Atom Transfer Radical Dispersion Polymerization of Styrene in the Presence of PEO-based Macromonomer

Commercially available poly(ethylene oxide) macromonomers are successfully used as reactive stabilizers for atom transfer radical dispersion/precipitation polymerization of styrene. Polystyrene particles with PEO chains covalently anchored on the surfaces are obtained. Control over both the particle size and polymer chain growth is achieved using a two-stage technique consisting of an initial free radical polymerization (FRP) for the nucleation followed by a reverse atom transfer radical polymerization (ATRP) for the controlled polymerization process. The limited monomer conversion at the FRP step ensures that the overall polymerization process is mainly controlled by the reverse ATRP step, resulting in the formation of particles containing well-defined polymer chains.