Predicting MWD and Branching Distribution of Terminally Branched Polymers Undergoing Random Scission

A new semi-analytical approach to model simultaneous chain scission and branching is described that assumes the separation of the scission and the branching problem. The required properties of the linear segments or primary polymers forming the branched architectures are found by a kinetic model. The general rules for the construction of branched architectures from populations of linear segments then lead to an analytical expression for the branching distribution and a semi-analytical expression for the bivariate length/branching distribution. The method is applied to the scission of an initially branched polymer and subsequent terminal branching on scission points and activated terminal double bonds. Exact agreement is found with Monte Carlo sampling results.