Document 44oNRv84kMxQN8K5jYDjj22LQ

THE DOW CHEMICAL COMPANY Abbott Road Buildings, Midland PLAINTIFF'S EXHIBIT TECHNICAL SERVICE AND DEVELOPMENT OOH> ; <<; Schober, A. E. AA-1001 11-28-58 EVALUATION OF VINYL CHLORIDE AS A PROPELLANT FOR AEROSOL PAINTS A propellant system comprised of 80# vinyl chloride and 20pro pane performs satisfactorily in aerosol paints. Flammability of a paint system containing this system is very similar to current commercial formulations. Polymerization of vinyl chloride did not occur under severe test conditions in the presence of known poly merization catalysts FeCl^, 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 dichlorodifluoromethane (Freon 12, Genetron 12, Isotrcn 12). Based on 1957 production figures, 11.9 million pounds of dichloro difluoromethane were consumed in aerosol paints and thus a 5 to 10 million pound potential exists for vinyl chloride based on.50 to 100# replacement. ns1'-- CtP^. v;T! l! rfi'ls% A K. A CC7:"L EESEARC! IMDEX !Kl. (9 220 00 - Halocarbons, Miscellaneous New Applications)i S.W.E. SEP 24 '59 type of report1 Ls&P CAtoHY. LPACES:______ RESEARCH CLASSIFICATION: MATERIALUSE.TYPE OUTWiimOHi ( * COMPLETE REPORT) * M10LAND CRI 00*1..) EXECUTIVE RESEARCH *J. C. Van Horn *A. J. Pastor *E. W. Larabee, ARB *W. U. Seller, 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 -------------------------- STAGE-------------------------DISTRIBUTION--------------------------- IN MIOLAND CRI 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 8&S168022 FOR USE OF DO* EMPLOYEES ONLY R&S168022-1 Page OOt uCC manual.max RiS,168023 I 2- - mil :K|l|IUUiIlimuuiNi<iMtiiiiii 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 dichlorodifluoromethane, (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 6o paint concentrate and Propellant 12. This combination exerts a pressure of about 38 psig at 7(?F. Vinyl chloride boils at -13.27 C. and at 7C?F. 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 7CfF. For 70 psig at 70F., 76-9 vinyl chloride and 23.156 propane were required. This combination when packaged with 6056 paint concentrate produced a satisfactory spray. The 6o concentrate and Ho& R&St68023 uCC manual.max R&S168022-3 -3- Page 003 propellant mix exerted a pressure of 42 psig at 7CfF. 42 pslg 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, 80# vinyl chloride) and 60# paint concentrate exerted an acceptable pressure of 37 psig at 7<fF. 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: Methylisobutylketone Butyl acetate Isopropanol Butyl Cellosolve (Dowanol EB) Toluene No. 1 75# - 10J6 105^ 5# No. 2 - 75# 10# 10# 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 TBC Inhibit the polymerization? R&SI 68024 iRStS,168024 uCCjrianual.max -4- III H8IR&S. 16802511,11 Air, 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 chlorides' 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. 10056 vinyl chloride/propane + air 2. IOO56 vinyl chloride/propane + air + 500 ppm TBC* 3. 100 vinyl chloride/propane, no air 4. IOO56 vinyl chloride/propane, no air + 500 ppm TBC 5. 4056 vinyl chloride/propane + 6056 No. 1 6. 4056 vinyl chloride/propane + 6056 No. 1 + 500 ppm TBC 7. 4o vinyl chloride/propane + 6056 No. 2 8. 4oj6 vinyl chloride/propane + 6056 No. 2 500 ppm TBC 9. 4o vinyl chloride/propane + 6056 No. 1 O.I56 anhydrous FeCl^ 10. 4oj6 vinyl chloride/propane + 6056 No. 1 + O.I56 anhydrous FeCl^ + 500 ppm TBC 11. 4056 vinyl chloride/propane + 6056 No. 1 + O.I56 anhydrous A1C1, 12. 4o$6 vinyl chloride/propane + 6056 No. 1 4- O.I56 anhydrous AlCl^ + 500 ppm TBC 13. 4oj6 vinyl chloride/propane + 6056 No. 1 O.I56'.distilled water 14. 4o vinyl chloride/propane + 6056 No. 1 +' 0.156:.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. ii MlilllliMIi Tertiary butyl catechol R&S168022-4 Page 004 R&SJ 68025 uCC manual.max 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*^ 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 1441 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 111 lllilllHIliUllIU R&S168022-6 Page 006 R8.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 IS! lllll!!IUil!illlIIII R&S168022-7 Page 007 uCC_manual.max R&S168028