Polystyrene-block-poly(butyl acrylate) and polystyrene-block-poly[(butyl acrylate)-co-styrene] block copolymers prepared via controlled free-radical miniemulsion polymerization using degenerative iodine transfer

Polystyrene-block-poly(butyl acrylate) and polystyrene-block-poly[(butyl ac rylate)-co-styrene] block copolymers were prepared in an aqueous dispersed system via controlled free-radical miniemulsion polymerization using degene rative iodine transfer. The first step is patch miniemulsion polymerization of styrene in the presence of C6F13I as transfer agent. The second step co nsists of the addition of butyl acrylate to this seed latex, either in one shot or continuously. The addition was started before the consumption of st yrene was complete in order to perform a copolymerization reaction able to moderate the rate of propagation in the butyl acrylate polymerization step and, therefore, to favor the transfer reaction. Kinetics of polymerization and control of the molar masses were examined according to the experimental conditions and particularly to the rate of butyl acrylate addition. The fo rmed block copolymers were analyzed by size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NM R).