When Do Water-Insoluble Polyion-Surfactant Ion Complex Salts "Redissolve" by Added Excess Surfactant?

The redissolution of water-insoluble polyion-surfactant ion complexes by added excess of surfactant has systematically been investigated in experimental and theoretical phase equilibrium studies. A number of stoichiometric polyion-surfactant ion "complex salts" were synthesized and they consisted of akyltrimethylammonium surfactant ions of two different alkyl chain lengths (C(12)TA(+) and C(16)TA(+)) combined with homopolyions of polyacrylate of two different lengths (PA(-)(25) and PA(-)(6000)) or copolyions of acrylate and the slightly hydrophobic nonionic comonomers N-isopropylacrylamide (PA(-)-co-NIPAM) or N,N-dimethylacrylamide (PA(-)-co-DAM). The complex salts were mixed with water and excess alkyltrimethylammonium surfactant with either bromide or acetate counterions (C(n)TABr or C(n)TAAc). Factors promoting efficient redissolution were (i) very short polyions, (ii) a large fraction of NIPAM or DAM comonomers, and (iii) acetate, rather than bromide, as the surfactant counterion. Added C(12)TAAc gave an efficient redissolution of C(12)TAPA(25) but virtually no redissolution of C(12)TAPA(6000). A very efficient redissolution by added C(12)TAAc was obtained for PA(-)-co-NIPAM with 82 mol % of NIPAM. The C(12)TAPA-co-NIPAM/C(12)TAAc/H(2)O ternary phase diagram closely resembled the corresponding diagram for the much-studied pair cationic hydroxyethyl cellulose-(sodium) dodecyl sulfate. The simple Flory-Huggins theory adopted for polyelectrolyte systems successfully reproduced the main features of the experimental phase diagrams for the homopolyion systems, including the effect of the surfactant counterion. The efficient redissolution found for certain copolyion systems was explained by the formation of soluble polyion-surfactant ion complexes carrying an excess of surfactant ions through an additional hydrophobic attraction.