Preparation of block copolymer particles by two-step atom transfer radical polymerization in aqueous media and its unique morphology

Submicron-sized poly(i-butyl methacrylate)-block-polystyrene particles were successfully prepared by two-step atom transfer radical polymerization (ATRP) in aqueous media: ATRP in miniemulsion (miniemulsion–ATRP) followed by ATRP in seeded emulsion polymerization (seeded-ATRP). When PiBMA particles, which were prepared by the miniemulsion–ATRP process with polyoxyethylene sorbitan monooleate (Tween 80, nonionic emulsifier) of 6–10 wt % based on iBMA, were used as seed in the seeded-ATRP of styrene, the block copolymer particles having narrow molecular weight distribution and pre-determined molecular weight were prepared at high conversion. Some block copolymer particles had an ‘onion-like’ multilayered structure. In this way, controlled/living free radical polymerization can be employed to obtain unique particle morphologies that may not be easily accessible using conventional free radical polymerization.