Facile Iron‐Mediated Dispersant‐Free Suspension Polymerization of Methyl Methacrylate via Reverse ATRP in Water

An iron-mediated reverse ATRP of methyl methacrylate (MMA) is successfully carried out in water in the absence of any dispersants, using a water-soluble 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50) as the initiator and the stabilizer, and using an oil-soluble N,N-butyldithiocarbamate ferrum (Fe(S2 CN(C4 H9 )2 )3 ) as the catalyst without adding any additional ligands. Micron-sized PMMA particles with UV light-sensitive -S2 CN(C4 H9 )2 end group are obtained, and monomer droplet nucleation and suspension polymerization mechanism are proposed. Polymerization results demonstrated typical "living"/controlled characteristics of ATRP: first-order polymerization kinetics, linear increase of molecular weights with monomer conversion and narrow molecular weight distributions for the resultant PMMA particles. NMR spectroscopy and chain-extension experiments under UV light irradiation confirm the attachment and livingness of UV light-sensitive -S2 CN(C4 H9 )2 group in the chain end.