Equibinary (cis-1,4—1,2)Polybutadiene

Furukawa Junji, Kobayashi Eiichi, Kawagoe Takahiro

doi:10.1295/polymj.5.231

The equibinary (cis-1,4—1,2)polybutadiene was prepared using a catalyst of molybdenum compound—aluminum compound. The preparative conditions for this polybutadiene were studied.The catalyst of R′₃Al/MoCl₃(OR)₂ with molar ratio of less than 4 gave the 1,2-polybutadiene, whereas a molar ratio of more than 6 yielded the equibinary (cis-1,4—1,2)polybutadiene. Two kinds of catalytic species were formed by changing the Al/Mo molar ratio. The catalysts MoCl₅ and MoO₂(AA)₂ were also investigated. An experiment with a ternary catalyst of MoO₂(AA)₂—Et₃Al—Et₂AlCl suggests that the amount of Et and Cl is an influential factor in the catalyst for the preparation of equibinary (cis-1,4—1,2)polybutadiene. Various kinds of halogen compounds such as CBr₄, t-BuCl, and I₂ can be used as the halogen component. There was no temperature dependence for the microstructure of the polybutadiene.<BR>The ¹³C-NMR analysis of the polymer showed that the sequence distribution of the dyad was nearly random and far from an alternating one. The sequence distribution suggests that the polymerization proceeded via random polymerization of the cis-1,4-and 1,2-coordinated monomer or the head-to-head or the tail-to-tail polymerization of the monomer pair of the cis-1,4-and 1,2-coordinated on the catalyst.

Equibinary (cis-1,4—1,2)Polybutadiene

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