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, n-butyl acrylate, and styrene. Stable dispersions of particles with sizes between 100 and 200 nm are obtained, with very low amounts of coagulum (<0.5 wt %). The particles are stabilized by the PMAA segment of amphiphilic block copolymers formed during the polymerization. Remarkably, low amounts of PMAA chains (from 1.5 down to 0.75 wt %) are enough to ensure particle stabilization. Only traces of residual PMAA macroRAFT agents are detected in the final latexes, showing that most of them are successfully chain extended and anchored on the particle surface. The glass transition temperature of the final material is adjusted by the composition of the hydrophobic monomer mixture so that film formation occurs at room temperature. Conventional cross-linking strategies using additional hydrophobic comonomers, such as 1,3-butanediol diacrylate (BuDA), diacetone acrylamide (DAAm), and (2-acetoacetoxy)ethyl methacrylate (AAEM), are successfully applied to these formulations as attested by gel fractions of 100%. When particles are internally cross-linked with BuDA, chain interdiffusion between particles is restricted, and a weak and brittle film is formed. In contrast, when DAAm-containing chains undergoes cross-linking during film formation, full coalescence is achieved along with the creation of a cross-linked network. The resulting film has a higher Young’s modulus and tensile strength as a result of cross-linking. This synthetic strategy advantageously yields a surfactant-free latex that can be formed into a film at room temperature with mechanical properties that can be tuned via the cross-linking density.

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