Modeling Gel Swelling in Binary Solvents: A Thermodynamic Approach to Explaining Cosolvency and Cononsolvency Effects

If gel swells in binary solvents, two unusual phenomena may appear. Two solvents with relatively low swelling ability may become a good solvent for the polymer with high swelling ability when mixed, which is known as a cosolvency effect. In contrast, a cononsolvency effect indicates polymer is less soluable in solvent mixtures than it is in each of the cosolvents. In this work, we develop a thermodynamic theory to describe the equilibrium swelling behaviors of gels in binary solvents based on the Flory–Huggins lattice model. The model can reproduce both cosolvency and cononsolvency effects, showing that these effects are caused by the preferential absorption of the solvent by polymer together with solvent–solvent interactions. The model is also applied to describe experimentally observed cosolvency and cononsolvency effects in the literature, which shows an acceptable agreement.