Densely Arrayed Cage-Shaped Polymer Topologies Synthesized via Cyclopolymerization of Star-Shaped Macromonomers

Mato, Yoshinobu; Sudo, Maho; Marubayashi, Hironori; Ree, Brian J.; Tajima, Kenji; Yamamoto, Takuya; Jinnai, Hiroshi; Isono, Takuya; Satoh, Toshifumi

Densely Arrayed Cage-Shaped Polymer Topologies Synthesized via Cyclopolymerization of Star-Shaped Macromonomers

Mato, Yoshinobu; Sudo, Maho; Marubayashi, Hironori et al.

Macromolecules, 2021, 54(19), 9079-9090

Permalink : https://hdl.handle.net/2115/86801

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アクセス権	open access
URI	https://hdl.handle.net/2115/86801
タイトル	Densely Arrayed Cage-Shaped Polymer Topologies Synthesized via Cyclopolymerization of Star-Shaped Macromonomers
著者	Mato, Yoshinobu ; Sudo, Maho ; Marubayashi, Hironori ; Ree, Brian J. ; Tajima, Kenji ; Yamamoto, Takuya ; Jinnai, Hiroshi ; Isono, Takuya ; Satoh, Toshifumi
著者名 Mato, Yoshinobu
著者名 Sudo, Maho
著者名 Marubayashi, Hironori
著者名 Ree, Brian J.
著者名 Tajima, Kenji
著者名 Yamamoto, Takuya
著者名 Jinnai, Hiroshi
著者名 Isono, Takuya
e-Rad_Researcher 80291235 著者名 Satoh, Toshifumi
言語	英語
キーワード	Cyclopolymerization
	Mass spectrometry
	Mathematical methods
	Cyclization
	Polymers
発行日	2021-10-12
出版者	American Chemical Society
収録物名	Macromolecules
巻(号)	54(19)
ページ	9079-9090
抄録	This work reports a facile and versatile ring-opening metathesis polymerization of three- and four-armed star-shaped poly(epsilon-caprolactone) (PCL) macromonomers bearing a norbornenyl group at each chain end using Grubbs' third-generation catalyst under diluted condition to obtain graft polymers (GPs) comprising densely arrayed three- and four-armed cage-shaped grafted PCLs (GPCLs) with narrow dispersity (1.19-1.35) and a controllable number of cage repeating units up to 40 (molecular weight: similar to 320 000 g mol(-1)). The GPCLs were characterized using nuclear magnetic resonance spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The cyclopolymerization proceeded via repetitive rapid intramolecular reactions to form cage-shaped units followed by slow intermolecular propagation. This synthesis was applicable to star-shaped poly(L-lactide), poly(trimethylene carbonate), and poly(ethylene glycol). Investigating the structure-property relationships regarding crystallization behavior, hydrodynamic diameter, and viscosity revealed that cage-shaped topological side chains reduced the chain dimensions and mobility compared to their linear and cyclic counterparts.
資源タイプ	学術雑誌論文
出版タイプ	Accepted Manuscript
権利情報	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 see https://pubs.acs.org/articlesonrequest/AOR-AWSPR2UWDVGWNQUEN7SU.
PISSN	0024-9297
関連情報 (isVersionOf)	出版社版DOI https://doi.org/10.1021/acs.macromol.1c01230