共聚物
聚合
硼氢化
单体
高分子化学
聚丙烯
化学
配位聚合
催化作用
聚合物
自由基聚合
材料科学
有机化学
作者
Yuanhao Zhong,Iskander Douair,Tiantian Wang,Chung‐Chih Wu,Laurent Maron,Dongmei Cui
标识
DOI:10.1002/anie.201914747
摘要
Abstract Preparation of polyethylenes containing hydroxy groups has been already industrialized through radical copolymerization under harsh conditions followed by alcoholysis. By contrast, hydroxy‐functionalized polypropylene has proven a rather challenging goal in polymer science. Propylene can't be polymerized through a radical mechanism, and its coordination copolymerization with polar monomers is frustrated by catalyst poisoning. Herein, we report a new strategy to reach this target. The coordination polymerization of allenes by rare‐earth‐metal precursors affords pure 1,2‐regulated polyallenes, which are facilely transformed into poly(allyl alcohol) analogues by subsequent hydroboration/oxidation. Strikingly, the copolymerization of allenes and propylene gives unprecedented hydroxy‐functionalized polypropylene after post‐polymerization modification. Mechanistic elucidation by DFT simulation suggests kinetic rather than thermodynamic control.
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