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Access to Hydroxy‐Functionalized Polypropylene through Coordination Polymerization
Author(s) -
Zhong Yuanhao,
Douair Iskander,
Wang Tiantian,
Wu Chunji,
Maron Laurent,
Cui Dongmei
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914747
Subject(s) - hydroboration , copolymer , polymerization , monomer , polymer chemistry , chemistry , polypropylene , coordination polymerization , catalysis , polymer , radical polymerization , organic chemistry
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.