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(kβ) = (1.49 ± 0.28) × 109 s−1, Ea(kβ) = 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(CtrS) = 107 ± 13, Ea(CtrS) = 35.4 ± 0.8 kJ · mol−1] by fitting simulated dependencies to the experimental data. magnified image