tert-Butyl Esters as Potential Reversible Chain Transfer Agents for Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization of Vinyl Ethers and Oxiranes

Hotta, Daisuke; Kanazawa, Arihiro; Aoshima, Sadahito

Macromolecular Rapid Communications, 2021, 42(8), 2000479

Number of Access:236（2025-09-08 19:20 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100942

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Title
tert-Butyl Esters as Potential Reversible Chain Transfer Agents for Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization of Vinyl Ethers and Oxiranes
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
Subject
cationic polymerization
chain transfer agents
oxiranes
ring-opening polymerization
vinyl ethers
Description
This is the peer reviewed version of the following article: Hotta D., Kanazawa A., Aoshima S.. tert-Butyl Esters as Potential Reversible Chain Transfer Agents for Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization of Vinyl Ethers and Oxiranes. Macromolecular Rapid Communications 42, 2000479 (2021), which has been published in final form at https://doi.org/10.1002/marc.202000479. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Abstract
tert-Butyl esters are demonstrated to function as chain transfer agents (CTAs) in the cationic copolymerization of vinyl ether (VE) and oxirane via concurrent vinyl-addition and ring-opening mechanisms. In the copolymerization of isopropyl VE and isobutylene oxide (IBO), the IBO-derived propagating species reacts with tert-butyl acetate to generate a copolymer chain with an acetoxy group at the ω-end. This reaction liberates a tert-butyl cation; hence, a polymer chain with a tert-butyl group at the α-end is subsequently generated. Other tert-butyl esters also function as CTAs, and the substituent attached to the carbonyl group affects the chain transfer efficiency. In addition, ethyl acetate does not function as a CTA, which suggests the importance of the liberation of a tert-butyl cation for the chain transfer process. Chain transfer reactions by tert-butyl esters potentially occur reversibly through the reaction of the propagating cation with the ester group at the ω-end of another chain.
Publisher
John Wiley and Sons Inc
Source Title
Macromolecular Rapid Communications
Volume (Issue)
42(8)
Page
2000479
Date of Issued
2021-04-01
Language
English
Handle URL
https://hdl.handle.net/11094/100942
PISSN
10221336
eISSN
15213927
Relation.isVersionOf
DOI (Publisher Version)
https://doi.org/10.1002/marc.202000479
Access Rights
open access
CopyRight
© 2020 Wiley-VCH GmbH
oaire:version
Accepted Manuscript
Category
学術雑誌論文 Journal Article