Cationic Terpolymerization of Vinyl Ethers, Oxetane, and Ketones via Concurrent Vinyl-Addition, Ring-Opening, and Carbonyl-Addition Mechanisms: Multiblock Polymer Synthesis and Mechanistic Investigation

Kanazawa, Arihiro; Aoshima, Sadahito

Macromolecules, 2017, 50(17), 6595-6605

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Identifier to cite or link to this item: https://hdl.handle.net/11094/100928

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Title
Cationic Terpolymerization of Vinyl Ethers, Oxetane, and Ketones via Concurrent Vinyl-Addition, Ring-Opening, and Carbonyl-Addition Mechanisms: Multiblock Polymer Synthesis and Mechanistic Investigation
Creator
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
NRID
1000050183728 1000050183728
CreatorName
Aoshima, Sadahito
Description
Kanazawa A., Aoshima S.. Cationic Terpolymerization of Vinyl Ethers, Oxetane, and Ketones via Concurrent Vinyl-Addition, Ring-Opening, and Carbonyl-Addition Mechanisms: Multiblock Polymer Synthesis and Mechanistic Investigation. Macromolecules 50, 6595 (2017); https://doi.org/10.1021/acs.macromol.7b01250.
Abstract
Cationic terpolymerization of an alkyl vinyl ether (VE) with oxetane and methyl ethyl ketone (MEK) proceeded via concurrent vinyl-addition, ring-opening, and carbonyl-addition mechanisms. Highly selective crossover reactions occurred in a one-way cycle, resulting in the generation of multiblock polymers with constitutional repeating units comprising a poly(VE) block, a polyoxetane block, and a single MEK unit. The ketone efficiently functioned as a non-homopolymerizable monomer, which reacted with the oxetane-derived oxonium ion to generate an alkoxy group-adjacent carbocation or an oxocarbenium ion. Furthermore, the resulting carbocation allowed to react with only VEs. The polymerization, which was induced with an initiating system of Ph3C+PF6-, 2,6-di-tert-butylpyridine, and 1,4-dioxane, was partly mediated by long-lived propagating species. NMR analysis of the chain end structures revealed that mono- and difluorophosphate moieties generated via the hydrolysis of PF6- were partially responsible for the generation of these long-lived species.
Publisher
American Chemical Society
Source Title
Macromolecules
Volume (Issue)
50(17)
Page
6595-6605
Date of Issued
2017-09-12
Language
English
Handle URL
https://hdl.handle.net/11094/100928
PISSN
00249297
eISSN
15205835
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1021/acs.macromol.7b01250
Access Rights
open access
CopyRight
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.7b01250
oaire:version
Accepted Manuscript
Category
学術雑誌論文 Journal Article