Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts

Sugiyama, Moeno; Suzuki, Ryota; Ayakawa, Hiroto; Gao, Tianle; Li, Feng; Yamamoto, Takuya; Isono, Takuya; Satoh, Toshifumi

Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts

Sugiyama, Moeno; Suzuki, Ryota; Ayakawa, Hiroto et al.

Polymer journal, 2025, 57(11), 1153-1163

Permalink : https://hdl.handle.net/2115/98048

このアイテムのアクセス数:14件（2026-09-06 08:46 集計）

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アクセス権	open access
URI	https://hdl.handle.net/2115/98048
タイトル	Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts
著者	Sugiyama, Moeno ; Suzuki, Ryota ; Ayakawa, Hiroto ; Gao, Tianle ; Li, Feng ; Yamamoto, Takuya ; Isono, Takuya ; Satoh, Toshifumi
著者名 Sugiyama, Moeno
著者名 Suzuki, Ryota
著者名 Ayakawa, Hiroto
著者名 Gao, Tianle
e-Rad_Researcher 30902788 著者名 Li, Feng
e-Rad_Researcher 30525986 著者名 Yamamoto, Takuya
e-Rad_Researcher 70740075 著者名 Isono, Takuya
e-Rad_Researcher 80291235 著者名 Satoh, Toshifumi
言語	英語
キーワード	crystalline polyesters
	isobutylene oxide
	ring-opening alternating copolymerization
	organobase catalyst
	self-switchable polymerization
発行日	2025-11
出版者	Springer Nature
収録物名	Polymer journal
巻(号)	57(11)
ページ	1153-1163
抄録	Ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and epoxides is a promising approach for the well-controlled synthesis of polyesters with versatile structures. ROAC typically yields amorphous polyesters owing to challenges in controlling the main-chain stereochemistry, whereas most applied polyesters are crystalline. Isobutylene oxide (IBO), a highly symmetric epoxide, can overcome this issue, thus facilitating the synthesis of crystalline polyesters via ROAC. However, low reactivity and potential side reactions remain major obstacles to achieving an IBO-based ROAC in a controlled manner. In this study, we successfully developed a well-controlled ROAC of cyclic anhydrides and IBO using environmentally benign organobase catalysts. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (& Dstrok; <= 1.1). This method was extended to other cyclic anhydrides and initiators, enabling the synthesis of polyesters with diverse structures. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer of P(PA-alt-IBO) and P(PA-alt-butylene oxide), as well as block copolymer comprising P(PA-alt-IBO) and poly(trimethylene carbonate). This study not only expands the scope of epoxides in ROAC but also provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs.
資源タイプ	学術雑誌論文
出版タイプ	Accepted Manuscript
権利情報	This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: http://dx.doi.org/10.1038/s41428-025-01087-9
PISSN	0032-3896
関連情報 (isVersionOf)	出版社版DOI https://doi.org/10.1038/s41428-025-01087-9