| 摘要 |
Elastomeric diene polymers are prepared by aqueous emulsion polymerization of conjugated dienes in the presence of a catalyst comprising (A) a chelate complex of trivalent chromium, manganese or cobalt, tetravalent cerium or divalent copper with a 1,3-dicarbonyl compound and (B) an organic halogen compound inert to water. Specified dienes are butadiene, isoprene, chloroprene, 2,3 - dimethylbutadiene, cyclo-octadiene- 1,3 1 -cyclohexyl butadiene and 2-phenylbutadiene, which may be copolymerized with minor proportions of other monomers such as acrylic and methacrylic acids, esters and nitriles, maleic and fumaric esters, vinyl ethers and vinyl aromatic compounds. Many suitable dicarbonyl compounds and organic halogen compounds are listed. Polymerization may be effected batchwise or continuously, preferably to a conversion of 55 to 60%, in the presence of conventional emulsifiers, e.g. salts of paraffin sulphonates, sulphonated alkyl phenols and fatty acids, and protective colloids, e.g. dextrans, cellulose ethers and polyvinyl alcohol; regulators, e.g. dodecyl mercaptan; and stabilizers for the polymers, e.g. trinonyl phosphite. The polymers may be precipitated with complex-forming compounds, e.g. alkali metal cyanides and phosphates and ethylene diamine tetra-acetic acid, to give catalyst-free products. Examples describe emulsion polymerizations using (1) butadiene, cobaltic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (2) butadiene manganic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (3) butadiene, styrene or (4) butadiene, vinyl ethyl ether with cobaltic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (5) butadiene, styrene or (6) butadiene, styrene, acrylonitrile with cobaltic salicylate, carbon tetrachloride and potassium rosin soap; (7) butadiene, manganic methylbutenyl acetoacetate, chloroform and fatty acid soap; (8) 2,3-dimethyl butadiene, n-butyl acrylate, di-n-butyl fumarate, ceric acetylacetonate, cupric acetoacetic ethyl ester trichlorethylene, ammonium oleate and octylphenol/ethylene oxide condensate; (9) as (8) using isoprene as monomer; (10) butadiene, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, cobaltic malono dialdehyde, chromic acetoacetic ethyl ester, chloral, potassium rosin soap and oleic acid/ethylene oxide condensate; and (11) butadiene, t.-butyl acrylate, vinyl methyl ether, cobaltic benzoylacetonate, nickelous acetoacetic ethyl ester, n-butyl chloride, bromoform and potassium stearate. |
