Abstract
Compleximers are a novel class of materials that combine the properties of thermoplastics and thermosets, due to their reversible network structure facilitated by ionic interactions moderated by hydrophobic attenuators. In this study, we investigate the structural and dynamic properties of various architectures of these relatively unexplored, water-free polyelectrolyte complex materials using molecular dynamics simulations. We find that decreasing the number of charges per unit mass, either by increasing the length of neutral side chains or by decreasing the charge density of the polymers, leads to a decrease in density. This is related to a decrease in cohesive energy and in the number of contacts between oppositely charged beads. These structural changes result in an enhancement of the dynamics and a lowering of the glass transition temperature (T(g)), which correlates with the number of oppositely charged contacts in the first coordination shell of the monomers. The fragility, represented in Angell plots, was found to be universal for all systems, irrespective of charge density. Compleximers also follow the universal correlation between the structural relaxation time and the rattling amplitude in glass-forming liquids.