Molecular Weight and Branching Distribution Modeling in Radical Polymerization with Transfer to Polymer and Scission Under Gel Conditions and Allowing for Multiradicals

Abstract

A population balance model for the prediction of molecular weight distribution (MWD) in a continuous stirred tank reactor (CSTR) has been developed accounting for multiradicals and gel formation in the framework of Galerkin-FEM. In the absence of recombination, gel does not form, but accounting for multiradicals leads to a better prediction of the long MWD tail. Results of the multiradical model with topological scission are well in line with Monte Carlo (MC) simulations. For the case of recombination without scission the multiradical model leads to perfect agreement with MC simulations as regards prediction of the gel fraction and chain length distribution. The classical monoradical model fails to describe the gel regime. We account for gel fragmentation in systems with gelation and scission. Results for this case are in agreement with MC simulations. A nongel assuming variant allows properly detecting the gelpoint and the associated distribution. The scission model adopted, linear or topological scission, turns out to be of extreme importance for the gel regime prediction.