Dynamics of Polymer Chains in Disperse Melts: Insights from Coarse-Grained Molecular Dynamics Simulations.

Abstract

Synthetic polymers have a distribution of chain lengths which can be characterized by dispersity, Đ. Their macroscopic properties are influenced by chain mobility in the melt, and controlling Đ can significantly impact these properties. In this work, we present a detailed study of the static and dynamic behavior of fully flexible polymer chains that follow the Schulz-Zimm molecular weight distribution up to Đ = 2.0 using coarse-grained molecular dynamics simulations. We analyze the behavior of test chains with molecular weights that are equal to, above, or below the molecular weight (M_w) of the melt. Static analysis shows that the conformation of these test chains remains unaffected by the heterogeneity of the surrounding chains. To study the dynamics, we computed the mean-squared displacement of test chains in melts of the same M_w and different dispersities. The mobility of test chains with N > M_w steadily increases with dispersity, due to the shorter chains contributing to early onset of disentanglement of the long chains. However, the dynamics of test chains of length N < M_w is nonmonotonic with respect to dispersity; this behavior arises from a trade-off between the increased mobility of shorter chains and the corresponding slowdown caused by the presence of longer chains. We examine the dynamic structure factor and find a weakening of tube confinement, with the effects becoming less pronounced with increasing dispersity and M_w. These findings provide insights into the rich dynamic heterogeneity of disperse polymer melts.