The effect of different aluminum-based cocatalysts (MAO, pMAO, and TMA) on butadiene (Bd) polymerization catalyzed by VO(P204)2 was investigated. The bimodal dependence of the polymer yield on the [MAO]/[V] molar ratio was revealed, and an highest polymer yield was achieved at a rather low [MAO]/[V] molar ratio ([MAO]/[V] = 13). The microstructures of the resulting poly(Bd)s were also significantly influenced by the ratio. In the TMA or pMAO system, the polymer yields were also very sensitive to the [Al]/[V] molar ratio. However, the microstructures of the resulting poly(Bd)s were almost independent of the ratio. In relation to the microstructures of poly(Bd)s obtained by the MAO and TMA systems at various temperatures, the 1,2-unit contents were found to be the most abundant microstructure for both systems. In the pMAO system, the trans-1,4-units were the most abundant. The results of the additions of Lewis bases (THF and TPP) into Bd polyerization system comfirmed the existing of the two types of the reactions of VO(P204)2-MAO catalyst and had the polymerization process controlled to some extent. The different thermal behaviors of these catalytic systems also show that multiple types of active centers were formed during the reaction between VO(P204)2 and MAO. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
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