05/00899 Phase behavior applications of SAFT based equations of state — from associating fluids to polydisperse, polar copolymers

Abstract

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 χ 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°C higher than the lower critical solution temperature of the (non-crosslinked) polymer solution.