RUBBER COMPOSITIONS AND PROCESS FOR PRODUCING THEM PROCESS FOR PRODUCING HYDROGENATED HYDROCARBON POLYMERS OIL EXTENDED

1,151,598. Hydrogenating diene polymers. BRIDGESTONE TIRE K.K. 11 July, 1966 [19 July, 1965], No. 31079/66. Headings C3E and C3P. A solution of a hydrocarbon polymer containing olefinic bonds is reacted with hydrogen at less than 50 atmospheres pressure at a temperature of 0-120‹ C. in the presence of a catalyst soluble in said solution, the catalyst being obtained by reacting (1) at least one metal carboxylate of formula (RCOO) n M wherein M is nickel, cobalt, iron, chromium, or manganese, R is a C 1 -C 50 hydrocarbon radical and n is the valence number of M, with (2) at least one compound of formula AlR1 2 R11 wherein R1 is a C 1 -C 12 hydrocarbyl radical and R11 is hydrogen, a C 1 -C 12 hydrocarbyl radical or a C 1 -C 12 hydrocarbyloxy radical, at a temperature of -78‹ to 100‹ C., the mole ratio of M to Al lying within the range of from 1: 0À2 to 1:10. The catalyst may be prepared beforehand or prepared in the polymer solution. Polymers treated include natural rubber, polybutadiene, butadiene-styrene copolymer, and butadiene-isoprene copolymer. A random butadiene-isoprene copolymer of 94À7% cis configuration is prepared by reacting the monomers in solution in hexane at 40‹ C. in the presence of a catalyst mixture of nickel naphthenate, boron trifluoride etherate and triethylaluminium (Example 43). A block-graft copolymer of butadiene and styrene is prepared by reacting butadiene in solution in toluene at 40‹ C. in the presence of the same catalyst and then further polymerizing a mixture of butadiene and styrene. The butadiene units had the configuration: 87À8% cis-1,4-, 7À2% trans-1,4-, 5À0% vinyl. The invention also comprises a cured, rubbery, hydrogenated random styrene-butadiene copolymer and a cured, rubbery, hydrogenated cis-1,4-polybutadiene having less than 9% of its double bonds saturated with hydrogen. Reference has been directed by the Comptroller to Specification 1,030,306.