Grafting of polymethyl methacrylate from poly(ethylene-co-vinylacetate) copolymer using atom transfer radical polymerization

Atom transfer radical polymerization was employed for the first time to prepare graft copolymer having by ethylene-vinyl acetate (EVA) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches. The polymerization of MMA was initiated by EVA carrying chloropropionate groups as macroinitiator, in the presence of copper chloride (CuCl) and bipyridine (bpy) at 80 °C. The macroinitiator was prepared by esterification of partially hydrolyzed EVA with 2-chloropropionyl chloride. Successful graft copolymerizations were performed both in toluene/γ-butyrolactone mixed solvent and in toluene solution, with grafting efficiency of 12% and 6%, respectively. Molecular weight distribution of the PMMA segments around 1.2 has been achieved with pure toluene solution. The ATRP graft copolymerization was supported by an increase of the molecular weight of the graft copolymers, as compared to that of the macroinitiator and also by their monomodal molecular weight distribution.