Abstract
In this paper we calculate the phase diagrams of polyelectrolyte solutions taking into account the possibility of ion pair formation between counterions and ions on polymer chains with their subsequent aggregation in multiplets. Multiplets play a role of reversible physical crosslinks between different polymer chains. Furthermore, we assume that the dielectric constant, and hence the binding energy of ion pairs and multiplets, depends on the volume fraction of polymer in the solution. We have shown that ion pairing and multiplet formation leads to instability of the homogeneous phase, so that at some conditions the phase separation can proceed even in doog solvent. Another qualitatively new feature of the behavior of polyelectrolyte solutions is the emergence of a triple point on the phase diagram. The effect of the solvent polarity and the polarity of the dry polymer on the general form of the phase diagram is studied in detail.
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