Theory of self-coacervation in semi-dilute and concentrated zwitterionic polymer solutions

Based on the random phase approximation, we develop a molecular theory of self-coacervation in zwitterionic polymer solutions. We show that the interplay between the volume interactions of the monomeric units and electrostatic correlations of charged groups on a polymer backbone can result in liquid–liquid phase separation (self-coacervation). We analyse the behavior of the coacervate phase polymer concentration depending on the electrostatic interaction strength – the ratio of the Bjerrum length to the bond length of the chain. We establish that in a wide range of polymer concentration values – from a semi-dilute to a rather concentrated solution – the chain connectivity and excluded volume interaction of the monomeric units have an extremely weak effect on the contribution of the electrostatic interactions of the dipolar monomeric units to the total free energy. We show that for rather weak electrostatic interactions, the electrostatic correlations manifest themselves as Keesom interactions of point-like freely rotating dipoles (Keesom regime), while in the region of strong electrostatic interactions the electrostatic free energy is described by the Debye–Hückel limiting law (Debye regime). We show that for real zwitterionic coacervates the Keesom regime is realized only for sufficiently small polymer concentrations of the coacervate phase, while the Debye regime is approximately realized for rather dense coacervates. Using the mean-field variant of the density functional theory, we calculate the surface tension (surface free energy) of the “coacervate–solvent” interface as a function of the bulk polymer concentration. Obtained results can be used to estimate the parameters of the polymer chains needed for practical applications such as drug encapsulation and delivery, as well as the design of adhesive materials.