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Sequence-controlled multi-block copolymerization of acrylamides via aqueous SET-LRP at 0 °C

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Alsubaie, Fehaid, Anastasaki, Athina, Wilson, Paul and Haddleton, David M. (2015) Sequence-controlled multi-block copolymerization of acrylamides via aqueous SET-LRP at 0 °C. Polymer Chemistry, 6 (3). pp. 406-417. doi:10.1039/c4py01066c

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Official URL: http://dx.doi.org/10.1039/C4PY01066C

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Abstract

Aqueous single electron transfer living radical polymerization (SET-LRP) has been employed to synthesize multi-block homopolymers and copolymers of a range of acrylamide monomers including N-isopropylacrylamide (NIPAM), 2-hydroxyethyl acrylamide (HEAA), N,N-dimethyl acrylamide (DMA) and N,N-diethylacrylamide (DEA). Disproportionation of Cu(I)Br in the presence of Me6TREN in water was exploited to generate reactive Cu(0) and [CuII(Me6TREN)]Br2in situ resulting in unprecedented rates of reaction whilst maintaining control over chain lengths and molecular weight distributions (Đ < 1.10). Kinetic studies enabled optimization of iterative chain extensions or block copolymerizations furnishing complex compositions in a matter of minutes/hours. In the multi-block copolymer system, the monomer sequence was successfully varied and limiting effects on the polymerization have been comprehensively examined through a series of control experiments which imply that the rate of ω-Br chain end loss is enhanced in tertiary acrylamides (DMA, DEA, N-acryloylmorpholine NAM) relative to secondary acrylamides (NIPAM, HEAA).

Item Type: Journal Article
Divisions: Faculty of Science > Chemistry
Journal or Publication Title: Polymer Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1759-9954
Official Date: 2015
Dates:
DateEvent
2015Published
26 September 2014Accepted
3 August 2014Submitted
Volume: 6
Number: 3
Page Range: pp. 406-417
DOI: 10.1039/c4py01066c
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access

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