Soeriyadi, Alexander H., Li, Guang-Zhao, Slavin, Stacy, Jones, Mathew W., Amos, Catherine M., Becer, C. Remzi, Whittaker, Michael R., Haddleton, David M., Boyer, Cyrille and Davis, Thomas P.. (2011) Synthesis and modification of thermoresponsive poly(oligo(ethylene glycol) methacrylate) via catalytic chain transfer polymerization and thiol–ene Michael addition. Polymer Chemistry, Vol.2 (No.4). pp. 815-822. ISSN 1759-9954

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Abstract

Various poly(oligo(ethylene glycol) methyl ether methacrylate)s (POEGMEMAs) have been prepared by Catalytic Chain Transfer Polymerization (CCTP) using a range of OEGMEMA monomers (molecular weight from 180 to 1100 g mol−1). The chain transfer constants of bis(boron difluorodimethylglyoximate) cobalt(II) (CoBF) were determined and are reported for each monomer. The copolymerization of POEGMEMA (Mn = 475 g mol−1) with diethylene glycol methyl ether methacrylate (DEGMEMA) yielded thermoresponsive polymers. The lower critical solution temperatures (LCSTs) of the polymer chains can be tuned by the copolymer composition over the range 30 °C to 95 °C. In addition, the presence of the vinylic end-group, characteristic of CCT polymerization, provided further scope for post-synthetic modification via thiol–ene click chemistry, through nucleophilic Michael addition with various functional thiol compounds such as 2-mercaptoethanol, 3-mercaptopropionic acid, benzyl mercaptan and 1-dodecanethiol. The thiol–ene reaction was rigorously tested, optimized and characterized in this study in terms of solvents and most importantly the choice of the catalyst: dimethyl phenyl phosphine, tertiary amine or hexylamine. The optimum conditions reported allow near-quantitative functionalization of these macromonomers without significant side reactions. The effect of the end-group on the LCST has also been investigated, as well as thermal stability temperature of the copolymers.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Polymerization, Organic compounds -- Synthesis, Copolymers
Journal or Publication Title:	Polymer Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1759-9954
Date:	April 2011
Volume:	Vol.2
Number:	No.4
Page Range:	pp. 815-822
Identification Number:	10.1039/c0py00372g
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Australian Research Council (ARC), University of New South Wales (UNSW), Commonwealth Scholarship Commission in the United Kingdom, University of Warwick, European Union (EU)
URI:	http://wrap.warwick.ac.uk/id/eprint/36956

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