Macromolecules, Vol.54, No.4, 1783-1800, 2021
Dynamic Coupling in Unentangled Liquid Coacervates Formed by Oppositely Charged Polyelectrolytes
We develop a scaling theory that predicts the dynamics of symmetric and asymmetric unentangled liquid coacervates formed by solutions of oppositely charged polyelectrolytes. Symmetric coacervates made from oppositely charged polyelectrolytes consist of polycations and polyanions with equal and opposite charge densities along their backbones. These symmetric coacervates can be described as mixtures of polyelectrolytes in the quasi-neutral regime with a single correlation length. Asymmetric coacervates are made from polycations and polyanions with unequal charge densities. The difference in charge densities results in a double semidilute structure of asymmetric coacervates with two correlation lengths, one for the high-charge-density and the other for the low-charge-density polyelectrolytes. We predict that the double semidilute structure in asymmetric coacervates results in a dynamic coupling, which increases the friction of the high-charge-density polyelectrolyte. This dynamic coupling increases the contribution to the zero-shear viscosity of the high-charge-density polyelectrolyte. The diffusion coefficient of the high-charge-density polyelectrolyte is predicted to depend on the concentration and degree of polymerization of the low-charge-density polyelectrolyte in the coacervate if the size of the low-charge-density polymer is smaller than the correlation length of the high-charge-density polymer. We also predict a non-monotonic salt concentration dependence of the zero-shear viscosity of asymmetric coacervates.