The Effect of Intramolecular Transfer to Polymer on Stationary Free‐Radical Polymerization of Alkyl Acrylates, 3 – Consideration of Solution Polymerization up to High Conversions

Abstract

AbstractThe kinetics of butyl acrylate solution polymerization up to high conversion are studied both experimentally and theoretically. New expressions taking into account both inter‐ and intra‐molecular transfer to polymer are derived for polymerization rate, average chain‐length and branching level. These expressions are used for comparative analysis of these two chain transfer events and for evaluation of the backbiting rate coefficient, kbb, and the constant of chain transfer to solvent (xylene), CtrS. Using batch experiments performed at 50, 60 and 70 °C, the Arrhenius parameters for kbb and CtrS are estimated to be, respectively, A(kbb) = (7.4 ± 1.5) × 107 s−1, Ea(kbb) = (32.7 ± 0.5) kJ · mol−1 and A(CtrS) = 10.5 ± 3.5, Ea(CtrS) = (26.9 ± 1.9) kJ · mol−1.magnified image