Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters

Higuchi, Motoki; Kanazawa, Arihiro; Aoshima, Sadahito

doi:https://doi.org/10.1002/pol.20210197

Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters

Higuchi, Motoki; Kanazawa, Arihiro; Aoshima, Sadahito

Journal of Polymer Science, 2021, 59(22), 2730-2741

Number of Access:258（2025-09-09 02:35 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100941

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Title	Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters
Creator	CreatorName Higuchi, Motoki
	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
	copolymerization
	depolymerization
	ring-opening polymerization
	sequence control
Description	This is the peer reviewed version of the following article: Higuchi M., Kanazawa A., Aoshima S.. Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters. Journal of Polymer Science 59, 2730 (2021), which has been published in final form at https://doi.org/10.1002/pol.20210197. 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	A temperature change-dependent sequence transformation of copolymer chains was demonstrated by a method based on tandem depolymerization and transacetalization reactions during the cationic ring-opening copolymerization of cyclic acetals and cyclic esters. In this study, the position of polymerization-depolymerization equilibrium was controlled by the reaction temperature rather than by the decrease in monomer concentration under vacuum conditions, as in our previous study. First, the conditions for efficient copolymerization were optimized, with a particular focus on the structures of cyclic acetals and cyclic esters. Subsequently, sequence transformation induced by temperature change was examined during the copolymerization of 2-methyl-1,3-dioxepane (generated in situ from 4-hydroxybutyl vinyl ether) and δ-valerolactone using EtSO3H. The homosequence length of cyclic acetals decreased during depolymerization (unzipping) at the oxonium chain ends upon increasing the temperature from 30 to 90 °C, while transacetalization (scrambling) of the main chain transferred midchain cyclic acetal homosequences to the oxonium chain ends. As a result of the cycle of unzipping and scrambling reactions, an alternating-like copolymer was obtained. Interestingly, the possibility of reversible sequence transformation upon heating and cooling was also demonstrated.
Publisher	John Wiley and Sons Inc
Source Title	Journal of Polymer Science
Volume (Issue)	59(22)
Page	2730-2741
Date of Issued	2021-11-15
Language	English
Handle URL	https://hdl.handle.net/11094/100941
PISSN	26424150
eISSN	26424169
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1002/pol.20210197
Access Rights	open access
CopyRight	© 2021 Wiley Periodicals LLC
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Journal of Polymer Science. 2021, 59(22), p. 2730-2741
DC.title	Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters
DC.creator	Higuchi, Motoki
	Kanazawa, Arihiro
	Aoshima, Sadahito
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2021-11-15
DC.identifier	https://doi.org/10.1002/pol.20210197
DC.subject	cationic polymerization
	copolymerization
	depolymerization
	ring-opening polymerization
	sequence control
DC.description	This is the peer reviewed version of the following article: Higuchi M., Kanazawa A., Aoshima S.. Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters. Journal of Polymer Science 59, 2730 (2021), which has been published in final form at https://doi.org/10.1002/pol.20210197. 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.
DCTERMS.abstract	A temperature change-dependent sequence transformation of copolymer chains was demonstrated by a method based on tandem depolymerization and transacetalization reactions during the cationic ring-opening copolymerization of cyclic acetals and cyclic esters. In this study, the position of polymerization-depolymerization equilibrium was controlled by the reaction temperature rather than by the decrease in monomer concentration under vacuum conditions, as in our previous study. First, the conditions for efficient copolymerization were optimized, with a particular focus on the structures of cyclic acetals and cyclic esters. Subsequently, sequence transformation induced by temperature change was examined during the copolymerization of 2-methyl-1,3-dioxepane (generated in situ from 4-hydroxybutyl vinyl ether) and δ-valerolactone using EtSO3H. The homosequence length of cyclic acetals decreased during depolymerization (unzipping) at the oxonium chain ends upon increasing the temperature from 30 to 90 °C, while transacetalization (scrambling) of the main chain transferred midchain cyclic acetal homosequences to the oxonium chain ends. As a result of the cycle of unzipping and scrambling reactions, an alternating-like copolymer was obtained. Interestingly, the possibility of reversible sequence transformation upon heating and cooling was also demonstrated.
DC.rights	© 2021 Wiley Periodicals LLC
DC.format	100941
citation_title	Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters
citation_author	Higuchi, Motoki
	Kanazawa, Arihiro
	Aoshima, Sadahito
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2021-11-15
citation_journal_title	Journal of Polymer Science
citation_volume	59
citation_issue	22
citation_firstpage	2730
citation_lastpage	2741
citation_doi	https://doi.org/10.1002/pol.20210197
citation_public_url	https://hdl.handle.net/11094/100941

Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters

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