Effects of Ionic Group Distribution on the Structure and Dynamics of Amorphous Polymer Melts

Ionizable groups tethered to a polymer backbone often associate to form ionic clusters, whose features are determined by the balance of the polymer backbone and electrostatics. These assemblies impact the dynamics of the macromolecules and their ability to transport ions. Here, using fully atomistic molecular dynamics (MD) simulations, we investigate the effects of the distribution of ionizable groups along the polymer backbone on cluster characteristics and the resulting impacts on the structure and dynamics of amorphous polymers. Particularly, we probe polystyrene sulfonates (PSS) with random, precise, and block configurations of the SO3- sulfonate groups along the backbone with Na+ as the counterion. We find that the distribution of the ionic groups affects the shape and distribution of the clusters as well as the internal packing of the ionizable groups in the cluster and the number of unique chains that participate in each cluster, affecting the structure and the dynamics of the polymers. The signature of ionic clusters, observed in the static structure factor S(q) for all three distributions, is significantly more pronounced for the precise and blocky polymers compared to the random one. Remarkably, we find that the local mobility of the polymer segments is not only affected by the number and size of the clusters but also by the number of polymer chains associated with clusters.

Automated summary

In this study, the effects of the distribution of ionizable groups along the polymer backbone on cluster characteristics and the resulting impacts on the structure and dynamics of amorphous polymers were investigated using atomistic molecular dynamics simulations. The distribution of ionic groups was found to affect the shape, distribution, and internal packing of the clusters, as well as the number of unique chains participating in each cluster, thus influencing the structure and dynamics of the polymers. The mobility of the polymer segments was found to be affected by not only the number and size of the clusters, but also by the number of polymer chains associated with clusters.