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 °C over a range of monomer and initiator levels. A PREDICI model has been developed to describe the experiments, taking into account chain backbiting, β ‐scission, and addition of macromonomer. The model is used to estimate Arrhenius parameters for the rate coefficients of β ‐scission [ A ( k β ) = (1.49 ± 0.28) × 10 9  s −1 , E a ( k β ) = 63.9 ± 0.9 kJ · mol −1 ], for the ratio of the termination rate coefficients of secondary and midchain radicals ${\left[ {A(k_{{\rm t}} /k_{{\rm t}}^{{\rm t}} ) = 0.74\pm 0.08,\;\;\,E_{{\rm a}} (k_{{\rm t}} /k_{{\rm t}}^{{\rm t}} ) = {-} (11.2\pm 0.5){\rm kJ}\cdot {\rm mol}^{{-} 1} } \right]}$ 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.