Synthesis of poly(ethyl methacrylate-co-methyl methacrylate) obtained via ATRP using ruthenium benzylidene complexes

Atom-Transfer Radical Copolymerization (ATRP) of methyl methacrylate (MMA) and ethyl methacrylate (EMA) under different reaction conditions was conducted using Grubbs 1st (1) and 2nd (2) generation catalysts. Initially, the study focused on the reactivity of the catalysts in ATRP of EMA individually, then the syntheses of poly(MMA-co-EMA) were also conducted in different mixtures of monomers ([MMA]/[EMA] = 100/200 and [MMA]/[EMA] = 200/100). Conversion and semilogarithmic kinetic plots as a function of time were related to the different catalysts and reaction conditions. The values of M-n and PDI also changed when different catalysts were used in the presence of Al(OiPr)(3), and more controlled polymerizations were achieved using 1. In the syntheses of poly(MMA)-co-(EMA), conversion of 60% was reached for both catalysts at different [MMA]/[EMA] ratios for 16 h; however, for shorter time, 4 h, better conversion values were obtained using 1 as catalyst for both [MMA]/[EMA] = 100/200 or 200/100.