Uniform Polymer Microspheres by Photoinduced Metal‐Free Atom Transfer Radical Precipitation Polymerization

Abstract Herein, a photoinduced method is introduced for the synthesis of highly cross‐linked and uniform polymer microspheres by atom transfer radical polymerization (ATRP) at room temperature and in the absence of stabilizers or surfactants. Uniform particles are obtained at monomer concentrations as high as 10% (by volume), with polymers being exempt from contamination by residual transition metal catalysts, thereby overcoming the two major longstanding problems associated with thermally initiated ATRP‐mediated precipitation polymerization. Moreover, the obtained particles have also immobilized ATRP initiators on their surface, which directly enables the controlled growth of densely grafted polymer layers with adjustable thickness and a well‐defined chemical composition. The method is then employed successfully for the synthesis of molecularly imprinted polymer microspheres.