Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007