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Synthesis of N-acryloxysuccinimide copolymers by RAFT polymerization, as reactive building blocks with full control of composition and molecular weights
Authors:Arnaud Favier  Marie-Thérèse Charreyre  Christian Pichot
Affiliation:Unité Mixte CNRS-bioMérieux, École Normale Supérieure de Lyon, 46 Allée d'Italie, 69364 Lyon Cedex 07, France
Abstract:The reversible addition-fragmentation chain transfer (RAFT) polymerization process was used to synthesize well-defined N-acryloxysuccinimide (NAS) based copolymers, very useful reactive building blocks for various applications. Kinetic studies of RAFT copolymerization of NAS with a bi-substituted acrylamide derivative, N-acryloylmorpholine (NAM), were performed in the presence of tert-butyl dithiobenzoate (tBDB). An excellent control was reached with very high conversions (>95%), molecular weights (MW) up to 80?000 g mol−1 and very narrow molecular weight distributions (MWD) (polydispersity indices, PDI<1.1), as determined by aqueous size exclusion chromatography with on-line light scattering detector (SEC/LS). In addition, the comparison of RAFT and conventional NAM/NAS free radical copolymerization indicated that the apparent reactivity ratios in RAFT are similar to the reactivity ratios determined from conventional copolymerization. An identical azeotropic composition (60/40 NAM/NAS molar ratio) was obtained providing perfectly random poly(NAM-co-NAS) copolymers with full control of composition and MW. These copolymer chains with regularly-distributed reactive functions can be integrated into more complex architectures. As an example, poly(NAM-co-NAS)-b-NAM] block copolymers with length-varying poly(NAM) block were synthesized with a very efficient control over MW, MWD and composition.
Keywords:RAFT copolymerization  Watersoluble reactive copolymers  Activated ester derivative
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