Influence of the chain composition on the thermodynamic properties of binary and ternary polymer solutions

Thermodynamic properties of binary and ternary polymer solutions (one or two uncharged polymers in one solvent) were studied. Poly(vinyl pyrrolidone) (PVP), fully hydrolyzed poly(vinyl alcohol) (PVA) homopolymers, and water-soluble poly(vinyl alcohol-co-vinyl acetal, vinyl propional, and -vinyl butiral) copolymers with various acetal content and chain structure, respectively. were used in the experiments. The hydrophilic/hydrophobic character of the PVA-based macromolecules and their compatibility with the PVP homopolymer were systematically regulated by changing the chemical structure of the copolymers (acetal content and/or length of side chains). The water activities in binary and ternary, solutions of the chemically different polymers were determined by a gel-deswelling method developed here for ternary solutions. On the basis of the Flory-Huggins theory, the relevant solvent-segment and segment-Segment pair interaction parameters Q) have been calculated. The x(12) segment-solvent interaction parameters proved to be sensitive indicators for changes in the chemical structure of the copolymers. With increase of either the acetal content or the length of side chains in the copolymer. x(12) approached the value characteristic of a theta condition. No significant differences could be revealed in the segment-segment interaction parameters obtained for the PVP-copolymer mixtures with various acetal derivatives. when the x(12) and x(13) interaction parameters determined in binary solutions were used in the calculations for x(23). Determination of the parameters x(1,23) as suggested by Panayiotou, however, showed that increasing the acetal content or the length of the hydrophobic side chains in the copolymer resulted in a reduction in the interaction between the PVA "acetals" and PVP molecules.