Generation of "living" Species Using Perfluoroalkylsulfonic Acids in Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization via Crossover Reactions

Hotta, Daisuke; Kanazawa, Arihiro; Aoshima, Sadahito

Macromolecules, 2018, 51(20), 7983-7992

Number of Access:261（2025-09-09 02:35 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100929

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Title
Generation of "living" Species Using Perfluoroalkylsulfonic Acids in Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization via Crossover Reactions
Creator
CreatorName
Hotta, Daisuke
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
Hotta D., Kanazawa A., Aoshima S.. Generation of "living" Species Using Perfluoroalkylsulfonic Acids in Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization via Crossover Reactions. Macromolecules 51, 7983 (2018); https://doi.org/10.1021/acs.macromol.8b01686.
Abstract
"Living" species-mediated propagation reactions were demonstrated to occur in the cationic vinyl-addition and ring-opening copolymerization of isopropyl vinyl ether and isobutylene oxide (IBO) with CF3SO3H (TfOH) as an initiator. The polymerization proceeded by the carbocations as propagating species formed by the dissociation of a terminal covalent carbon-OTf bond. Importantly, the covalent species were generated exclusively at the IBO-derived propagating end, which was indicated by both the incorporation of a quencher fragment into the ω-end of the product copolymer and 19F NMR analysis of the copolymerization reaction. The generation of reversibly dissociable covalent species, or "dormant" species, from one of the two monomers was crucial for allowing the even propagation of the propagating chains. Moreover, the reaction conditions were optimized to suppress side reactions such as chain transfer via β-proton elimination. Copolymers with molecular weights that agree relatively well with the theoretical values were produced using C4F9SO3H as an initiator in less polar solvents at lower temperature.
Publisher
American Chemical Society
Source Title
Macromolecules
Volume (Issue)
51(20)
Page
7983-7992
Date of Issued
2018-10-23
Language
English
Handle URL
https://hdl.handle.net/11094/100929
PISSN
00249297
eISSN
15205835
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1021/acs.macromol.8b01686
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.8b01686
oaire:version
Accepted Manuscript
Category
学術雑誌論文 Journal Article