Emulsion Polymerization of Vinyl Acetate in the Presence of Different Hydrophilic Polymers Obtained by RAFT/MADIX

The surfactant-free emulsion polymerization of vinyl acetate (VAc) was achieved using RAFT/MADIX-mediated polymerization-induced self-assembly (PISA) process in water. First, well-defined hydrophilic macromolecular RAFT agents (macroRAFT) bearing a xanthate chain end were synthesized by RAFT/MADIX polymerization of N-vinylpyrrolidone (NVP) and N-acryloylmorpholine (NAM) or by post-modification of commercial poly(ethylene glycol). Chain extension of the macroRAFT with VAc in water led to the block copolymer nanoscale organization and the subsequent formation of stable and isodisperse PVAc latex nanoparticles with high solids content (35–37 wt %). The influence of various parameters, including the nature and functionality of the macroRAFT agent precursor, on the polymerization kinetics and particle morphology was also studied.