High-temperature solution polymerization of butyl acrylate/methyl methacrylate: Reactivity ratio estimation

Solution copolymerizations of butyl acrylate/methyl methacrylate in toluene were performed over an expanded temperature range (60-140 degrees C) compa red to more typical ranges that do not exceed 80 degrees C. From a large am ount of data collected independently at two laboratories, reactivity ratios were estimated at five different temperatures. The reactivity ratios were estimated from low conversion copolymer composition data using both the err or-in-variables model method and a nonlinear parameter estimation based on the integrated copolymer composition equation. Using all of the available d ata, temperature-dependent expressions were developed for the reactivity ra tios and compared to previously published bulk copolymerization values. No significant differences appeared to exist between the bulk and solution pol ymerization reactivity ratios. Furthermore, the copolymer composition data conformed to the Mayo-Lewis kinetic model over the entire temperature range . (C) 2000 John Wiley & Sons, Inc.