Redox-Initiated Reversible Addition-Fragmentation Chain Transfer (RAFT) Miniemulsion Polymerization of Styrene using PPEGMA-Based Macro-RAFT Agent.

Redox-initiated reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerizations are successfully conducted with an employment of trithiocarbonate-based macro-RAFT agents and surfactant. Two macro-RAFT agents-hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA ) and amphiphilic poly(poly(ethylene glycol) methyl ether methacrylate)-b-polystyrene (PPEGMA -b-PS )- are examined for the miniemulsion polymerization of styrene. The use of PPEGMA (in the presence of sodium dodecyl sulfate (SDS)) results in a slow polymerization rate with a broad particle size. In the absence of SDS, the use of PPEGMA -b-PS results in a broad particle size distribution due to its inability to form uniform initial droplets whereas the same amphiphilic block copolymer in the presence of SDS yields resulting products with a uniform particle size distribution. The latter exhibits a fashion of controlled polymerization with a high consumption of monomer (98% in 100 min) and a narrow molecular weight distribution throughout the polymerization. This is attributed to the formation of uniform droplets facilitated by SDS in a miniemulsion. The amphiphilic macro-RAFT agent is able to anchor efficiently on the monomer droplet or particle/water interface and form stabilized particles of well-defined PPEGMA -b-PS block copolymer, confirmed using dynamic light scattering and transmission electron micrographs.