Atom transfer radical polymerization of monomers containing amide and ester moieties monitored by dilatometric method

The kinetics of atom transfer radical polymerization of N-(S)-alpha-methylbenzylmethacryloylamine (S-(-)-alpha-MBMA) and alpha-methylbenzylmethacrylate (alpha-MBM) monomers, as assessed by % conversion, were determined at 48 A degrees C in a toluene/ethanol mixture (60:40) by a dilatometry method. The effect of the presence of - CONH- or - COOR- moieties on the ATRP polymerization of such monomers was investigated. Controlled polymerizations were performed with the catalyst system [M] / [R - X]/[Mt(n) - Y]/[L] at molar ratios of 100:15:15:15; 200:15:15:15; 300:15:15:15; and 400:15:15:15, where R-X was EBIB or MCP, M (t) (n) -Y(CuBr or CuCl) and L (Me(6)TREN). Also with N-S-(-)-alpha-MBMA, some studies used ATCA and ABPA as R-X. Plots of the ln[M](0)/[M] vs t as well as from the log Rp vs log [M] showed that the ATRP processes followed a pseudo first-order kinetics with respect to the monomer concentration and that the molecular weight of the resulting polymers increased with the conversion. The ATRP results for both monomers showed a similar trend and revealed that the presence of N-S-(-)-alpha-MBMA (amide group) affects the polymerization, i.e. it did not react when the EBIB/CuBr/Me(6)TREN catalyst system was used. The M(n) and M(w) were determined by (1)H-NMR and GPC. PDI values fell between 1.19 and 1.5, and indicated that the majority of the systems showed good control of polymerization.