Synthesis of ethylene or propylene/1,3-butadiene copolymers possessing pendant vinyl groups with virtually no internal olefins

Abstract

In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyľ)2]ZrCl2 (Indenyl’ = generic substituted indenyl), after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (l-indenyl)zirconium dichloride (1), rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl)] zirconium dichloride (2), rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl)]zirconium dichloride (3), rac-dimethylsilyl- bis(2-ethyl-4-phenylindenyl) zirconium dichloride (4), rac-dimethylsilyl-bis[l-(2-n-propyl -4- (1-naphthyl)indenyl)]zirconium dichloride (5), rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2- dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenyl)indenyl))][1-(2-n-propyl-4-(5-(2,2- dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenyl)indenyl))]zirconium dichloride (6), rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium di chloride (7), and rac-dimethylsilyl-bis[l-(2-«-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride (8). We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.