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Formation of polyionic polymer complexes (PIC) by the reaction of sodium poly(styrenesulfonate) (NaSS) with some cationic polymers of an integral type, which have cationic sites in the polymer backbone, have been studied in comparison with polycationic species of a pendant type. The reaction in aqueous solution was rapid and stoichiometric, and led to the formation of the precipitate of PIC. The infrared spectra of the precipitates coincided with that of the equimolar mixture of polycations and polyanions. The solubility of each component was completely different, so an ionic cross-linked structure was suggested. By the use of cationic polymers of an integral type as polycationic components, PIC once formed could be dissolved again when excess NaSS was added. This phenomenon seemed to be due to electrostatic interaction between polycationic sites which were not protected by hydrophobic moiety and other polyanionic sites of NaSS to loose salt-like bond. The behavior in resolution of PIC was different according to the structure of each polycation. Phase diagram of PIC containing cationic polymer of an integral type for a ternary solvent (water-organic solvent-simple salt electrolyte) had fairly smaller dissolution region than that of PIC of the pendant-pendant type.

The Reaction in the Formation of Polyionic Polymer Complexes