Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

Catalysts

Kenji Michiue¹  Makoto Mitani²  Terunori Fujita² 

[1] Mitsui Chemicals Inc., 1-2, Waki 6-chome, Waki-cho, Kuga-gun, Yamaguchi 740-0061, Japan;Mitsui Chemicals Inc., 580-32 Nagaura, Sodegaura, Chiba 299-0265, Japan; E-Mail:

关键词: 1;    3-butadiene;    C₂-symmetric zirconocene;    insertion mode;    vinyl groups;    internal olefins;    vinylenes;   

DOI  :  10.3390/catal5042001

来源: mdpi

【 摘 要 】

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(Indenyl’)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(1-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-dimethy1si1y1-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 dichloride (7), and rac-dimethylsilyl-bis [l-(2-n-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.

【 授权许可】

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