Polymer, Vol.39, No.14, 3279-3283, 1998
Molecular thermodynamics for volume-change transitions in temperature-sensitive polymer gels
A molecular-thermodynamic model is presented to predict volume-change transitions in temperature-sensitive polymer gels. The model uses an extended Flory-Huggins theory as a mixing contribution and a new interpolated affine model suggested by Birshtein as an elastic contribution. The Flory chi parameter is given by the product of a temperature-dependent and a composition-dependent term. Our model also differs from those presented previously because the temperature-dependent term is given by the incompressible lattice-gas model by ten Brinke and Karasz that accounts for specific interactions such as hydrogen bonding. Following conventional practice, the van't Hoff equation is introduced to represent the effect of a small number of ionizable segments in the network chain. Calculated swelling-ratio curves for neutral and weakly ionized aqueous N-isopropylacrylamide gels use molecular parameters obtained from phase-equilibrium data for (non-crosslinked) polymer solutions. In agreement with experiment, the calculated volume-transition temperature of the gel is about 1 degrees C higher than the lower critical solution temperature of the (non-crosslinked) polymer solution.
Keywords:N-ISOPROPYLACRYLAMIDE GELS;GLOBULE TYPE TRANSITIONS;PHASE-TRANSITIONS;LINEAR MACROMOLECULES;IONIC GELS;NETWORKS;SYSTEMS;EQUILIBRIA;COLLAPSE;BEHAVIOR