Study of the solution and aqueous emulsion copolymerization of vinylidene chloride with methyl acrylate in the presence a poly(ethylene oxide) macromolecular RAFT agent |
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Authors: | Emilie Velasquez,Jutta Rieger,Franç ois Stoffelbach,Bernadette Charleux,Franck D'Agosto,Muriel Lansalot,Pierre-Emmanuel Dufils,Jé rô me Vinas |
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Affiliation: | 1. UPMC Univ. Paris 6, Sorbonne Universités and CNRS, Laboratoire de Chimie des Polymères, UMR 7610, 3 rue Galilée, 94200 Ivry, France;2. Université de Lyon, Univ Lyon 1, CPE Lyon, CNRS, UMR 5265, C2P2 (Chemistry, Catalysis, Polymers & Processes), Team LCPP Bat 308F, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne, France;3. SOLVAY, High Barrier Polymers, Avenue de la République, F-39500 Tavaux, France;4. SOLVAY, High Barrier Polymers, Rue de Ransbeek 310, B-1120 Brussels, Belgium |
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Abstract: | The reversible addition-fragmentation chain transfer (RAFT) copolymerization of vinylidene chloride (VDC) with methyl acrylate (MeA) was studied in the presence of poly(ethylene oxide)-based macromolecular RAFT (macroRAFT) agents of the trithiocarbonate type (PEO-TTC) in solution and in aqueous emulsion. Firstly the formation of PEO-b-P(VDC-co-MeA) diblock copolymers was performed in toluene solution at 30 °C and a good control over the polymerization with high chain-end functionality was shown. A first aqueous emulsion copolymerization of VDC with MeA was performed using one of the amphiphilic PEO-b-P(VDC-co-MeA) diblock copolymers as macromolecular stabilizer. Then, in a series of experiments the PEO-TTC macroRAFT agents were directly tested as both chain transfer agents and stabilizing agents in similar conditions (aqueous batch emulsion copolymerization of VDC with MeA at 70 °C). The influence of the nature and concentration of the initiating system and the presence or not of a buffer were studied. We demonstrated that in simple conditions, nanometric latex particles composed of amphiphilic PEO-b-P(VDC-co-MeA) diblock copolymers formed by polymerization-induced self-assembly (PISA). It can thus be concluded that PEO-TTC macroRAFT agents are valuable non-ionic macromolecular stabilizers in the emulsion copolymerization of VDC and MeA and allow the formation of core–shell diblock copolymer particles in the absence of free surfactant. However, when rather high molar masses of the hydrophobic PVDC-based block were targeted, the determined molar masses deviated from the theoretical values. |
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Keywords: | RAFT polymerization Emulsion polymerization Vinylidene chloride |
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