• atom transfer radical polymerization (ATRP);
  • living radical polymerization;
  • miniemulsiom;
  • N, N-n-butyldithiocarbamate copper;
  • reverse ATRP;
  • soap-free emulsion


A facile soap-free miniemulsion polymerization of methyl methacrylate (MMA) was successfully carried out via a reverse ATRP technique, using a water-soluble potassium persulfate (KPS) or 2,2′-azobis(2-methylpropionamidine) dihydrochloride (V-50) both as the initiator and the stabilizer, and using an oil-soluble N,N-n-butyldithiocarbamate copper (Cu(S2CN(C4H9)2)2) as the catalyst without adding any additional ligand. Polymerization results demonstrated the “living”/controlled characteristics of ATRP and the resultant latexes showed good colloidal stability with average particle size around 300–700 nm in diameter. The monomer droplet nucleation mechanism was proposed. NMR spectroscopy and chain-extension experiments under UV light irradiation confirmed the attachment and livingness of UV light sensitive [BOND]S[BOND]C([DOUBLE BOND]S)[BOND]N(C4H9)2 group in the chain end.