Monte carlo simulation of emulsion polymerization — linear, branched, and crosslinked polymers

Abstract

AbstractA new Monte Carlo approach for the kinetics of emulsion polymerization is discussed. The diameters of polymer particles produced in emulsion polymerizations are in the submicrometer range; therefore, it is straightforward to simulate the formation processes of all polymer molecules in each polymer particle by application of the Monte Carlo method with a well‐designed algorithm. In the Monte Carlo technique, virtually any kinetic event, such as the desorption of oligomeric radicals, chain‐length‐dependent reaction kinetics, branching and crosslinking reactions, can be accounted for. In principle, neither idealizations nor approximations, which are usually required in the analytical approaches, are not necessary. As a consequence one can observe the structure of each polymer molecule directly; therefore, very detailed information can be obtained easily, including the full distributions of the dead and live polymer molecular weights, and the spatial distribution of the branched and crosslinked polymer chains in the case of nonlinear polymerizations. Monte Carlo simulations promise to provide greater insight into the complex molecular processes which occur during emulsion polymerizations.