray pattern similar to commercial systems. Propane was chosen as it is an inexpensive liquifiable gas exerting a pressure greater than 70 psig at 7CPF. For 70 psig at 70F., 76.9 vinyl chloride and 23.1$ propane were required. This combination when packaged with 60$ paint concentrate produced a satisfactory spray. The 60$ concentrate and J40$ R&St 68023 uCC manual.max -3- tllilllll |l!i in hIIIIhH lllliillulil IIIIMItll !ill llll R&S168022-3 Page 003 propellant mix exerted a pressure of 42 pslg at 7CfF. 42 psig is In excess of allowable package pressure. Commercial systems are packaged In containers in which the pressure may not exceed 4o psig at 70F. Forty percent of a propellant system (20* propane, 8o* vinyl chloride) and 60* paint concentrate exerted an acceptable pressure of 37 psig at 70 F. and produced a satisfactory spray pattern. This 80:20 mixture was used for further evaluation. POLYMERIZATION OF VINYL CHLORIDE Because vinyl chloride monomer will undergo polymerization under certain conditions, it was necessary to determine if this could occur In aerosol paint systems. Dow vinyl chloride contains 1000 ppm phenol as a polymerization inhibitor. A literature search revealed that t-butyl catechol is also an effective polymerization inhibitor, while air and certain metals and their salts catalyze polymerization. Tertiary butyl catechol was considered as an alternate inhibitor in the event aerosol packagers considered phenol too toxic. Aerosols were prepared with two lacquer solvent systems using the vinyl chloride/propane mix as the propellant. System No. 1 is suggested in the CSMA Aerosol Guide while System No. 2 was sug gested in the literature. ' They are: No. 1 No. 2 Methyllsobutylketone Butyl acetate Isopropanol Butyl Cellosolve (Dowanol EB) Toluene 75* - - 75* 10* 10* 10* 10* 5* 5* Aerosol samples were prepared containing variables which could occur in aerosol containers. Our object being to determine if these variables catalyzed polymerization of the phenol containing vinyl chloride and if so. would TEC inhibit the polymerization? R&S168024 uCC manual.max -4- Alr, ferric chloride, aluminum chloride and HgO were chosen as variables being possible in present aerosol systems. Air can-be introduced during the filling operation, particularly If: the pressure fill technique is employed. Ferric and aluminum chloride? can re sult if there is any hydrolysis of vinyl chloride and subsequent attack of the steel or aluminum container. Water can be present either as a contaminant during the filling operation or coupled with solvents. Samples were prepared with the following variables: 1. IOC# vinyl chloride/propane + air 2. 100# vinyl chloride/propane + air + 500 ppm TBC* 3. IOC# vinyl chloride/propane, no air . 4. 100# vinyl chloride/propane, no air + 500 ppm TBC 5. 4o# vinyl chloride/propane + 6C# No. 1 6. 4o# vinyl chloride/propane + 60# No. 1 .+ 500 ppm TBC 7. 4o# vinyl chloride/propane + 6C# No. 2 8. 4o# vinyl chloride/propane + 60# No. 2 9. 40# vinyl chloride/propane + 6C# No. 1 500 ppm TBC 0.1# anhydrous FeCl^ 10. 4o# vinyl chloride/propane + 60# No. 1 + 0.1# r anhydrous FeCl^ + 500 ppm TBC 11. 4c# vinyl chloride/propane + 60# No. 1 + 0.1# anhydrous AlCl^ 12. 40# vinyl chloride/propane + 60# No. 1 + 0.1# anhydrous AlCl^ + 500 ppm TBC 13. ^0# vinyl chloride/propane + 60# No. 1 +' 0.1#'.distilled water 14. 40# vinyl chloride/propane + 60# No. 1 + 0.1#'.distilled water + 500 ppm TBC After two months storage at 12CfF., the containers were examined. Samples 1-8 were in excellent condition. No corrosion or polymeri zation was evident. Samples 9-12 had crystal formations in the liquid phase. The crystals were collected and analyzed. Analysis showed these crystals to be inorganic with no organic material present. - Tertiary butyl catechol III! lllllllllillllllllllllllli R&S168022-4 n Page 004 R&S168025 uCC manual.max 1111! lillllliliHH R&S168022-5 Page 005 FLAMMABILITY: Present aerosol paint formulations containing 6056 concentrate and 40# Propellant 12 are very flammable. The completed formulation when sprayed is capable of subataining a flame when the source of ignition Is removed. Aerosol paint containing 60$> of solvent sys tem No. 1, 32 vinyl chloride and 8# propane were prepared and subjected to the same flame test. No appreciable difference was noted between this formulation and the above mentioned commercial formulation as far as flammability was concerned. The flame of the vinyl chloride-propane containing system was blue while the other system was a typical yellow. MARKET POTENTIAL: Vinyl chloride was considered primarily a propellant for aerosol paints. However, It should be applicable In any aerosol formulation where flammability is not a drawback. This would Include presently flammable formulations and formulations used only outdoors such as weed killers and outdoor insecticides. In 1937, 36.5 million cans of aerosol paints were produced*. To fill these cans 29*7 million pounds of complete formulations was required. Most formulations consisted of 60# concentrate and 4c$ Propellant 12. Based on this ratio, 11.9 million pounds of-Propel lant 12 were consumed. At present it Is difficult to determine the sales volume of aerosol weed killers and outdoor Insecticides. Propellant 12 is 26.3 cents per pound in tank cars. The use of the vinyl chloride/propane propellant system would result in a savings of 5-4 cents per 16 ounce container, assuming the propellant to constitute 4o of the weight. This savings would be the primary reason for any manufacturer using vinyl chloride/propane rather than Propellant 12. At present vinyl chloride is being used as a propellant in Japan and Germany. The reason expressed for Its lack of usage in the United States at present 1b its flammability and the subsequent *AA Report 907 uCC manual.max R&S168026 6- - dangers encountered in filling. However, current aerosol paints are flammable and many manufacturers have installed explosion proof equipment to avoid such accidents as happened to Thomasson of Pennsylvania (Krylon) several years ago when the paint concentrate caught fire destroying the entire operation. Therefore, the use of vinyl chloride/propane should not entail expensive modification of existing filling equipment. CONCLUSIONS: 1. Eighty percent vinyl chloride and 20$ propane can be used as a replacement for Propellant 12 in aerosol paints resulting in a savings of 5-4 cents per 16 ounce can. 2. Under most conditions encountered in aerosols, polymerization of vinyl chloride would not occur. 3. Flammability of aerosol paints containing vinyl chlorides/ propane is not noticeably greater than commercial systems. 4. In most aerosol plants filling equipment would not have to be altered to use vinyl chloride/propane. 5. If vinyl chloride/propane were used exclusively In 1957. 9-5 million pounds of vinyl chloride would have been required. The following companies are engaged in production of aerosol paints: Aerolite Products, Incorporated 106 Ashland Avenue West Orange, New Jersey Capital Packaging l44l South Circle Avenue Forest Park, Illinois T. J. Dunham Paint Company 115 Woodward Avenue Yonkers, New York Inland Paint and Chemical Company 2144 West 49th Street Chicago, Illinois Kerr Chemical Company 9 South Farvlew Avenue Park Ridge, Illinois R&Jol 68022-6 Page 006 R&S168027 R&S,168027 uCC manual.max -7- Red Ram Chemical Company 755 Utica Avenue Brooklyn 3 New York Red Devil Chemicals, Incorporated 30 North West Street Mount Vernon, New York Red Lion Chemical Co. 146 North Charles Street Red Lion, Pennsylvania Ronor Corporation 1360 West Ninth Street Cleveland, Ohio SprayOn Products Company 2075 East 65th Street Cleveland, Ohio Stalfort Pressure-Pak 321 West Pratt Street Baltimore 1, Maryland Thomasson of Pennsylvania, (Krylon) Norristown, Pennsylvania Cleveland Aerosol Packaging 9801 Harvard Avenue Cleveland 5 Ohio caj I! Illlliliilllllllltllllllillli R&S168022-7 Page 007 uCC manual.max R&S168028 Mr. P. G. M-gr'**"1 292 Marilann Arenua - Hth floor Mr. P. A. Corlo Dr. C. U. Darnahi May 27, 1959 TSCHIZCAL SXRVICX Dtr Mr. Kaprnaacn: We an attaching a copy of a lattar fron Tha Pantaaota Company concerning a toxicity prohlan that they --countered la the um of rlnyl chloride. They ban previously apohea with Dr. Dexnahl on the telephone about tola problem, and Um lattar U w a nanlt of oor ra^uavt that they adrlaa ua in writing of juat wfcnt type of lAforaa&lan thny would Ilka ua to iod than. Dr. Dez--fcl baa adrlaad that working up the Information on eaaa hietoriaa would Da ratbar tlaa f and remire a oonalderahls amouat of work on aowona'a part. Va aewd to decide bow anefc information and bow nuefc tlaa wa wlch to apand In supplying this lnfeznatlen to this cuetomer. We would appreciate your dlscuaafag It with Dr. Dexaakl and advicing him bow far ha abould w> la getting together Infomat lna that would ba halpful to Tba Pantnaota Ceapaay. CnteClnllaad/nf Attach--nt ary truly youra, . . OR'G'Nii :"; :d C. P. h\ Cl.^La.v-i UCC12997-1 Page 001 uCC manual.max ucc 012997 REPORT HO. AA-1154 ROOnaiR'SfH lo 0928 THE DOW CHEMICAL COMPANY Midland. Mlchigan PROBLEM NO. 9 2l8 00 09261 TECHNICAL SERVICE AND DEVELOPMENT Kaufman, J. DT3 AA-H5T 7-2^-59! EVALUATION OF VINYL C RIDE AS A PROPELLANT FOR AEROSOLS Experimental Vd/k has been conducted on mixtures of vinyl chloride with chlorofluorocarbon aerosol propellants to determine flash point characteristics and explosive limits. Tills work has shown that a mixture of 25$ vinyl chloride, 37 1/2$-Propellant 11 and 37 l/2$ Propellant 12 could replace a 50-50 mix of propellants 11 and 12 without increased hazard during filling operations or exces sive flammability of the final product. This 50-50 mix of 11 and 1 Ts representative of the propellant component of many commercial aerosols.. Further, the work has shown that a mixture of 16$ .vinyl chloride, 4$ Propane and 80$ Propellant 12 could similarly replace the pure Propellant 12 now used for pressurizing aerosol paints. These aerosols would represent a potential total market for 30,000, )00 pounds of vinyl chloride based on present aerosol sales. Since vinyl chloride does not have strong odor or strong solvency proper ties and is more easily evaporated than methylene chloride or Chlorothene, it would not meet the sales resistance on these points .that those.two products have. The patent picture is encouraging. Since customers have some reservations about handling highly flam mable propellants, it will probably make necessary the sale by Dow of blended mixtures. Although more work on this project seems de sirable, the influence of current sales policy and profit considers tions must be weighed before proceeding. (9 218 00 Halocarbons In Aerosols, General) TTPe of report. Laboratory and Market Research Report _L3_. PACES:. RESEARCH CLASSFICATWH; MATERIAL . CHSTRIBUTtOH. ( -IPLETE REPORT) -TYPE DISTRIBUTION EXECUTIVE RESEARCH *J. C. Van Horn *A. J. Pastor *E. V. Larabee, ARB *R. K. Treichler, Fpt., A-2421 *E. R. Cowherd, ARB *W. G. Bauman, ARB *J. D. Kerr *D. K. Baliman, 47 T. J. Christiansen, ARB *R. H. Smith, Fpt., B-121 *M. E. Pruitt, Fpt., B-1215 *M. J. StoeBser, Sarnia -R. A. Lindsay synJtlfatMJb J. D. Kaufman - - : Problem File 9 218 00 TS&D Files 0. C. Cessna ' JN WIOLAND CRI MAY 2 5 1999 j1 iL CENTRAL RESEARCH INDEX -DLXD: BI.R.UJG 14 fete R&S168008-1 Page 001 uCC manual.max 2- - INTROPUCTION In AA Report 1001, A. E. Schober discussed the potential for vinyl chloride in aerosols. Laboratory work lndicated-rthat Propellant D (80$ vinyl chloride, 2C$ propane) would serve as a complete replacement for Propellant 12 (dichlorodifluoromethane) in aerosol paints. This investigation covered vapor pressure characteristics, polymerization difficulties, and flammability problems. Paints seemed to be the major market for a vinyl chloride based propellant since many flammable solvents are used in a paint concentrate and the finished product is very flammable. It was felt that the potential for vinyl chloride in other areas would be restricted due to the necessity for precautionary labeling on cans and modification of filling lines to handle more dangerous materials. A study of markets for propellants in that report indicated a 5 to 10 million pound potential for vinyl chloride If Propel lant D was employed as a total replacement for Propellant 12 In paint aerosols. Price authorization was obtained (0.12 per pound F.O.B. Freeport In 4000 gallon cars) and extensive field contacts were made to determine customer Interest. Questions raised by customers indicated that further informa tion about the material would be necessary, but that the cost saving appeared quite appealing. Customer contact indicated that while flammability considera tions relating to labeling were important, the requirements of the ICC In relation to shipping flammable aerosols were more important. These ICC requirements demand that the flash point of the contents of a standard aerosol container be above 20F. This is not difficult to achieve when a fluorochloro- carbon is used as a propellant but limits the applicability of vinyl chloride severly since the pure material has a flash point of -108F. ,, ill IlllllSIllllllllllllIlilUllllilUl R&S168008-2 R&S168009 uCC manual.max -3- Paints use pure Propellant 12 as a pressurizing agent since the paint concentrate depresses the pressure of 12 to less than 40 pounds at 70P., in the finished product - a require ment for beer can type aerosols. Other aerosols use. mixtures of Propellant- 11 (trichioroflucromethane) and Propellant 12 to attain a pressure of 38 pounds at 70P. Pure vinyl chloride by itself exerts a pressure of 38 pounds at 70aF. The propane is added to Propellant D to raise the pressure of the mixture to that of Propellant 12. Various customers pointed out that mixtures of vinyl chloride with Propellants 11 and 12 might produce a finished aerosol which would pass the ICC test. Further, a mixture which had no explosive limits could probably be used safely in all present filling equipment without modification. Although the ICC regulations seemed to sharply reduce the potential for vinyl chloride in paint aerosols, the other possiblity and customer Interest opened up broad new markets for vinyl chloride. Further laboratory work was In order to determine the flammabil ity and explosive characteristics of mixtures of vinyl chloride. Propellant 11 and Propellant 12. EXPERIMENTAL The laboratory work covered in this report breaks down quite naturally into two areas, the Investigation of flash points of finished aerosols containing flammable propellants and the explosive hazards of mixtures of vinyl chloride with the fluorinated propellants. A. FLASH POINT DETERMINATIONS ON PROPELLANT D MIXTURES Some years ago, the ICC regulations required the use of a special container for aerosols classified as flammable. Due to the higher cost of this container, a special exemption was granted allowing the shipping of a flammable product in Will lj!IIHIIIIIIf!l!!llllllinillllllII!lll R&S168008-3 Page 003 uCC manual.max R&S168010 -4- a regular container, provided the contents flashed above 20F. This requirement seems to cause little difficulty at present as shown by tests 1-4: TABLE I Sample No. Propellant Concentrate Flash Point 1 100$-12 Formula III* 119F. 2 100$-D 100$-12 Formula III ** Comral. cone. No, <-25"F96F. 100$-12 Comml. cone. No. 2 86F. 5 30$-D Comml. cone. No. 1 38F. 70$-12 6 30$-D Comml. cone. No. 2 38 F. 70$-12 7 30$-D Formula III 38 F. 70$-12 8 30$-D Formula III 38 F. 70$ With 50$ of MIBK replaced with methylene chloride 9 10$-BCDF Formula III 62 F. 30$-D ' 60$-12 10 10$-BCDF Formula III <-22F. 40$-D 50$-12 * From Pressurized Packaging by Herzka and Pickthall. It contains 24.4% solids "{nitrocellulose 43.5$, non oxidizing alkyd 43.5$, dibutyl phthalate 13.0$) and 75*6$ solvents (MethylIsobutyl ketone 80$, Dowanol EB 10$, isopropanol 5$, Ethanol 5$) and is mixed 50$ by weight concentrate, 50$ Propellant 12. ** Obtained from aerosol fillers Three samples were prepared using Propellant 12 as the sole pressurizing agent. When Propellant D replaced the Propellant 12 entirely, flash points well below 0F. were obtained. Extensive testing showed a straight line relationship between $ of Propellant D in the pressurizing portion and the flash point of the finished product when the $ ill! !l!ilini!IRII!!lll!ll!illl R&S 168008-4 Page 004 R&S168011 uCC manual.max -5- of Propellant D In the total propellant mix did not exceed 35$. (See Figure I) When the ratio of D to 12 was 35/65, the flash point of finished paint was approxi mately 20F. Increasing the ratio of Propellant i) above this value seemed to result in a sharp decline in flash point to well below 0F. It appears that If the per centage of D is below 35, the propane flammability is suppressed by the Propellant 12. Concentrations of D over 35$, result In a concentration of propane over 7$ in the total propellant mix. Since propane is the most volatile flammable component. It would be expected to give very low flash points when present even In low concentra tions. A ratio of 30$ Propellant D, 70$ Propellant 12 was chosen to give a margin of safety and this propellant mix tested with several aerosol paint concentrates and all flashed at 38F. Concentrates 1, 2 and 3 above, were tested as well as another commercial concentrate. Even when 1/2 of the methyl lsobutyl ketone in concentrate No. 1 was replaced with methylene chloride, the end product flashed at 38F. (See Table I, tests 5-8). Various mixtures of bromochlorodifluoromethane with Propellant 12 and Propellant D were tested. A mixture of 10$ bromochlorodifluoromethane, 30$ Propellant-D, 60$ Propellant 12, was used as pressurizing agent with concentrate No. 1 and the product flashed at 6lcF., but when a mixture of 10$ bromochlorodifluoromethane, 40$ Propellant D, 50$ Propellant 12 was mixed with concentrate, it flashed at -22F. This would tend to show that bromo chlorodifluoromethane would be of limited value in raising the flash point of aerosol paints, since it is quite a bit more expensive than Propellant 12 or Propellant D. (See Table I, tests 9-10). mill! R&S168008-5 Page 005 uCC manual.max -6- B. FLASH POINT DETERMINATIONS ON VINYL CHLORIDE MIXTURES To determine the applicability of vinyl chloride in non paint aerosols, a series of experiments using viny\_ chloride itself rather than Propellant D were carried out. Various mixtures of Propellant 12 with vinyl chloride and one of the three commonly used vapor pressure depressants were prepared. These were tested by themselves without any concentrate for flash point. A mixture of 36.4$ Propel lant 11, 36.4$ Propellant 12, 27.2$ vinyl chloride, gave no flash to dryness. This mixture possibly could be used as a replacement for 50$ Propellant 11, 50$ Propellant 12 mixtures now sold for such products as space deodorants, hair sprays, insecticides, etc., if other factors were all right. This mixture was tested for pressure with a pressure cylinder and gauge arrangement used in earlier pressure determinations in Technical Service and Development. Theoretical calcula tions show that any mixture of 50$ Propellant 11, 50$ Propellant 12, with vinyl should have a pressure of 38 psig at 72F., if they, form an ideal solution. The actual readings taken were 5 pounds higher at 70F., which would exceed the pressures allowed in beer can type aerosols. Lower pressures could be easily obtained by reducing the ratio of Propellant 12 to Propellant 11 which would also reduce costs since Propellant 12 costs roughly $0.05 per pound more than Propellant 11. Mixtures of Propellant 12, vinyl chloride and methylene chloride or Propellant 12, vinyl chloride and Chlorothene were tested but these latter two compounds seemed less effective than Propellant 11 in suppressing flash points. C. EXPLOSIVE LIMIT DETERMINATIONS From the safe handling standpoint, a propellant which ill iiiiisiiiiigDiiiiiiiiiinEiiiiiiiiiiii R&S168008-6 Page 006 uCC manual.max R&S168013 -7 presents no explosion hazards Is desired by aerosol fillers. Equipment was available In the gas laboratory for running explosive limits of various materials. The equipment differed in several details from that used by the Bureau of Mines for similar tests. Although these differences may have some effect on the data derived, it is felt that the information obtained is reasonably close to that which would have been obtained with the other equipment. However, some anomalous results were recorded with the gas laboratory equipment and it is felt that any further work should be done with apparatus which is similar in all respects to the Bureau of Mines apparatus. The literature indicates that propane forms explosive mixtures with air when propane is present in quantities from 2$ to 9$. Vinyl chloride has limits of 4$ to 22$. The gas laboratory reported that Propellant D had limits of 4$ to 15$. Following work on flash points, a mixture was prepared in an aerosol can which consisted of 70$ Propellant 12, 30$ Propellant D. When this liquid was vaporized and tested, it exploded in the range of 9-5$ to 23-5$ of the mixture in air. Various ratios of Propellant D to Propellant 12 were formulated and tested. . $ Propellant D $ Propellant 12 30 70 25 65 80 18 82 Lower Limit Upper Limit 9.5 23.5 13.0 Not tested for 17.0 " 19.5 No explosive mixtures found Mixtures of 50$ Propellant 11, 50$ Propellant 12, with vary ing quantities of vinyl chloride were prepared and tested. Illll llllllllllllillllllllllilttlllli R&S168008-7 Page 007 R&S1680K uCC manual.max -8- $ Vinyl Chloride $50-50 Mixture 27-2 26.4 26.0 72.8 73.6 7^.0 Lower Limit Upper Limit 18 26.5 19.5 26.5 No explosive mixtures found CONCLUSIONS FROM LABORATORY WORK 1. Mixtures of Propellant D with Propellant 12 can not exceed 35$ Propellant D if the final aerosol paint is to pass the ICC test for flammability. A 30-70 mix gives a desired margin of safety. 2. Bromochlorodifluoromethane does not effect flammability sufficiently but may have more influence on explosive limit s. 3. A mixture of 27-2$ vinyl chloride, 36.4$ Propellant 12 and 36.4$ Propellant 11 with no concentrate had no flash point to dryness. Since most concentrates are non-flammable, finished aerosols using this mixture for pressurizing should pass the 20F. flash test easily. 4. Mixtures of less than 26$ vinyl chloride in a 30-50 mix of 11 and 12 had no explosive limits. 5. Mixtures of less than 20$ Propellant D with 80$ Propellant 12 had no explosive limits. AREAS FOR FUTURE LABORATORY WORK 1. Determine the explosive limits with equipment constructed in accordance with the Bureau of Mines suggestions. 2, Determine the effect of bromochlorodifluoromethane and related materials on explosive limits. Although bromochlorodifluoromethane did not appreciably change flash point characteristics, it might have greater effect on explosive mil iiiii]iiiiiiiiiniili!!!E R&S168008-8 Page 008 R&S168015 uCC manual.max -9- llmits at economically feasible concentrations. 3. Explore the effect of vinyl chloride in various formulations. Although it has low odor, evaporates readily and has only moderate solvency (these have been objections to both methylene chloride and Chlorothene) there may be other factors which need to be considered. 4. Explore possibility of obtaining patents on various mixtures for use in aerosols. A Canadian patent (No. 5^1*786) has been issued for a mixture of Propellant 11, Propellant 12, and isobutane and an American patent is understood to be applied for. 5. Explore the possibility of modifying ICC regulations con cerning shipping aerosols. The 20F., flash point seems very arbitrary and It Is conceivable that another test could be devised which would be a better Indication of safety but would allow the inclusion of more vinyl chloride. 6. Investigate further the flash point and explosive charac teristics of mixtures of Chlorothene, vinyl chloride and Propellant 12, as well as mixtures of methylene chloride, vinyl chloride and Propellant 12. Though these two How products are less effective than Propellant 11, supressing flash points, they may be worth considering since they sell for less than Propellant 11. DISCUSSION These areas of investigation are interesting but It was decided that sufficient data was now available to determine the market potential for vinyl chloride in aerosols to enable a decision concerning continued activity in this area. The potential markets can be broken down as follows: ill!! !H:S!;!!!!!!!!!!!!!!!!!S!!l!"!!l!!!!:iji R&S168008-9 Page 009 uCC manual.max R&S168016 -10- Product Hair Sprays SpB C6 Insecticides Room Deodorants Residual Insecticides Paints Cans Filled Estimated In 1$?5 Average (XlOc11 Can Size 120 1/2 lb. Estimated $ Propellant In Can 70 Cost Saving Estimated To Filler Propellant Per -10,000 Consumed Lbs. Cans* (X10&) $ 78.00 42 39 3/4 lb. 60 1/2 lb. 90 95 $150.00 $106.00 20 30 24 3/4 lb. 40 1 lb. 80 45 $133.00 $108,00 15 18 * Based on a delivered price of vinyl chloride or Propellant D of $0.l4 per pound. These figures are very close to those obtained when a filler uses Chlorothene or methylene chloride as a 50$ replacement for Propellant 11. The first four categories represent a market for vinyl chloride alone, since they predominantly use mixtures of Propellant 11 and Propellant 12. Paints would utilize Propellant D, since they currently use Propellant 12 exclusively. Since experimental work indicates a maximum of 20$ Propellant D, 80$ Propellant 12 or 25$ vinyl chloride, 75$ Propellant 11- mix form non-explosive mixtures, the total potential market in these products is as follows: Product Lbs. Total Propellant Lbs. Propellant' D ' Vinyl Chloride Paints Hair Sprays Space Insecticides Room Deodorants Residual Insecticides 18,000,000 42,000,000 20,000,000 30,000,000 15,000 j 000 3,600,000 2,800,000 10,500,000 5,000,000 7,500,000 3,750,000 29,550,000 Since the propane raw material cost is very low. We may consider Propellant D as little different from pure vinyl chloride. Thus, the total potential market for vinyl chloride in these aerosol products is 30,000,000 lbs. It would seem reasonable to expect Dow to capture 33$ of this market or 10,000,000 lbs. II llll!0IIIIIIIIIilllll!lllllIIIIIIUIIII R&S 168008-10 Page 010 R&S168017 uCC manual.max -11- These five product areas represent 280,000,000 cans. 100,000,000 cans of products such as shaving lather and dental cream were produced last year, but represent little potential for vinyl chloride. Smaller miscellaneous uses add up to another '90,000,000 cans which might represent some market for vinyl chloride but are difficult to evaluate at present. The aerosol market has grown at 20^ per year in the past and is still growing quite rapidly. The potential for vinyl chloride would expand along with this growth. FACTORS INFLUENCING A DECISION CONCERNING FURTHER WORK 1. Advantages A. Laboratory and market data indicate a reasonable Dow market for vinyl chloride in aerosols of 10,000,000 lbs. In proportions indicated above. It would present no fire hazard, and would not seem to cause difficulty from odor, wet spray or high solvency as do methylene chloride and Chlorothene. The cost saving to the aerosol filler for mixtures of vinyl chloride or Propellant D would be about the same as those obtained with methylene chloride or Chlorothene. The product would therefore seem to present few sales hurdles.' B. Good possibility exists for patenting a mixture of vinyl chloride with some of the fluorlnated propellants. This patent could be licensed even if no effort was made by Dow to sell vinyl chloride. Maximum sales of vinyl chloride would require active promotion by Dow, C. If Dow chose to market a Propellant 11-12 vinyl chloride mixture, a discount on purchases by Dow of the Propellant 11-12 mix would appear reasonable, since Dow would be providing the sales and technical service effort. Ill lilllillilll!!*!!!!!!!!!! R&S168008-11 Page Oil uCC manual.max R&S168018 -12- D. It would establish Dow as a propellant supplier and would thereby aid sales of methylene chloride, and Chlorothene. E. The sale of 10 million pounds of vinyl chloride for blending would entail the purchase of about 30 million pounds of fluorinated materials. This would establish Dow as the major consumer of these chemicals. Such a status would likely strengthen our sales position as a supplier of carbon tetrachloride and chloroform to the propellant producers. P. It is possible that small quantities of bromlnated hydro carbons would favorably influence the explosive characteristics of vinyl mixtures. This might mean greater percentages of vinyl as well as the inclusion of other Dow products. 2. Disadvantages A. It would be necessary to handle at terminal points and sell, approximately three pounds of fluomiated propellants for each pound of vinyl chloride unless the customers bought the vinyl chloride directly and did their own mixing. It Is not know at present how many customers would be willing or able to do this. B. Heavier technical service would be requested. It is estimated that 5-10 people would be necessary to develop and promote the material. C. The product would compete in some areas with Chlorothene and methylene chloride and could reduce the sales of these products. D. The accepted M.A.C. for vinyl chloride is 500 ppm which should not represent a serious hazard. However, our . nil! iiiiiiiiEiiiniiiiiiiiiiiiuiiiiiiiii R&S168008-12 Page 012 uCC manual.max R&S16801SI -13- Biochemistry Laboratory Indicates that it may request a lowering of this M.A.C. by the Conference of Governmental Industrial Hygienists as a result of experimental work now in progress. CONCLUSIONS 1. From a technical and market standpoint, a sizeable potential exists for vinyl chloride. Before conducting further work in this area, guidance by management based on sales policy and profitability is required. INDEX HEADINGS Vinyl Chloride, Propellant For Aerosols Flash Point, Mixtures of Vinyl Chloride With Dichlorodifluoromethane and Trichlorofluoromethane Explosive Limits, Mixtures of Vinyl Chloride With Dichlorodifluorome thane and Trichlorofluorome thane Flash Point, Mixtures of Propellant D With Dichlorodifluoromethane and Trichlorofluoromethane. Bromochlorordifluoromethane, Flash Point Supression of Propellant D and Dichlorodlfuloromethane. in iiiiiiiiiiiiiiifiiiiiiniiiiiiiiiiii R&S168008-13 Page Q13 uCC manual.max R&SI 68020 K*H 3 X S TO THC INCH 359-2 KiurriL * (an* Co. u*i tv ii.a.a. -14 FIGURE I R&Sl 68021 0\ 1 : 5t J >0 1 }Relationship of Flash Point Of ": *fierosol Can Contents To Of i 1 I5ropellant D In The Propellant I'ortlon (Various Paint Concen- *> * ii tirate s Used . 1i __ 1__ !1 ii 1 --i i i i i T'" * i 0 *1 J X :c x * y li ii ii -- ;4 j. i i -- - _ . _ . -4- =g= x\--it m . .. 5m= O ooo 2 - ! co i ii ,i j : 1i ;-- 0| i i i 0t L_ 1 ii ( "1 < x X ; ;i =? WJ (Q i ~ d .1. . == *!f i1 j... == -- .. - i- ... 1...... . ii1__-_! _i_! ,____ i. 1f - j 0 ---1i-- i | -11--- 1-- --ii-- 3 Li.L _1L _ 1 ji 1 i LJ.- ! : t i__ : ! 'jI --- 1--- i| ii 1 --i ---i1---! ! 1! Jr i >' r 1 ' / j --^ ` "i i1 i 1 !!1 1 __ ii__ 1 1 Ir & S ,1 6 8 0 2 1 Sjcoarpt fro. latter written1* Dr* ** Mastromatteo, Dividon of Industrial Hjr giane, Departemnt of Health ?r0T^nc* o{ Ontario, dated October 13, 1959, re , fVinyl Chloride experiments ? animals._--- ------------------------------------- 7 On April 1U, 1959, groupe of nlaala comprising 5 aloe, 5 rata and 5 guinea plgB vra exposed to varyii* ao"?c*ntrmtion ct vi^l chloride in air for a period of 30 minutes. fta axpoai** " eondisted in a special animal chamber. Cancan trati one of 10, 20 and 30 pi*1* of ohlari.de in air vara us ad. An addendum to this latter will daaciiti11* theee ooncantrationa vara calculated. An additional group of 5 guinea pigs ? *P--* * conemitration of Up5f vinyl chloriia in air on tha sans data. In all # eaparintal animals vara involved, including 15 control animals. Ihe control Y**"*^* oonprised 5 mioa, 5 rats and 5 guinea plga, and these control animals earned* *** *" nil stocks and vara fad and housed in tha same mnnor as ths salmis. A summary of ths results obtained is given balovi Tbn Par Cant Viqyl Jhlorlds in Air JtLcs Hats All vara lying down st the rr 'jjf A0 mi* amoving tremors and tvitchingj reoovsiy vaJ sir) no dealhs. 4 All vara 2H_r still at ua* ^nd of tha experiment) reoovery was quick in fresh air) no dsatha. Guinea 0ns was in aids poeitlonj four vara standing) recovery was Pigs quick) no deaths. TVenty Per Cent Vinyl Chloride in Air Mice One mouse vas dead) four vara urmorsdous) reoovery in fresh air took about ten minutes. Rats All unconscious with shallow, rapid rss, irations) recovery took about tan minutes in fresh air) no deaths. Guinea All wars in side position) reoovery in fresh air took about Pigs 20 minutes) no deaths. Thirty Par Cent Vinyl Qrlorlde in Air Mice All firm mice dead.' Rats All five rats dead. Guinea Piga *n five vara alive but unoonselous with ahaHo* rapid respiration, 0ns guinea pig from this group died after 2li hours. Forty Per Cent Vinyl Chloride in Air Guinea Piga Only guinea pigs vara exposed. One vas dead and four vara unoonselous at tha and of tha experiment. Another one died within 2li hours after exposure. Recovery after exposure to fresh air in those which survived vas alara BFG3761-1 Page 001 BFG03761 20532001 uCC manual.max _-cerpt continued Dost Morten Examination All animals which died aa a result of exposure to vinyl chloride on April liith, 1559, were dissected within two hours. I carried out these dissections and I node observations on the gross changes present. Various tissues were rsnored and preserved in five per cent formalin for later detailed micros copic study. The two guinea pigs showing delayed death were likewise dissected the following day. All exposed animals which survived were killed on April 27, 1959 (13 day* after they were exposed to vinyl chloride). I performed dissections on all of these and tissue specimens were also taken end preserved in five per cent formalin. Control animals froe the same animal stocks and housed under similar laboratory conditions were killed in die same manner and post mortem examinations con ducted in the same way. There was, of oourse, no exposure to vinyl chloride with this group. In general, all animals ihieh died as a result of exposure to vinyl chloride shoved congestion and/or haemorrhage of the lungs and congestion of the liver and spleen. The control animals did not show these changes* I transported the tissues preserved in formalin to Dr. H. Dancigar of Welland. Dr. Danziger had agreed to prepare these sections for microscopic study, and to examine them. Tours very truly, (Signed) E. Kastromatteo, X.D*, Division of Industrial Hygiene BFG3761-2 uCC manual.max & BFG03762 V APPs?on Concentrations of vinyl chloride gas srixed with air, ranging fTo* $% to hOi vinyl chloride, were delivered to a 56-liter capacity animal teat chaaber. Vixyl chloride gaa and air ware delivered through a rubber tube to the animal chaaber. "Elia tube had a glase Vwith connections to 1) a "Viaher* flow rater and the vinyl chloride supply tank, and 2) a "Precision* wet-test gas meter and standard air pump. The flow rat* of vinyl chloride was ad justed by means of a valve os the supply tank and of the air by adjusting the pusp rate* Fresh air and vinyl chloride in the desired proportions were obtained by the flow pool through the Y tube and rubber tube froa the measured and controlled sources. The corned.ned rate of flow for the 5% to 2Q concen trations was 12 liters per min. and for the 30 and U0J5 concentrations the rate was 8 and 6 liters per ninute respectively. coozccoz BFG3761-3 Page 003 uCC manual.max BFG03764 Inter-Company Cohrrspondence Or"".) COMPANY. LOCATION______Mellon Institute TO f.OCATTOM ATTUrnOH Con To Dr. T. W. `..`ale -ew York Office Dr. 3. H. Weidlei.i, Dr. A. W. Downes Dear Ton: You will recall that the current threshold limit for vinyl chloride Is 500 p.p.m., based largely on single guinea pig Inhalation studies by the Bureau of Hines about 25 years ago. An off-the-record phone call from V. K. Howe gives me incomplete data on their current repeated inhalation study. Six months at 500; 200 and ICC p.p.s. has not found a no-effect level. Even 100 p.p.m. produced organ weight changes and gross pathology, with micropathology expected. Vinyl chloride monomer Is more toxic than has been believed. Rove expects to get sore information before he decides whether or not this has any bearing on the safety of packaging uses of vinyl resins. Dow has been, disturbed at sales efforts saying chloroform Is less toxic than carbon tet. They have completed six months inhalation and find chloroform like carbon tet. This means Its threshold limit will be lowered, as I have suggested for years. It was originally set by analogy with carbon tet, and never lowered when that for carbon tet was reduced. I suggest that these personal cccmini,cations not be quoted until Dow publishes. 11Very truly .yours, 0<sj Henry ?. s^yth, Jr. *nri TNI* mm n INTItaiHV*NV (UINNKHHirNIIICMCM lI.V 011-1959-00003891 iiiiiiniigiiiisiiiiiBniiRiBiMii Vinyl CJUanSt Cifttd Wocra Jtvr-Vior* <>**) 5U-1S3J RECS.VE0 0V 2 7 1359 lawuru."x' *- *''k-- ucc 0EH923 uCC manual.max A A -121t) . xu uso:> ` . THE DOW CHEMICAL COMPANY `Midland PROBLEM NO. 9 2l8 00 TECHNICAL SERVICE AND DEVELOPMENT Kaufinan, J. D. AA-1216 11-30-59 <?& VINYL CHLORIDE AS AN AEROSOL PROPELLANT Since AA-II54, Evaluation of Vinyl Chloride as a Propellant for AeroBole was written, new information has come to light which i modifies the outlook for vinyl chloride in aerosols. Experiments *S fcy Biochem which show much higher toxicity than heretofore realized, and the serious competition offered by propellant mixtures containing petroleum hydrocarbons are the most Important factors. The possible reaction of vinyl chloride with components of perfumes, the difficulty of patenting the mixture of vinyl chloride-Propellant 11-Propellant 12, the competition this mixture would offer to Chlorothene and methylene chloride, and the evidence of corrosivity of vinyl chloride also are discouraging. "I5. view of all the above factors, the conclusion is reached that development work on vinyl chloride as an aerosol propellant should be discontinued. (ESfAftCH CLASSIFICATION! MATERIAL------------------------- USE---------------------------- TYPE------------------------------- STAGEDISTRIBUTION Awbtioni r compete report! /* MIDLAND CRI QPpl.i] EXECUTIVE RESEARCH J. C. Van Horn, TS&D- G ~ R. A. Lindsay, TS&D *A. J. Pastor, Fpt., B-121S . *J* D, Kaufman, TS&D -- * -- *F- W. Larabee, ARB 0. C. Cessna, ARB *R. K. Treichler, Fpt-, A-2421'-o-- *E. R. Cowherd, ARB -- o - *V. C. Bauman, ARB *J. D. Kerr, TS&D *A. W. Smith, TS&D --a-- *B. G. Hoflneyer, TS&D *D. K. Ballman, 47 T. J. Christiansen, ARB *R. H. Smith, Ppt.,B-121 *M. E. Pruitt, Ppt., B-1215 *M. J. Stoesser, Sarnia E. B. Barnes, Ppt., B-1210 TS&D Piles *A. E. Schober, ARB *N. R. Peterson, 433 *W. A. Henson. 433 *W. 17. Seiler, ARB *R. C. Hand, 433 WOB,3170 \VAV /Vn-/ LRJ\J^iI 7t 0-1I Page 001 toPlEO IN MlOtANe CRT MAY 2 5 1995 FOR USE OF DO* EMPLOYEES ONLY OJOS 3110 uCC manual.max OTTZTTas 15:23 4oa aj 6084 nhKSCHEL HUiwu.' -3- Shortly after the work began. It became apparent that the 500 ppm level was having definite detrimental effect on the animals. Now that the first stage of the program is complete, it has been found that some detrimental effect is shown at a 100 ppm leveJLafter six months on some animals. This was the lowest level tested, sc it will be necessary to repeat the experiment to determine the actual safe working level. This level will have to be set somewhere below 100 ppm, however. Methyl chloride, which has an MAC of 100 ppm has never been widely used in aerosols. The toxicity of methyl chloride is frequently cited as a reason for its limited application. Aerosol packages are filled by two methods. In the cold fill technique the concentrate is chilled and added to the caxi. The cold propellant is added next and finally a valve is placed on top and crimped. Between the time the propellant is added and the valve is crimped, the propellant evaporates into the working area. This is not serious while the line is in operation, for the cans are exposed for only a few seconds before sealing. When the line stops, however, the cans may be left open for prolonged periods. Propellant losses normally run from 2 - 5/^ but some fillers report that 10 - of their purchased propellant is lost. In the pressure filling technique, the concentrate is added warm. The valve is attached next and the final operation is the "gassing" of the propellant through the valve. This addition of propellant is slower and consequently, pressure filling lines normally produce fewer cans per minute than cold filling lines. Xn pressure filling, it is necessary to remove as much of the air as possible from the can before the propellant is added. If this air is not removed, the pressure in the finished aerosol package may be excessive. This is done in some lines by squirting a small amount of propellant into the can before the valve is crimped. This propellant evaporates and displaces the majority of the air. The lost propellant is low in thl3 operation, but still some of the material does evaporate into the working space and represents a toxicity hazard. WOB3170-3 Page 003 W03.3172 uo& 3m uCC manual.max T'ZTTSTT T5TZZ ^y4tiw oo 0084 HhKSCHEL 1WOJU.' wuJ 2 INTRODUCTION: Vinyl chloride has been Investigated entenslvely as a propellant for aerosols. In AA-lOOl, the early work on mixtures of vinyl chloride and propane (Propellant D) for aerosol paints was reported. This study covered vapor pressure investigations, possibility of polymerization in aerosol cans, flammability and market potential. In AA-1154, the flammability of vinyl chloride and its mixtures with fluorinated propellants were investigated more thoroughly. The market potentials were modified in light of discoveries concerning the flammability of mixtures of vinyl chloride with fluorinated propellants . Following publication of this report the decision was made to discuss the matter with a consultant to obtain advice on proceeding further with the development. Dr. Winston H. Reed was selected because of his previous work with Propellant A, a blend of butane with the fluorinated hydrocarbon propellants. The consultation session verified some of our findings, but raised new points which have bearing on the potential for vinyl ohloride in aerosols. This report will review the data developed to date and summarize the reasons why the writer feels that development work on this product should be stopped. DISCUSSION: A. Toxicity The established safe concentration of vinyl chloride for an eighthour working day exposure by human beings is 500 ppm. This value was based on work done a number of years ago and had not been thoroughly checked out by Dow. In view of the fact that the proposed use for vinyl chloride represents the first time the consuming public would come into contact with the monomer of vinyl chloride, the Biochemistry Research Department instituted studies of the vapor toxicity of vinyl chloride. WO B3170-2 Page 002 KvOB, 3* . . ujo6 3ini uCC manual.max -4- In Europe where vinyl chloride Is used extensively, the majority or filling lines use the pressure fill technique. This method reduces the fire hazard during filling and also diminishes the toxicity problem. In the U.S.A., the majority of lines^are cold fill- lines. As a result the fire hazard of flammable propellants has sharply limited their use. While it would be possible to install adequate ventilation to control vapor concentrations, this would represent an additional expense to the filler. As will be shown later, the filler can obtain similar cost savings without adding such equipment by using other propellant modifications. The M.A.C. concentration has little direct connection with the hazard to the aerosol user, since no aerosol is sold at present which would expose the user to fumes from the propellant for periods of over a few minutes. The aerosol loaders are not technically qualified to understand the intricacies of toxicity and would probably conclude that a low M.A.C. means an Increase consumer hazard. They would be leary of utilizing a product with a low value. The fluorinated propellants have an M.A.C. of 1,000 and even this high value is not a real maximum. It could have not been set higher on the basis of toxicological data. The low M.A.C. value for vinyl chloride would make it hazardous during filling operations and would be a serious sales hurdle in the minds of aerosol loaders. Since the level will have to be below 100 ppm, further work on vinyl chloride seems unjustified. B. Competition From Other Products In 1956 the development of Propellant A was announced. This was a mixture of lsobutane. Propellant 11 arid Propellant 12. Experiments indicated that if the concentration of isobutane did not exceed 10j6 in such a mixture, the combination was not flammable or explosive. No further information has been seen in the literature and it was assumed that the product had encountered difficulties, possibly from the odor often associated with petroleum hydrocarbons. WOB3170-4 Page 004 UJ0f3 3/73 uCC manual.max u*, *:4/yy ij.i4 Xy409 oJo DU34 -5 - Dr. Reed indicated that difficulties (he did not indicate the nature of these problems) had delayed the further promotion of Propellant A, but that he expected these to be cleared up shortly and felt that the product would be actively promoted in the near ^future. Since lsobutane sells for $0.03 Per pound, the cost savings experienced by replacing 10$ of the Propellant 11-Propellant 12 mix (which sells for approximately $0.23 per pound) would be nearly as great as the savings obtained by replacing 25/6 of the Propellant 11Propellant 12 mix with vinyl chloride which sells for $0.12 per pound. Since Dow does not currently produce Propellant 11 or Propellant 12, it would be necessary for us to interest one of the current producers in buying the vinyl chloride from us and mixing. Pew aerosol loaders are equipped to mix propellants or to handle as flammable a material as pure vinyl chloride. Those few that are so equipped would probably prefer to purchase the less expensive petroleum hydrocarbon propellants. One of the obstacles to the development of Propellant A has been the lack of Interest on the part of the propellant producers in promoting the sale of the mixture. Dr. Reed indicated that they object to purchasing tank car quantities of lsobutane, since only a small amount is used in each tank car of the Propellant A sold. The rest must be carried in inventory. The following example shows that the problem would' also apply to vinyl chloride. ' 8,000 gal. of lsobutane weigh 32,000 lbs. 8,000 gal. of Propellant A requires 8,000 lbs. of lsobutane The sale of four tank cars of Propellant A would be required to move one tank car of lsobutane. 8,000 gal. of vinyl chloride weigh 60,000 lbs. 8.000 gal. of a 25$ vinyl chloride 75$ Propellant 11-Propellant 12 mix would require 20.000 lbs. of vinyl chloride. The sale of three tank cars of the vinyl chloride mixture would be required to move one tank car of vinyl chloride, lllilll fl; I III! ! MIHIIIIi.il WOB3170-5 Page 005 ujoe 3/7V uCC manual.max 09/^4/a is:24 ^J409 J 0U54 6- - W03,3175 - The tank car of Isobutane would cost only about $900.00, while the tank car of vinyl chloride would cost $7,"200.00. Any objections that propellant manufacturers would have against isobutane would be even more vigorous in regard to vinyl chloride. Further, since more.of the manufacturers product would be replaced {?5^ versus 10^), the Interest Of the propellant manufacturers would be reduced even more. The competition offered by Propellant A would appear to be more serious than previously anticipated. Any effort to promote a vinyl chloride mixture would probably meet with increased activity by the holders of rights to Propellant A to promote their products. Dr. Reed Indicated that over 5>000,000 cans of various products (including Brldgeports Brass's "Goodaire" room deodorant) have been made and sold using Propellant A. The manufacturing, storage and marketing information compiled on Propellant A would be substantial. -Since vinyl chloride is a new material in this country, it would require time to develop similar background information. During this period, sales would be more difficult since fillers desire a great deal of data on valve leakage, effect on filling machinery, etc. C. Reactivity In AA-1001, the possibility of polymerization of vinyl chloride in the aerosol can was investigated. No evidence was found of reaction in the test performed, even though known polymerization catalysts were included. Dr. Reed raised a question concerning the possibility of reaction between vinyl chloride and the perfumes used in various aerosols. Perfumes are a complex mixture of various ingredients and the likelihood of reaction with some of these over a period of time is good. Such reactions would probably ohange the nature of the odor. iitiiiuitiiiiiiiiiiiiniiiiiiiiiiliilllllillll liillliiStllillHHItlfl HIHilMl 111! u ill ......... WOB3170-6 Page 006 UJOQ zns uCC manual.max 08/24/69 15:25 409 838 8084 HERSCHEL HOBSON '' - 7 - . Xn the area of hair sprays, the perfume used, in various products Is extremely important. The companies selling hair sprays have been reluctant to modify their perfume for fear of unfavorable consumer relation. This would appear to be a relatively minor point, but considerable sales resistance to Chlorothene in hair sprays has been encountered because of its odor. Since it would be almost impossible to show that there is no reaction between vinyl chloride and the perfume, this argument might be a difficult one to overcome if any customers raised it. The potential market for vinyl chloride of 30,000,000'pounds per year included 10,000/000`pounds per'year for hair'sprays which would now appear more difficult to obtain. D. Patentability The Patent Department has been consulted concerning the prospect for obtaining patents on the use of vinyl chloride in aerosols. They have indicated that the cost savings feature of mixtures of vinyl chloride with the fluorinated propellants would probably not be sufficient to base a patent on, particularly since the savings would not be much greater than that obtained from Propellant A. A much stronger position would be possible if the mixture containing vinyl chloride possessed some unique features which mixtures lacking vinyl chloride did not have. To date, the higher solvency power of vinyl chloride as compared with Propellant 11 and Propellant 12 is the only unique property uncovered and the magnitude of this effect is not great. It is possible that further study might uncover such unique features, but in view of the other factors mentioned above, such work does not seem Justified. E. Adverse Effect on Other Dow Products The cost savingB realized from the use of a 25$ vinyl chloride 75$ Propellant 11-Propellant 12 mixture are almost identical with those obtained from using Chlorothene or methylene chloride as a 50$ replacement for Propellant 11. It is difficult to estimate how much !lllE3l!IIEIIIIIlUSI[||llllttlli!lll!III WOB3170-7 Page 007 U)0(.3 3/76 uCC manual.max WOB , 3177 1 6084 HbKjLntL HOBS -8 llliiiiiiiiiiiiiiiiiiiiiiiiiiiiiinuhiiiiii WOB3170-8 Page 003 T Chlorothene or methylene chloride business would be lost if vinyl chloride were actively promoted, but since all three products are potentially useful In the same kind of aerosol products, the effect would probably be significant. Since a large amount of_informatlon is available on Chlorothene and since this is an exclusive Dow product, it would 3eem wise to devote anyadditlonal effort in the aerosol area to promoting its sale rather than to develop a competitive material. - Corrosivity of Vinyl Chloride The literature indicates that vinyl chloride is less subject to hydrolysis than Propellant 11 or Propellant 12. No corrosion studies have been instituted here to check this information, however, some data obtained as a result of another study would indicate that this is open to question. . A series of aerosol cans were partially filled with various solvents used in pressurized paints. Half of the cans were pressurized with Propellant 12 and half with Propellant D. Pressure readings were taken to determine if significant difference existed when 'Propellant 12 was replaced with Propellant D. No marked differences were noted and the cans were placed in room temperature storage for six months. When these cans were opened after aix months marked corrosion was observed in the cans containing methyl ethyl ketone and methyl lsobutyl ketone which also contained Propellant D. No corrosion occurred with the cans containing Propellant 12 with Onl Since the solve^it ill both uuseg was identical in all respects, the increased corrosion must have been due to the presence of the Propellant D. No noticeable corrosion was observed in cans containing butanol, ethanol, butyl acetate, acetone, VM&P solvent, or toluene but a definite discoloration of the nylon valve body waB seen in nearly every can containing Propellant D but none was seen in the cans with Propellant 12. It Is not known how serious this discoloration is since no valve leakage data was Obtained. The presence of corrosion and valve discoloration, however, would indicate that extensive testing studies would be required before vinyl chloride could be marketed. UJ0& 3/77 uCC manual.max -9- T CONGUISXONS: 1. A lower M.A.C. for vinyl chloride, which appears Inevitable on the basis of recent experiments, would make Its sale as an aerosol propellant much more difficult. 2. Propellant A, which contains isobutane, appears to possess 'many of the desirable features of a vinyl chloride-Propellant 11- Propellant 12 mixture without some of Its disadvantages. Extensive promotion of Propellant A is anticipated in the near future. 3. The possibility of reaction between vinyl chloride and perfumes would reduce its acceptance In aerosol hair sprays, a major projected market. ' 4. The patent picture on vinyl chloride does not appear bright unless some unique benefit could be found for the material. 5. Competition with other Dow materials reduces the appeal of vinyl chloride. 6. Corrosion and valve discoloration observed to date would indicate the necessity of extensive testing before vinyl chloride could be marketed. 7* In view of the above six factors, further work to develop vinyl chloride as an aerosol propellant does not seem Justified. INDEX HEADINGS: Vinyl chloride, propellant for aerosols Aerosols - vinyl chloride as a propellant for WOB3170-9 Page 009 uCC manual.max ouob an? the DOW CHEMICAL COMPANY Midland PROBLEM NO. _9 2l8 00 TECHNICAL SERVICE AND DEVELOPMENT i-->I Kaufman, J. D. AA-1216 11-30-59 CI--VJI t VINYL CHLORIDE AS AN AEROSOL PROPELLANT < < Since AA-1154, Evaluation of Vinyl Chloride as a Propellant for Aerosols was written, new information has come to light which REPORT MO. modifies the outlook for vinyl chloride in aerosols. Experiments by Biochem which show much higher toxicity than heretofore realized, and the serious competition offered by propellant mixtures containing petroleum hydrocarbons are the most important factors. The possible reaction of vinyl chloride with components of perfumes, the difficulty of patenting the mixture of vinyl chloride-Propellant 11-Propellant 12, the competition this mixture would offer to Chlorothene and methylene chloride, and the evidence of corrosivity of vinyl chloride also are discouraging. Tn view of all the above factors, the conclusion Is reached that development work on vinyl chloride as an aerosol propellant should be discontinued. R&Sl 67999 TTPI OF REPORT: ________________ FI flfll PAGES: 9 RESEARCH O-ASUFICATKJHi MATERIAIUSEtype STAGE--------------------- DISTRIBUTION RIHmOHs ('COMPLETE REPORT) MIDLAND CRI (3Cpl) EXECUTIVE RESEARCH J. C. Van Horn, TS&D *A. J. Pastor, Fpt., B-1215 *F. V. Larabcc, ARE *R. K. Treichler, Fpt., A-2421 *W. C. Bauman, ARB *A. W. Smith, TS&D *D. K. Ballman, 47 *R. H. Smith, Fpt., B-121 *M, J. Stoesser, Sarnia TS&D Files *N. R. Peterson, 433 *W. U. Seiler, ARB R. A. Lindsay, TS&D *J. D. Kaufman, TS&D 0. C. Cessna, ARB *E. R. Cowherd, ARB *J. D. Kerr, TS&D *B. G. Hofmeyer, TS&D T. J. Christiansen, ARB *M. E. Pruitt, Fpt., B-1215 E. B. Barnes, Fpt., B-1210 *A. E. Schober, ARB *W. A. Henson, 433 *R. C. Hand, 433 ill! Illllilllllllllllllliillliil R&S167999-1 Page 001 :\l M'DLANti Cm MAY ? 5 f999 FOR USE OF DO* EMPLOYEES ONLY uCC manual.max 2 INTRODUCTION: Vinyl chloride has been investigated entensively as a propellant for aerosols. In AA-1001, the early work on mixtures of vinyl chloride and propane (Propellant D) for aerosol paints j?as reported. This study covered vapor pressure Investigations, possibility of polymerization in aerosol cans, flammability and market potential. In AA-1154, the flammability of vinyl chloride and its mixtures with fluorinated propellants were Investigated more thoroughly. The market potentials were modified in light of discoveries concerning the flammability of mixtures of vinyl chloride with fluorinated propellants. Following publication of this report the decision was made to discuss the matter with a consultant to obtain advice on proceeding further with the development. Dr. Winston H. Reed was selected because of his previous work with Propellant A, a blend of butane with the fluorinated hydrocarbon propellants. The consultation session verified some of our findings, but raised new points which have bearing on the potential for vinyl chloride in aerosols. This report will review the data developed to date and summarize the reasons why the writer feels that development work on this product should be stopped. DISCUSSION: A. Toxicity The established safe concentration of vinyl chloride for an eighthour working day exposure by human beings is 500 ppm. This value waB based on work done a number of years ago and had not been thoroughly checked out by Dow. In view of the fact that the proposed use for vinyl chloride represents the first time the consuming public would come into contact with the monomer of vinyl chloride, the Biochemistry Research Department Instituted studies of the vapor toxicity of vinyl chloride. R&S167999-2 Page 002 uCC manual.max 00009ISTSU -3- Shortly after the work began, It became apparent that the 500 ppm level was having definite detrimental effect on the animals. Now that the first stage of the program is complete, it has been found that some detrimental effect Is shown at a 100 ppm leveJ^ after six months on some animals. This was the lowest level tested, so it will be necessary to repeat the experiment to determine the actual safe working level. This level will have to be set somewhere below 100 ppm, however. Methyl chloride, which has an MAC of 100 ppm has never been widely used in aerosols. The toxicity of methyl chloride is frequently cited as a reason for its limited application. Aerosol packages are filled by two methods. In the cold fill technique the concentrate is chilled and added to the can. The cold propellant is added next and finally a valve is placed on top and crimped. Between the time the propellant is added and the valve is crimped, the propellant evaporates into the working area. This is not serious while the line is in operation, for the cans are exposed for only a few seconds before sealing. When the line stops, however, the cans may be left open for prolonged periods. Propellant losses normally run from 2-5# but some fillers report that 10 - 12# of their purchased propellant is lost. In the pressure filling technique, the concentrate is added warm. The valve is attached next and the final operation is the "gassing" of the propellant through the valve. This addition of propellant is slower and consequently, pressure filling lines normally produce fewer cans per minute than cold filling lines. In pressure filling, it is necessary to remove as much of the air as possible from the can before the propellant is added. If this air is not removed, the pressure in the finished aerosol package may be excessive. This is done in some lines by squirting a small amount of propellant into the can before the valve is crimped. This propellant evaporates and displaces the majority of the air. The lost propellant is low in this operation, but still some of the material does evaporate into the working space and represents a toxicity hazard. ilili iiaiiHIURfll R&S167999-3 Page 003 R&S168001 uCC manual.max -4- In Europe where vinyl chloride is used extensively, the majority of filling lines use the pressure fill technique. This method reduces the fire hazard during filling and also diminishes the toxicity problem. In the U.S.A., the majority of lines-^are cold fill lines. As a result the fire hazard of flammable propellants has sharply limited their use. While it would be possible to install adequate ventilation to control vapor concentrations, this would represent an additional expense to the filler. As will be shown later, the filler can obtain similar cost savings without adding such equipment by using other propellant modifications. The M.A.C. concentration has little direct connection with the hazard to the aerosol user, since no aerosol is sold at present which would expose the user to fumes from the propellant for periods of over a few minutes. The aerosol loaders are not technically qualified to understand the intricacies of toxicity and would probably conclude that a low M.A.C. means an Increase consumer hazard. They would be leary of utilizing a product with a low value. The fluorlnated propellants have an M.A.C. of 1,000 and even this high value Is not a real maximum. It could have not been set higher on the basis of toxicological data. The low M.A.C. value for vinyl chloride would make it hazardous during filling operations and would be a serious sales hurdle in the minds of aerosol loaders. Since the level will have to be below 100 ppm, further work on vinyl chloride seems unjustified. B. Competition From Other Products In 1956 the development of Propellant A was announced. This was a mixture of Isobutane, Propellant 11 and Propellant 12. Experiments indicated that If the concentration of isobutane did not exceed 10$ in such a mixture, the combination was not flammable or explosive. No further Information has been seen in the literature and it was assumed that the product had encountered difficulties, possibly from the odor often associated with petroleum hydrocarbons. uCC manual.max R&S168002 -5 - Dr. Reed indicated that difficulties (he did not Indicate the nature of these problems) had delayed the further promotion of Propellant A, but that he expected these to be cleared up shortly and felt that the product would be actively promoted in the near-future. Since isobutane sells for $0,03 per pound, the cost savings experienced by replacing 10$ of the Propellant 11-Propellant 12 mix (which sells for approximately $0.23 per pound) would be nearly as great as the savings obtained by replacing 25$ of the Propellant 11Propellant 12 mix with vinyl chloride which sells for $0.12 per pound. Since Dow does not currently produce Propellant 11 or Propellant 12, it would be necessary for us to interest one of the current producers in buying the vinyl chloride from us and mixing. Pew aerosol loaders are equipped to mix propellants or to handle as flammable a material as pure vinyl chloride. Those few that are so equipped would probably prefer to purchase the less expensive petroleum hydrocarbon propellants. One of the obstacles to the developmentof Propellant A has been the lack of interest on the part of the propellant producers in promoting the sale of the mixture. Dr. Reed Indicated that they object to purchasing tank car quantities of isobutane, since only a small amount is used in each tank car of the Propellant A sold. The rest must be carried in inventory. The following example showsthat the problem would'also apply to vinyl chloride. 8,000 gal. of Isobutane weigh 32,000 lbs. 8,000 gal. of Propellant A requires 8,000 lbs. of Isobutane The sale of four tank cars of Propellant A would be required to move one tank car of isobutane. 8,000 gal. of vinyl chloride weigh 60,000 lbs. 8.000 gal. of a 25$ vinyl chloride 75$ Propellant 11-Propellant 12 mix would require 20.000 lbs. of vinyl chloride. The sale of three tank cars of the vinyl chloride mixture would be required to move one tank car of vinyl chloride. Si iiiiii!!i!iiiiiiii!iii3!il R&S167999-5 Page 005 R&S168003 uCC manual.max -6- The tank car of isobutane would, cost only about $900.00# while the tank car of vinyl chloride would cost $7/200.00. Any objections that propellant manufacturers would have against isobutane would be even more vigorous in regard to vinyl chloride. Further, since more of tfie manufacturers product would be replaced (25$ versus 10$), the interest of the propellant manufacturers would be reduced even more. The competition offered by Propellant A would appear to be more serious than previously anticipated. Any effort to promote a vinyl chloride mixture would probably meet with increased activity by the holders of rights to Propellant A to promote their products. . Dr. Reed Indicated that over 5,000,000 cans of various products (including Bridgeports Brass's "Goodaire" room deodorant) have been made and sold using Propellant A. The manufacturing, storage and marketing information compiled on Propellant A would be substantial. Since vinyl chloride is a new material in this country, it would require time to develop similar background information. During this period, sales would be more difficult since fillers desire a great deal of data on valve leakage, effect on filling machinery, etc. C. Reactivity . In AA-1001, the possibility of polymerization of vinyl chloride in the aerosol can was investigated. No evidence was found of reaction in the test performed, even though known polymerization catalysts were included. Dr. Reed raised a question concerning the possibility of reaction between vinyl chloride and the perfumes used in various aerosols. Perfumes are a complex mixture of various ingredients and the likelihood of reaction with some of these over a period of time is good. Such reactions would probably change the nature of the odor. R&S168004 uCC manual.max -8 - Chlorothene or methylene chloride business would, be lost If vinyl chloride were actively promoted, but since all three products are potentially useful in the same kind of aerosol products, the effect would probably be significant. Since a large amount of_inforraatlon is available on Chlorothene and since this is an exclusive Dow product, it would seem wise to devote any additional effort in the aerosol area to promoting Its sale rather than to develop a competitive material. F. Corrosivity of Vinyl Chloride The literature indicates that vinyl chloride is less subject to hydrolysis than Propellant 11 or Propellant 12. No corrosion studies have been instituted here to check this information, however, some data obtained as a result of another study would indicate that this is open to question. . A series of aerosol cans were partially filled with various solvents used in pressurized paints. Half of the cans were pressurized with Propellant 12 and half with Propellant D. Pressure readings were "taken to determine if significant difference existed when Propellant 12 was replaced with Propellant D. No marked differences were noted and the cans were placed in room temperature storage for six months. When these cans were opened after six months marked corrosion was observed in the cans containing methyl ethyl ketone and methyl isobutyl ketone which also contained Propellant D. No corrosion occurred with the cans containing Propellant 12 with these solvents. Since the solvent in both cases was identical in all respects, -the increased corrosion must have been due to the presence of the Propellant D. No noticeable corrosion was observed in cans containing butanol, ethanol, butyl acetate, acetone, VM&P solvent, or toluene but a definite discoloration of the nylon valve body was seen in nearly every can containing Propellant D but none was seen in the cane with Propellant 12. It is not known how serious this discoloration is since no valve leakage data was obtained. The presence of corrosion and valve discoloration, however, would indicate that extensive testing studies would be required before vinyl chloride could be marketed. |||||l!|j I1IIEHUllilIII 1111:11Vlillli R&S167999-8 Page 008 R&SI6B006 uCC manual.max -9 - CONCLUSIONS: 1. A lower M.A.C. for vinyl chloride, which appears inevitable on the basis of recent experiments, would make its sale as an aerosol propellant much more difficult. 2. Propellant A, which contains isobutane, appears to possess many of the desirable features of a vinyl chloride-Propellant 11- Propellant 12 mixture without some of its disadvantages. Extensive promotion of propellant A is anticipated In the near future. 3. The possibility of reaction between vinyl chloride and perfumes would reduce its acceptance in aerosol hair sprays, a major projected market. ` 4. The patent picture on vinyl chloride does not appear bright unless some unique benefit could be found for the material. 5. Competition with other Dow materials reduces the-appeal of vinyl chloride. 6. Corrosion and valve discoloration observed to date would indicate the necessity of extensive testing before vinyl chloride could be marketed. 7* In view of the above six factors, further work to develop vinyl chloride as an aerosol propellant does not seem Justified. INDEX HEADINGS: Vinyl chloride, propellant for aerosols Aerosols - vinyl chloride as a propellant R&S167999-9 Page 009 R&S168007 uCC manual.max -7- In the area of hair sprays, the perfume used In various products is extremely important. The companies selling hair sprays have been reluctant to modify their perfume for fear of unfavorable consumer relation. This would appear to be a relatively minor point, but considerable sales resistance to Chlorothene in hair sprays has been encountered because of its odor. Since it would be almost Impossible to show that there is no reaction between vinyl chloride and the perfume, this argument might be a difficult one to overcome if any customers raised it. The potential market for vinyl chloride of 30,000,000:pounds per year1 Included 10,000,000 pounds per'year for hair1sprays which would now appear more difficult to obtain. D. Patentability The Patent Department has been consulted concerning the prospect for obtaining patents on the use of vinyl chloride in aerosols. They have indicated that the cost savings feature of mixtures of vinyl chloride with the fluorinated propellants would probably not be sufficient to base a patent on, particularly since the savings would not be much greater than that obtained from Propellant A. A much stronger position would be possible if the mixture containing vinyl chloride possessed some unique features which mixtures lacking vinyl chloride did.not have. To date, the higher solvency power of vinyl chloride as compared with Propellant 11 and Propellant 12 is the only unique property uncovered and the magnitude of this effect is not great. It is possible that further study might uncover such unique features, but in view of the other factors mentioned above, such work does not seem Justified. E. Adverse Effect on Other Dow Products The cost savings realized from the use of a 25$ vinyl chloride 75$ Propellant 11-Propellant 12 mixture are almost identical with those obtained from using Chlorothene or methylene chloride as a 50$ replacement for Propellant 11. It is difficult to estimate how much miff iiiiiiifiiffiififfii R&S167999-7 Page 007 uCC manual.max R&S168005