Modification of RAFT-polymers via thiol-ene reactions: A general route to functional polymers and new architectures

Cyrille Boyer, Anthony Michael Granville, Thomas Paul Davis, Volga Bulmus

Research output: Contribution to journalArticleResearchpeer-review

193 Citations (Scopus)

Abstract

An investigation into the aminolysis of co-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.
Original languageEnglish
Pages (from-to)3773 - 3794
Number of pages22
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number15
DOIs
Publication statusPublished - 2009
Externally publishedYes

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