2024-03-29T11:35:19Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:00028209
2023-01-16T04:20:26Z
320:321:322
Controlled Radical Copolymerization of Cinnamic Derivatives as Renewable Vinyl Monomers with Both Acrylic and Styrenic Substituents: Reactivity, Regioselectivity, Properties, and Functions
Terao, Yuya
Satoh, Kotaro
Kamigaito, Masami
open access
“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Biomacromolecules], 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-xAWGtrJ8QmEBwdcHWqE4].”
A series of cinnamic monomers, which can be derived from naturally occurring phenylpropanoids, were radically copolymerized with vinyl monomers such as methyl acrylate (MA) and styrene (St). Although the monomer reactivity ratios were close to zero for all the cinnamic monomers, such as methyl cinnamate (CAMe), cinnamic acid (CA), N-isopropyl cinnamide (CNIPAm), cinnamaldehyde (CAld), and cinnamonitrile (CN), they were incorporated into the copolymers and significantly increased the glass transition temperatures despite the relatively low incorporation rates of up to 40 mol % due to their rigid 1,2-disubstituted structures. The regioselectivity of the radical copolymerization of CAMe was evaluated on the basis of the results of ruthenium-catalyzed atom transfer radical additions as model reactions. The obtained products suggest that the radicals of MA and St predominantly attack the vinyl carbon of the carbonyl side of CAMe and that the propagation of CAMe mainly occurs via the styrenic radical. The ruthenium-catalyzed living radical polymerization, nitroxide-mediated polymerization (NMP), and reversible addition–fragmentation chain transfer (RAFT) polymerization provided the copolymers with controlled molecular weights, narrow molecular weight distributions, and controlled comonomer compositions. The copolymers of N-isopropylacrylamide (NIPAM) and CNIPAm prepared via RAFT copolymerization showed thermoresponsivity with a lower critical solution temperature (LCST) that could be tuned by altering the comonomer incorporation and a higher LCST than the copolymers of NIPAM and St, which possessed similar molecular weights and similar NIPAM contents, due to the additional N-isopropylamide groups in the CNIPAm units compared to the St units.
ファイル公開:2020-01-14
ACS Publications
2019-01-14
eng
journal article
AM
http://hdl.handle.net/2237/00030405
https://nagoya.repo.nii.ac.jp/records/28209
https://doi.org/10.1021/acs.biomac.8b01298
1525-7797
Biomacromolecules
20
1
192
203
https://nagoya.repo.nii.ac.jp/record/28209/files/BIOMACROMOLECULES_20_1_2019_192-203.pdf
application/pdf
1.4 MB
2020-01-14