Effect of solvent on the rate constants in solution polymerization III. Butyl acrylate/vinyl acetate

Abstract

An experimental and modelling study has been carried out to explore the kinetics of the copolymerization of butyl acrylate and vinyl acetate (BuA-VAc) in solution. A series of batch free radical copolymerization experiments has been carried out using the system BuA-VAc in an ethyl acetate (EAc) solvent. Experimental data were obtained from gravimetric and NMR measurements. The pscudo-homopolymerization constants identified in Parts I and II of this work (McKcnna el ai, J. Polym. Sci., Polyin. clicin., in press) were used along with literature values for the propagation rate constants and reactivity ratios to model the different reactions presented here. It was found that the reactivity ratios of Dube and Penlidis [Polymer, 36, 587 (1995)] fitted the data much better than other literature values (rBuA = 5.93 and rVAc = 0.026), and that a model that allows the kinetic constants to vary as a function of monomer concentration fit the data extremely wellFree Radical Copolymerization Kinetics Solvent Effects Butyl Acrylate Vinyl Acetate Model.