Synthesis of cross-linked core-shell polymer particles by free-radical dispersion copolymerization of 4-vinylpyridine with polystyrene macromonomers in nonaqueous media

Abstract

Cross-linked core–shell polymer particles were synthesized by free-radical dispersion copolymerization of 4-vinylpyridine (4VP) and various kinds of cross-linking reagents with methacryloyl-terminated polystyrene (PS) macromonomers in nonaqueous media such as 1,4-dioxane and cyclohexane. Well-defined particles were obtained by copolymerization of 4VP with ethylene glycol dimethacrylate (EGDM) in a dioxane medium. The particle diameters ( D n =40–990 nm) decreased drastically both with increasing the feed concentration ratio of macromonomer to 4VP, [PS-M]/[4VP], and with increasing molecular weight of PS-M macromonomers. The particle size distribution ( D w / D n ) was in the range 1.02–1.10. PS-M macromonomers acted not only as comonomers but also as stabilizers. The particle diameters obtained in dioxane were smaller than those obtained in cyclohexane. Thus, we observed a tendency to smaller particle size as the media became more soluble for PS-M macromonomer.