期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 12, 页码 4947-4952出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201914747
关键词
allenes; copolymerization; hydroxylated polypropylenes; polar monomers; rare-earth metals
资金
- NSFC [21634007, 21774118, 21674108]
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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