The influence of the substituents of oxiranes on copolymerization with vinyl ethers: Via concurrent cationic vinyl-addition and ring-opening mechanisms

Miyamae, Yurika; Kanazawa, Arihiro; Tamaso, Ken-ichi et al.

Polymer Chemistry, 2018, 9(4), 404-413

Number of Access:368（2025-09-08 19:02 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100939

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Title
The influence of the substituents of oxiranes on copolymerization with vinyl ethers: Via concurrent cationic vinyl-addition and ring-opening mechanisms
Creator
CreatorName
Miyamae, Yurika
NRID
1000050621322 1000050621322
ORCID
0000-0002-8245-6014 0000-0002-8245-6014
researchmap permalink
arihiro-kanazawa arihiro-kanazawa
Scopus Author ID
9044912600 9044912600
CreatorName
Kanazawa, Arihiro
CreatorName
Tamaso, Ken-ichi
CreatorName
Morino, Kazuhide
CreatorName
Ogawa, Ryo
NRID
1000050183728 1000050183728
CreatorName
Aoshima, Sadahito
Description
Miyamae Y., Kanazawa A., Tamaso K.I., et al. The influence of the substituents of oxiranes on copolymerization with vinyl ethers: Via concurrent cationic vinyl-addition and ring-opening mechanisms. Polymer Chemistry 9, 404 (2018); https://doi.org/10.1039/c7py01292f.
Abstract
2,2-Disubstituted oxiranes with electron-withdrawing substituents were copolymerized with vinyl ethers (VEs) via concurrent cationic vinyl-addition and ring-opening mechanisms, leading to a design strategy for copolymerization via crossover reactions with high efficiency. β-Methylglycidyl ether (βMGE) and β-methylepichlorohydrin, which contain an alkoxy group and a chlorine atom, respectively, as electron-withdrawing groups, exhibited lower reactivity in copolymerization with VEs than isobutylene oxide, a dialkyl-substituted counterpart. Thus, VEs with appropriate reactivities depending on the reactivity of the oxirane were required. For example, 2-ethylhexyl βMGE (EHMGE) and phenyl βMGE ether were not efficiently consumed in the reaction with isopropyl VE but underwent copolymerization via crossover reactions with less reactive ethyl VE (Eve) or 2-chloroethyl VE. Specifically, the copolymerization of Eve and EHMGE yielded a copolymer with an Mn value of 7.5 × 103via 8.3 times crossover reactions from VE to βMGE per chain. The effects of oxirane substituents on the copolymerization behavior are discussed in terms of the reactivities of monomers and propagating species. In addition, a βMGE with an oxyethylenic chain was demonstrated to be effective for the generation of thermoresponsive copolymers.
Publisher
Royal Society of Chemistry
Source Title
Polymer Chemistry
Volume (Issue)
9(4)
Page
404-413
Date of Issued
2018-01-28
Language
English
Handle URL
https://hdl.handle.net/11094/100939
PISSN
17599954
eISSN
17599962
Relation.isVersionOf
DOI (Publisher Version)
https://doi.org/10.1039/c7py01292f
Access Rights
open access
CopyRight
Reproduced from Miyamae Y., Kanazawa A., Tamaso K.I., et al. The influence of the substituents of oxiranes on copolymerization with vinyl ethers: Via concurrent cationic vinyl-addition and ring-opening mechanisms. Polymer Chemistry 9, 404 (2018); https://doi.org/10.1039/c7py01292f with permission from the Royal Society of Chemistry.
oaire:version
Accepted Manuscript
Category
学術雑誌論文 Journal Article