Formation of Polyelectrolyte Complexes and Their Structures

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Abstract
When a polycation and a polyanion are mixed together in an aqueous solution, a polyelectrolyte complex is formed. In general, an equimolar complex is formed by mixing oppositely charged strong polyelectrolytes. However, integral-type polycations provide nonstoichiometric complexes. In the case of the complexation of polycations with weak polyacids, the composition and the structure of the polyelectrolyte complexes obtained depend on the degree of neutralization of the polyacid, polymer structure, hydrophobicity, the concentration of the complex, pH, ionic strength, and so on. Complex formation proceeds cooperatively, and the stability constant increases with the degree of polymerization, i.e., the charge number on one chain. When a polyelectrolyte is added to the polymer complex, a cooperative interpolymer substitution occurs if the adding polymer can interact more strongly with the constituent of the complex. The process of polyelectrolyte complex leading to the supermolecular structure can be divided mainly into three classes: 1) primary complex formation, 2) formation process within intracomplexes, and 3) intercomplex aggregation.

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