学術雑誌論文

学術雑誌論文

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

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

John Wiley and Sons Inc

英語

2021-04-01

https://doi.org/10.1002/marc.202000479

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.

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.

© 2020 Wiley-VCH GmbH

100942

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

John Wiley and Sons Inc

英語

2021-04-01

Macromolecular Rapid Communications

42

8

2000479

https://doi.org/10.1002/marc.202000479

https://hdl.handle.net/11094/100942