Living radical polymerizations using reversible addition−fragmentation chain transfer
(RAFT) have been conducted successfully in miniemulsions stabilized by nonionic surfactants. The
miniemulsion stability was found to be a key issue. Both anionic and cationic surfactants were not able
to maintain the original droplet morphology during the reaction. The application of nonionic surfactants
allowed the controlled polymerization of methacrylate and styrene monomers, resulting in stable
dispersions free of coagulate. Typical particle sizes for these latices were around 200−300 nm. The molar
mass of the polymer was close to the predicted value, and polydispersity was typically below 1.20, never
exceededing 1.40. The “living” character of the latex material was further exemplified by its transformation
into block copolymers. The increased polymerization rate of the compartmentalized system allowed for
improved block copolymer purity compared to that of homogeneous systems. Furthermore, it was shown
that latex blends containing particles with very different characteristics could be prepared in a single
polymerization by a careful choice of reaction conditions allowing the design of sophisticated materials.
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