Patent GB-476244-A (GB)
Title: Improvements in and relating to the manufacture of synthetic rubber-like materials
IPC: C08F236/04
Filed: 1936-06-04
Abstract: Rubber-like materials are prepared by interpolymerizing in aqueous emulsion a mixture of butadiene with not more than half its weight (preferably 25 to 40 per cent) of a methacrylic ester of the formula CH2=C(CH3).COOC2H4OR where R is an alkyl radical containing not more than 4 carbons or a phenyl, tolyl, or xylyl radical.  Butadiene as gas or liquid may be added to a mixture of water or ice and the ester, and the mixture agitated.  As emulsifying agent there may be used salts of bases of high molecular weight and organic or inorganic acids, e.g. diethylaminoethyloleylamide acetate or hydrochloride, cetyltrimethylammonium methyl sulphate, dimethylcetylsulphonium methyl sulphate, and cetylpiperidinium methosulphate.  There may be present: small proportions of one or more electrolytes, e.g. acetic acid with or without sodium acetate; substances evolving oxygen, e.g. hydrogen peroxide; chlorinated hydrocarbons, e.g. carbon tetrachloride.  The latex-like products may be coagulated, e.g. by ethyl alcohol, washed and dried.  The interpolymers may be mixed with carbon black, natural rubber or other synthetic rubber-like products and vulcanized.  In examples: (1), (2) 30 parts by weight of butadiene and (1) 15, (2) 14 parts of b -ethoxyethyl methacrylate are emulsified in an aqueous solution of trimethylcetylammonium methyl sulphate and acetic acid, agitated at 60 DEG  C. for five days, and coagulated by ethyl alcohol; (3) 216 parts of butadiene and 100 parts of b -ethoxyethylmethacrylate are emulsified in an aqueous solution of diethylaminoethyloleylamide acetate, acetic acid, and hydrogen peroxide with carbon tetrachloride and agitated at 60 DEG  C. for one day; (4) 30 parts of butadiene and 14 parts of b -ethoxyethyl methacrylate are emulsified in an aqueous solution of diethylaminoethyloleylamide acetate and acetic acid with carbon tetrachloride and agitated at 60 DEG  C. for four and a half days; (5) 28 parts of butadiene and 13 parts of b -methoxyethyl methacrylate are emulsified in an aqueous solution of trimethylcetylammonium methyl sulphate and acetic acid with carbon tetrachloride and polymerized as in example (3); (6) 35 parts of butadiene and 15 parts of b -phenoxyethyl methacrylate are emulsified in an aqueous solution of trimethylcetylammonium methyl sulphate and acetic acid and agitated at 60 DEG  C. for seven days.  The products are mixed with carbon black, stearic acid, zinc oxide, sulphur, and mercaptobenzthiazole, with or without tricresyl phosphate, and v vulcanized.  Specifications 405,699, 424,885, and 427,810 are referred to.  The Provisional Specification includes also examples in which 30 parts of butadiene and 14 parts of b -methoxyethyl methacrylate or 15 parts of b -ethoxyethyl methacrylate are emulsified in an aqueous solution of trimethylcetylammonium bromide and acetic acid, and agitated at 60 DEG  C. for 5 days.  It also states that R (see formula above) may be aryl in general. Aryloxyethyl methacrylates are made by esterifying methacrylic acid with monoaryl esters of ethylene glycol.