Reversible-deactivation radical polymerization (RDRP) is one of the most convenient approaches for tailor-making various kinds of hydrophilic polymers with complex architectures. Among the RDRP options available, RAFT/MADIX is a method of choice because of its high tolerance to water and ionic monomers. We recently focused our attention on two important challenges, namely the control of N-vinyl pyrrolidone (NVP) polymerization in water and the polymerization of acrylamido monomers with controlled molar masses up to 106 g.mol-1.We recently reported the first example of RDRP of NVP in water by means of a RAFT/MADIX redox-initiated process at room temperature in the presence of a O-ethyl xanthate. The use of the t-butyl hydroperoxyde/ascorbic acid initiator allowed a controlled polymerization of NVP polymerization. Later, the initiator system was greatly improved by replacing ascorbic acid with sodium sulfite. In particular, it became possible to polymerize NVP in a dilute aqueous medium without forming monomer-derived by-products. Consequently, several original P(NVP)-based double hydrophilic block copolymers were prepared.In another project, we pushed back the limits of molar mass control in aqueous RAFT/MADIX polymerization through a fast a quantitative gel polymerization of a series of acrylamido monomers. Unprecendently high Mn up to 106 g.mol-1 with low polydispersities (Mw/Mn<1.2) were achieved in homopolymerization, statistical and block copolymerization. The reasons for access to abnormally high kinetic chain length in the presence of a RAFT/MADIX agent are discussed.

Aqueous RAFT/MADIX polymerization: Pushing back the limits of control

248th National Meeting (2014)

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