Thermoreversible Gelation of Associating Polymers in Hydrogen-Bonding Mixed Solvents

The thermoreversible gelation of associating polymers in hydogen-bonding mixed solvents is studied theoretically on the basis of the model ternary solution in which polymers carrying functional group A are dissolved in a primary solvent SB (mainly water) and cosolvent SC. Functional group A forms intermolecular cross-links (A-A) leading to gelation. It can also form hydrogen bonds with either solvent molecule SB or SC (A-SB, A-SC). If bound to a solvent molecule, A becomes inert. Solvent molecules form complexes with variable association numbers (SB-SC). Ternary phase diagrams for sol-gel transition lines and their cross sections on the temperature-solvent composition plane are constructed. It is shown that a minimum in the polymer concentration along the sol-gel transition line appears at a special solvent composition which depends upon the structure of the complexes. At such an optimal gel point, the sol-gel transition temperature becomes the highest, thus leading to stable, strong gels. The degree of adsorption, preferential adsorption coefficient, average molecular weight of the complexes, and cross-link probability are calculated as functions of the solvent composition. At the optimal gel point, the preferential adsorption coefficient changes its sign and the average molecular weight of the complexes reaches a maximum. Results are compared with the experimental data on poly(vinyl alcohol) in a mixed solvent of water/dimethyl sulfoxide, dimethyl sulfoxide/urea, or water/methanol.