Aqueous MADIX/RAFT polymerization of diallyldimethylammonium chloride: Extension to the synthesis of poly(DADMAC)‐based double hydrophilic block copolymers |
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Authors: | Mathias Destarac Aymeric Guinaudeau Roland Geagea Stephane Mazieres Eric Van Gramberen Cecile Boutin Samy Chadel James Wilson |
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Affiliation: | 1. Laboratoire HFA, CNRS UMR 5069, University of Toulouse, 118 route de Narbonne, 31062 Toulouse Cedex, France;2. Rhodia Opérations, Centre de Recherches et Technologies d'Aubervilliers, 52 rue de la Haie Coq 93308 Aubervilliers Cedex, France |
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Abstract: | Macromolecular design by interchange of xanthates/reversible addition fragmentation chain transfer polymerization (MADIX/RAFT) of diallyldimethylammonium chloride (DADMAC) using the hydrophobic O‐ethyl‐S‐(1‐methoxycarbonyl) ethyl dithiocarbonate MADIX/RAFT mediating agent, Rhodixan A1, was investigated. Attempts to obtain an efficient control of DADMAC polymerization in a water/ethanol mixture failed because of significant chain transfer to ethanol. The use of a water‐soluble Rhodixan A1‐terminated acrylamide oligomer as the MADIX/RAFT agent enabled the controlled polymerization of DADMAC in water at 50 °C using the cationic azo initiator V‐50. An excellent agreement was found between experimental and theoretical Mn values throughout polymerization and over a broad range of initial concentration of xanthate. Polydispersity indexes (PDIs) at the end of the polymerization were abnormally high for a process showing a linear increase of Mn with monomer conversion (1.8 < PDI < 2.0). This feature was explained by the measurement of a high transfer constant to xanthate (Cx = 18.8 ± 1.6) but a low interchange transfer constant (Cex = 1.5). Nevertheless, poly(acrylamide)–poly(DADMAC) double hydrophilic block copolymers (DHBCs) of controlled Mn and composition could be successfully synthesized for the first time. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 |
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Keywords: | diallyldimethylammonium chloride diblock copolymers macromolecular design by interchange of xanthates (MADIX) reversible addition fragmentation chain transfer polymerization (RAFT) water‐soluble polymers |
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