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From Syndiotactic Homopolymers to Chemically Tunable Alternating Copolymers: Highly Active Yttrium Complexes for Stereoselective Ring‐Opening Polymerization of β‐Malolactonates
Author(s) -
Jaffredo Cédric G.,
Chapurina Yulia,
Guillaume Sophie M.,
Carpentier JeanFrançois
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310523
Subject(s) - copolymer , polymerization , polymer chemistry , yttrium , ring opening polymerization , alkyl , chemistry , materials science , ring (chemistry) , polymer , organic chemistry , oxide
Alternating copolymers constitute an attractive class of materials. It was shown previously that highly alternated poly(β‐hydroxyalkanoate)s (PHAs) can be prepared by ring‐opening polymerization (ROP) of mixtures of two different enantiomerically pure 4‐alkyl‐β‐propiolactones. However, the approach could not be extended to PHAs with chemically tunable functional groups, which is highly desirable to access original advanced materials. Reported herein is the first highly syndioselective and controlled ROP of racemic allyl and benzyl β‐malolactonates (MLA R ; R=allyl, benzyl) using an yttrium complex supported by a tetradentate dichloro‐substituted bis(phenolate) ligand. This highly active catalyst allows the nearly perfect alternating copolymerization of MLA Allyl and MLA Benzyl . Hydrogenolysis of the benzyloxycarbonyl or functionalization of the allyl pendant groups opens a route towards a new class of functional alternating copolymers.