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Polyether/Polythioether Synthesis via Ring-Opening Polymerization of Epoxides and Episulfides Catalyzed by Alkali Metal Carboxylates
| Title: | Polyether/Polythioether Synthesis via Ring-Opening Polymerization of Epoxides and Episulfides Catalyzed by Alkali Metal Carboxylates |
| Authors: | Gao, Tianle Browse this author | | Xia, Xiaochao Browse this author | | Tajima, Kenji Browse this author →KAKEN DB | | Yamamoto, Takuya Browse this author →KAKEN DB | | Isono, Takuya Browse this author | | Satoh, Toshifumi Browse this author →KAKEN DB |
| Keywords: | Cesium | | Ethers | | Organic compounds | | Organic polymers | | Ring-opening polymerization |
| Issue Date: | 21-Oct-2022 |
| Publisher: | American Chemical Society |
| Journal Title: | Macromolecules |
| Volume: | 55 |
| Issue: | 21 |
| Start Page: | 9373 |
| End Page: | 9383 |
| Publisher DOI: | 10.1021/acs.macromol.2c00656 |
| Abstract: | Alkali metal carboxylates were evaluated as simple and green catalysts for the ring-opening polymerization (ROP) of various epoxides (e.g., alkyl-substituted epoxides and glycidyl ethers) and episulfides (alkyl-substituted episulfides and thioglycidyl ethers). The thus-produced functional polyethers (end-functionalized polyethers, block copolyethers, polyether- polyester block copolymers, topologically unique polyethers, and isotactic-enriched polyethers) and polythioethers featured well-defined structures and controlled molecular weights (Mn,SEC = 1.0-32 kg mol-1). The most effective catalyst was identified as cesium pivalate, and the variation of carboxylate moieties and alkali metal cations enabled the tuning of acid/base character-istics and thus allowed one to control polymerization behavior and expand the scope of functional monomers and initiators. Kinetic analysis confirmed the controlled/living nature of the polymerization process, while mechanistic studies revealed that carboxylate moieties did not directly initiate the ring-opening of epoxide monomers via nucleophilic attack but rather activated the alcohol initiators/chain ends via H-bonding and thus rendered the corresponding OH groups sufficiently nucleophilic to attack the alkali metal cation-activated epoxides. |
| Rights: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work seehttps://pubs.acs.org/articlesonrequest/AOR-BTR4QWR958AZSCX33UMA. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/90596 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 佐藤 敏文
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