Phase Behavior of Ion-Containing Polymers in Polar Solvents: Predictions from a Liquid-State Theory with Local Short-Range Interactions

Abstract

The thermodynamic phase behavior of charged polymers is a crucial property underlying their role in biology and various industrial applications. A complete understanding of the phase behaviors of such polymer solutions remains challenging due to the multi-component nature of the system and the delicate interplay among various factors, including the translational entropy of each component, excluded volume interactions, chain connectivity, electrostatic interactions, and other specific interactions. In this work, the phase behavior of partially charged ion-containing polymers in polar solvents is studied by further developing a liquid-state (LS) theory with local shortrange interactions. This work is based on the LS theory developed for fully-charged polyelectrolyte solutions. Specific interactions between charged groups of the polymer and counterions, between neutral segments of the polymer, and between charged segments of the polymer are incorporated into the LS theory by an extra Helmholtz free energy from the perturbed-chain statistical associating fluid theory (PC-SAFT). The influence of the sequence structure of the partially charged polymer is modeled by the number of connections between bonded segments. The effects of chain length, charge fraction, counterion valency, and specific short-range interactions are explored. A computational App for salt-free polymer solutions is developed and presented, which allows easy computation of the binodal curve and critical point by specifying values for the relevant model parameters.