Reentrant conformation transition in poly( N, N-dimethylacrylamide) hydrogels in water–organic solvent mixtures

Abstract

Conformational changes in poly( N, N-dimethylacrylamide) (PDMA) networks swollen in aqueous solutions of organic solvents are studied both experimentally and theoretically. PDMA hydrogels of various charge densities were prepared by free-radical crosslinking copolymerization. Swelling behavior of the hydrogels was investigated in aqueous organic solvent mixtures as functions of solvent species and the concentration. With increasing volume fraction ϕ of acetone, tetrahydrofuran, or 1,4-dioxane in the aqueous solution, PDMA hydrogels exhibit reentrant conformation transition. During this transition, the gel first deswells in the range of ϕ between 0.4 and 0.9, and then rapidly reswells if ϕ is monotonically increased. The reswelling of the collapsed PDMA gel occurs in a narrow of ϕ above ϕ=0.97. It was shown that the reentrant transition in PDMA gels requires moderate hydrogen bonding organic solvents, so that the hydrophobic interactions between PDMA and the organic solvent dominate the swelling process. The results were interpreted using the theory of equilibrium swelling. The interaction parameters in the gel system as well as the partition parameter of the organic solvent between the gel and the solution phases were calculated.