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

The kinetics of butyl acrylate solution polymerization up to high conversion are studied both experimentally and theoretically. New expressions taking into account both inter- and intramolecular 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, k(bb), and the constant of chain transfer to solvent (xylene), C(trS). Using batch experiments performed at 50, 60 and 70 degrees C, the Arrhenius parameters for k(bb) and C(trS) are estimated to be, respectively, A(k(bb)) = (7.4 +/- 1.5) x 10(7) s(-1), E(a)(k(bb)) = (32.7 +/- 0.5) kJ . mol(-1) and A(C(trS)) = 10.5 +/- 3.5, E(a)(C(trS)) = (26.9 +/- 1.9) kJ . mol(-1).