Abstract
Polymerization of 2-(4-halophenyl)-1,3-butadiene (2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex (1) activated by [Ph3C][B(C6F5)4] and AliBu3 shows high cis-1,4-selectivity (>98%) for the polymerization of 2-XPB (2-XPB = 2-FPB, 2-ClPB and 2-BrPB) to afford halogenated plastic poly(dienes) with glass transition temperatures of 30–55 °C. Moreover, the copolymerization of 2-XPB with isoprene (IP) has also been achieved by this catalyst, and the insertion ratios of 2-XPB can be facilely tuned in a full range of 0%–100% simply by changing the 2-XPB-to-IP ratio. Quantitative hydrogenation of cis-1,4-poly(2-XPB) results in perfect alternating ethylene-halostyrene copolymers, and an alternating copolymer of 4-vinylbenzoic acid with ethylene is obtained by a consecutive reaction of ethylene-4-bromostyrene copolymer with nBuLi, CO2 and HCl.
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Acknowledgments
J. M. Huang acknowledge Mr. Zhen Zhang for his kindly help on the calculation of surface electrostatic potential distribution. This work was financially supported by the National Natural Science Foundation of China (Nos. 21634007 and 51773193) and the Department of Science and Technology of Jilin Province (No. 20180101171JC).
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Yttrium-catalyzed cis-1,4-Selective Polymerization of 2-(4-Halophenyl)-1,3-Butadienes and Their Copolymerization with Isoprene
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Huang, JM., Yao, CG., Li, SH. et al. Yttrium-catalyzed cis-1,4-Selective Polymerization of 2-(4-Halophenyl)-1,3-Butadienes and Their Copolymerization with Isoprene. Chin J Polym Sci 39, 309–315 (2021). https://doi.org/10.1007/s10118-021-2505-3
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DOI: https://doi.org/10.1007/s10118-021-2505-3