Hydrophilic MacroRAFT-Mediated Emulsion Polymerization: Synthesis of Latexes for Cross-Linked and Surfactant-Free Films

A major drawback of conventional emulsion polymers arises from the presence of migrating low molar mass surfactants that contribute to poor water barrier properties and low adhesion to substrates. In this paper, we demonstrate how living polymer chains obtained by reversible addition–fragmentation chain transfer (RAFT) can be used as an efficient stabilizer in emulsion polymerization, leading to the production of surfactant-free latexes, which then form cross-linked films with beneficial properties. Hydrophilic poly­(methacrylic acid) (PMAA) chains obtained by RAFT performed in water are used to mediate emulsion polymerization and produce film-forming latex particles from mixtures of methyl methacrylate, <i>n</i>-butyl acrylate, and styrene. Stable dispersions of particles with sizes between 100 and 200 nm are obtained, with very low amounts of coagulum (