Branching and Crosslinking in Coordination Terpolymerizations

A general kinetic method, based upon population balances of generating functions, is applied to the prediction of the microstructure and molecular size of non‐linear terpolymers obtained through the coordination polymerization of two monovinyl monomers and a non‐conjugated diene. A rather complex kinetic scheme involving crosslinking and long‐chain branching is considered. It is shown that even in these conditions it is possible to carry out the prediction of molecular size and mass distributions, sequence size distributions, and z‐average mean‐square radius of gyration of the polymers. The influence of some kinetic parameters on the properties of the products is studied, considering a homogeneous operation in a semi‐batch reactor. The used simulation method is able to predict these properties before and after gelation whenever it occurs.