A minimal amount of acrylonitrile turns the nitroxide‐mediated polymerization of methyl methacrylate into an almost ideal controlled/living system |
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| Authors: | Julien Nicolas Ségolène Brusseau Bernadette Charleux |
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| Institution: | 1. Laboratoire de Physico‐Chimie, Pharmacotechnie et Biopharmacie, Universitè Paris‐Sud 11, UMR CNRS 8612, Facultè de Pharmacie, 5 rue Jean‐Baptiste Clèment, 92296 Chatenay‐Malabry cedex, France;2. UPMC Universitè Paris 6, UMR 7610, Laboratoire de Chimie des Polyméres, 4 place Jussieu, 75252 Paris cedex 05, France;3. CNRS Universitè Paris 6, UMR 7610, Laboratoire de Chimie des Polyméres, 4 place Jussieu, 75252 Paris cedex 05, France;4. Universitè de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR 5265, Laboratoire de Chimie Catalyse Polyméres et Procèdès (C2P2), LCPP, Bat 308F, 43 Bd du 11 novembre 1918, F‐69616 Villeurbanne, France |
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| Abstract: | Nitroxide‐mediated controlled/living free‐radical polymerization of methyl methacrylate initiated by the SG1‐based alkoxyamine BlocBuilder was successfully performed in bulk at 80–99 °C with the help of a very small amount of acrylonitrile (AN, 2.2–8.8 mol %) as a comonomer. Well‐defined PMMA‐rich P(MMA‐co‐AN) copolymers were prepared with the number‐average molar mass, Mn, in the 6.1–32 kg mol?1 range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by 1H and 13C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain‐end functionalization by an alkoxyamine group was performed by means of 31P NMR spectroscopy and chain extensions from a P(MMA‐co‐AN)‐SG1 macroinitiator. It demonstrated the very high proportion of SG1‐terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 34–47, 2010 |
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| Keywords: | acrylonitrile block copolymer copolymerization kinetics (polym ) living radical polymerization (LRP) methyl methacrylate nitroxide‐mediated polymerization |
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