Markovian Approach to Free‐Radical Polymerization with Simultaneous Long‐Chain Branching and Scission: Effect of Branching and Scission Kinetics

Abstract The effect of branching and scission kinetics on the branched structure formation is investigated by using the analytic solution for the weight‐average chain length in a matrix formula, and the Monte Carlo simulation method, both based on the Markov chain statistics. The illustrative calculations, envisaged for the production of low‐density polyethylene, showed that the effect of different kinetics employed for the present study could be negligible when the final monomer conversion is smaller than about 25%, normally used for the commercial production processes. On the other hand, if the polymerization is continued up to higher conversion range, the functional forms for branching and scission kinetics start to show significant effects on the formed branched structure.