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

Summary: Polymer nanospheres are synthesized by free‐radical dispersion copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) with a methacryloyl‐terminated polystyrene (PS‐MC) macromonomer in cyclohexane. Such polymer nanospheres are stabilized sterically with polystyrene (PS)‐grafted chains in cyclohexane at temperatures greater than 34 °C (the Θ temperature for PS). Ordered microporous surface films are constructed by casting these core‐shell‐type nanospheres from hot cyclohexane solution at 20 °C. The results indicate the possibility of fixation or encapsulation of functional materials after microporous patterning of the core‐shell‐type nanospheres.