Modification of RAFT‐polymers via thiol‐ene reactions: A general route to functional polymers and new architectures |
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Authors: | Cyrille Boyer Anthony Granville Thomas P Davis Volga Bulmus |
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Institution: | 1. Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia;2. School of Biotechnology and Biomolecular Sciences (BABS), The University of New South Wales, Sydney, New South Wales 2052, Australia |
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Abstract: | An investigation into the aminolysis of ω‐end groups of RAFT‐polymers and simultaneous thiol‐ene reactions with ene‐bearing compounds is described. Three different polymers, P(MMA), P(HPMA), and P(NIPAAm), with low PDIs were synthesized using dithiobenzoate and trithiocarbonate RAFT agents. P(NIPAAm) synthesized with trithiocarbonate RAFT agent and P(HPMA) synthesized with dithiobenzoate RAFT agent were both functionalized with a methacrylate‐modified mannose and a maleimide‐modified biotin via one‐pot simultaneous aminolysis and thiol‐ene reactions with product yields above 85%. The presence of ene‐compounds during aminolysis was shown to prevent the formation of disulfide interchain crosslinking. Using the same approach, P(MMA), P(HPMA), and P(NIPAAm) were converted to (meth)acrylate macromonomers with high yields (>80%). In the case of P(MMA), the simultaneous aminolysis and thiol‐ene addition prevented any intrachain side reactions, i.e., thiolactone formation. New architectures such as graft and block copolymers were successfully generated from the macromonomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3773–3794, 2009 |
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Keywords: | aminolysis bioconjugation block copolymer graft copolymer radical polymerization reversible addition fragmentation chain transfer (RAFT) telechelics thiol‐ene |
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