Abstract
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.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.
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Furukawa, J., Kobayashi, E. & Kawagoe, T. Equibinary (cis-1,4—1,2)Polybutadiene. Polym J 5, 231–242 (1974). https://doi.org/10.1295/polymj.5.231
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DOI: https://doi.org/10.1295/polymj.5.231