Kinetic Modelling of Anionic Polymerization Involving a Dynamic Equilibrium between Two Growth Centres with Different Growth Rates

Abstract

Kinetic modelling of the molecular weight distribution (MWD) of polymer obtained by an anionic polymerization with two types of growth centres in a dynamic equilibrium, having different growth rates and lifetimes comparable to the polymerization time, was made for low monomer conversions. On the basis of distribution of the growth centres according to the total time spent in the fast growth state, it was shown that MWD of the resulting polymer are mostly bimodal at the beginning of the polymerization and change to unimodal MWD at sufficiently high polymerization degrees depending on the equilibrization rate. When all centres are in the fast state in the beginning, MWD are essentially unimodal throughout. A hint of trimodality is observed in some cases, in an extent hardly detectable in real chromatograms. Hence, a polymodal MWD can be explained only when more than two growth centres with different growth rates are assumed.