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Journal ArticleDOI

Concurrent cationic vinyl-addition and ring-opening copolymerization of vinyl ethers and oxiranes

Arihiro Kanazawa, +1 more
- 01 Jun 2016 - 
- Vol. 48, Iss: 6, pp 679-687
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TLDR
In this paper, a review on concurrent cationic vinyl-addition and ring-opening copolymerization of vinyl ethers and oxiranes is presented, with particular emphasis on the strategies required to generate crossover reactions between different types of monomers.
Abstract
In this review, our recent results on the concurrent cationic vinyl-addition and ring-opening copolymerization of vinyl ethers (VEs) and oxiranes are summarized, with particular emphasis on the strategies required to generate crossover reactions between different types of monomers. Most importantly, carbocation generation via the ring-opening reaction of the oxirane-derived oxonium ion is indispensable for the crossover reaction from oxirane to VE. Specifically, oxiranes with substituents that contribute to stabilizing these carbocations are suitable for concurrent copolymerization. Moreover, weak Lewis bases have been found to affect the frequency of crossover reactions through the promotion of the ring-opening reaction. This article also summarizes concurrent cationic vinyl-addition, ring-opening and carbonyl-addition terpolymerization via the one-way cycle of crossover reactions, the copolymerization of an alkoxyoxirane with VEs through the alkoxy group transfer mechanism, and the long-lived species-mediated cationic polymerization of vinyl monomers and cyclic formals. Our recent results in the concurrent cationic vinyl-addition and ring-opening copolymerization of vinyl ethers (VEs) and oxiranes are summarized with particular emphasis on the strategies required to generate crossover reactions between different types of monomers. Most importantly, carbocation generation via the ring-opening reaction of the oxonium ion is indispensable for the crossover reaction from oxirane to VE. This article also summarizes concurrent cationic vinyl-addition, ring-opening and carbonyl-addition terpolymerization, the copolymerization using an alkoxyoxirane through the alkoxy group transfer mechanism and the long-lived species-mediated polymerization using cyclic formals.

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Citations
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Macromolecular architectures based on organocatalytic ring-opening (co)polymerization of epoxides

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Recent advances in degradable synthetic polymers for biomedical applications – Beyond polyesters

TL;DR: A review of the latest developments of (bio-degradable) synthetic polymers beyond polyesters can be found in this paper , where the authors scrutinize the recent synthetic developments of these polymer classes throughout the last 10 years, putting them into the context of applications that have arisen for less novel materials.
Journal ArticleDOI

Concurrent Cationic Vinyl-Addition and Coordination Ring-Opening Copolymerization via Orthogonal Propagation and Transient Merging at the Propagating Chain End

TL;DR: In this paper, a graft copolymer consisting of a poly(VE) main chain and several poly(CL) side chains was generated via the unprecedented mechanisms consisting of orthogonal propagating reactions and transient merging.
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Synthesis of copolymer via hybrid polymerization: From random to well-defined sequence

TL;DR: In this paper, a review of the sequence structure of the obtained copolymers, which have gone through a process from producing random uncontrollable sequences, to constructing sequence-controlled copolymer and even sequence-on-demand copylmers, is presented.
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Cooligomerization of γ-butyrolactone with (meth)acrylates catalyzed by N-heterocyclic carbene: Low possibility of hybrid copolymerization

TL;DR: In this paper, the authors present cooligomerizations of γ-butyrolactone (γBL), a low polymerizable cyclic monomer, with (meth)acrylates catalyzed by an N-heterocyclic carbene (NHC) under conditions in which no reaction occurs in the absence of either comonomer.
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