Effect of Intramolecular Transfer to Polymer on Stationary Free-Radical Polymerization of Alkyl Acrylates, 5-Consideration of Solution Polymerization up to High Temperatures

Butyl acrylate solution polymerization has been studied at 80-170 degrees C over a range of monomer and initiator levels. A PREDICI model has been developed to describe the experiments, taking into account chain backbiting, beta-scission, and addition of macromonomer. The model is used to estimate Arrhenius parameters for the rate coefficients of beta-scission [A(k(beta)) = (1.49 +/- 0.28) x 10(9) s(-1), E-a(k(beta)) = 63.9 +/- 0.9 kJ . mol(-1)], for the ratio of the termination rate coefficients of secondary and midchain radicals [A(k(t)/k(t)(t)) = 0.74 +/- 0.08, E-a(k(t)/k(t)(t)) = -(11.2 +/- 0.5)kJ . mol(-1) and for the constant of chain transfer to xylene [A(C-trs) = 107 +/- 13, E-a(C-trs) = 35.4 +/- 0.8 kJ . mol(-1)] by fitting simulated dependencies to the experimental data.