Ionic Correlations in Random Ionomers

Understanding the electrostatic interactions in ion-containing polymers is crucial to better design shape memory polymers and ion-conducting membranes for multiple energy storage and conversion applications. In molten polymers, the dielectric permittivity is low, generating strong ionic correlations that lead to clustering of the charges. Here, we investigate the influence of electrostatic interactions on the nanostructure of randomly charged polymers (ionomers) using coarse-grained molecular dynamics simulations. Densely packed branched structures rich in charged species are found as the strength of the electrostatic interactions increases. Polydispersity in charge fraction and composition combined with ion correlations leads to percolated nanostructures with long-range fluctuations. We identify the percolation point at which the ionic branched nanostructures percolate and offer a rigorous investigation of the statistics of the shape of the aggregates. The extra degree of freedom introduced by the charge polydispersity leads to bicontinuous structures with a broad range of compositions, similar to neutral A–B random copolymers, as well as to desirable percolated ionic structure in randomly charged-neutral diblock copolymers. These findings provide insight into the design of conducting and robust nanostructures in ion-containing polymers.