Copolymerization of allyl butyl ether with acrylates via controlled radical polymerization

R. Venkatesh, F. Vergouwen, B. Klumperman

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The atom transfer radical polymn. (ATRP) and reversible addn.-fragmentation chain transfer (RAFT) of acrylates (Me acrylate and Bu acrylate) with allyl Bu ether (ABE) were investigated. Well-defined copolymers contg. almost 20 mol % ABE were obtained with Et 2-bromoisobutyrate as an initiator. Narrow molar mass distributions (MMDs; polydispersity index ? 1.3) were obtained from the ATRP expts., and they suggested conventional ATRP behavior, with no peculiarities caused by the incorporation of ABE.The comparable free-radical (co)polymns. resulted in broad MMDs. Increasing the fraction of ABE in the monomer feed led to an increase in the level of incorporation of ABE in the copolymer, at the expense of the overall conversion. Similarly, RAFT copolymns. with S,S'-bis(a,a'-dimethyl-a''-acetic acid)trithiocarbonate also resulted in excellent control of the polymn. with a significant incorporation of ABE within the copolymer chains. The formation of the copolymers was confirmed with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). From the obtained MALDI-TOF MS spectra for the ATRP and RAFT systems, it was evident that several units of ABE were incorporated into the polymer chain. This was attributed to the rapidity of the cross-propagation of ABE-terminated polymeric radicals with acrylates. This further indicated that ABE was behaving as a comonomer and not simply as a chain-transfer agent under the employed exptl. conditions
Original languageEnglish
Pages (from-to)3271-3284
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number13
Publication statusPublished - 2004


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