Dependence of Grafted Polymer Property on the Initiator Site Distribution in Surface-Initiated Polymerization: A Computer Simulation Study

Abstract

By molecular dynamics simulations coupled with the stochastic polymerization model, we show a certain dependence of the polymer chain polydispersity on the heterogeneity of the initiator sites distribution during surface-initiated polymerization. The heterogeneity of the initiators will lead to change of the mass distribution and the uncontrollability of polydispersity index (PDI) as compared to the homogeneous counterpart. We find a linear master curve of the polymer chain PDI on the interplay of heterogeneity parameter and initiator density, which actually reveals a quantitative dependence of polymer PDI on the free space between neighboring chains. This study helps to better understand and predict the chain polydispersity in the grafted materials via the surface-initiated polymerization.