Polyelectrolyte Complexes: Phase Diagram and Intrinsic Viscosities of the System Water/Poly(2‐vinylpyridinium‐Br)/Poly(styrene sulfonate‐Na)

In contrast to all earlier work on that subject, measurements are performed at high dilution up to total polymer concentrations wpol of 0.5 wt%. Aqueous solutions of poly(2-vinylpyridinium-Br) and of poly(styrene sulfonate-Na) are only fully miscible if wpol < 0.02 wt%. Decomposition into two liquid phases is observed upon an increase in wpol, where the extension of the miscibility gap is considerably larger at 60 than at 25 °C. Viscosity measurements demonstrate that the formation of the polyelectrolyte complexes may take hours. The intrinsic viscosity of the polyanion turns out to be 20 times larger than that of the polycation and to be much more sensitive toward the addition of extra salt. The [η] values of the blend pass a minimum as a function of its composition.