Functional multisite copolymer by one-pot sequential RAFT copolymerization of styrene and maleic anhydride

Guillaume Moriceau, Guillaume Gody, Matthias Hartlieb, Joby Winn, Hyungsoo Kim, Antonio Mastrangelo, Timothy Smith, Sébastien Perrier

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A Multisite copolymer with functionalizable units inserted at precise locations was synthesised by one-pot Reversible Addition-Fragmentation Chain-Transfer (RAFT) polymerization and sequential Single Monomer Unit Insertion (SMUI) and Chain Extension (ChainExt) using Styrene (Sty) and Maleic Anhydride (MAnh) as comonomers. The multisite copolymer was based on a polystyrene (PSty) backbone (ca. 5700 g mol-1) with MAnh units inserted locally at four positions in the backbone. First, a well-defined macroCTA (1400 g mol-1-D = 1.07) was synthesised by optimized RAFT polymerization (high conversion, high livingness and low dispersity) of styrene (DP = 10) using industrial grade butyl-2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl] propionate as chain transfer agent (CTA-Ester-80% pure). Subsequently, the polystyrene macroCTA was used for one-pot SMUI using a small excess of MAnh monomer (DPtarget = 1.5). The copolymer was chain extended by styrene leading to a polystyrene backbone with MAnh units (1.5 in average) located in the middle of the chain. By repeating SMUI and ChainExt, several units of MAnh were inserted locally along the polystyrene backbone (every 10 units on average) to give a functionalizable multisite copolymer (D = 1.35). Long alkyl chains (stearyl) were added by esterification of maleic anhydride moieties to obtain branched architecture.

Original languageEnglish
Pages (from-to)4152-4161
Number of pages10
JournalPolymer Chemistry
Issue number28
Publication statusPublished - 28 Jul 2017

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