Molecular weight distribution of metallocene polymerization with long chain branching using a binary catalyst system

Abstract In metallocene polymerization, termination by β‐hydride elimination generates polymer chains containing unsaturated vinyl groups at their chain ends. Further polymerization of these macromonomers produces branched polymers. Material properties of the branched polymers not only depend on molecular weight and branching density, but also on chain structure. This work presents analytical expressions to predict the bivariate distribution of molecular weight and branching density for polymer chains having dendritic and comb structures. It is shown that when a single metallocene catalyst is used the formation of dendritic polymers is favored with only a very small fraction of highly branched chains assuming comb structure. The use of a binary catalyst system is therefore proposed to obtain high content of comb polymers. One catalyst generates macromonomers and the other yields in‐situ branching. It is found that the comb polymers give much narrower molecular weight distributions than dendritic polymers with same branching densities.