Solvent diffusion in amorphous polymers: Polyvinyl acetate-toluene system

Abstract

In a previous publication (Tihminlioglu et al., J Polym Sci Part B: Polym Phys 1997, 35, 1279), we presented an extensive analysis of the polyvinyl acetate-toluene system. The inverse gas chromatography (IGC) technique was used to measure phase equilibria and diffusion coefficients above and near the glass-transition temperature of a polymer. At temperatures above the glass transition, the capillary column model developed by Pawlisch et al. (Macromolecules 1987, 20, 1564) was used. For the finite concentration region, the modified model of Tihminlioglu and Danner (J Chromatogr A 1999, 845, 93) was applied. Data obtained with the IGC method were in agreement with data measured with the gravimetric and piezoelectric sorption techniques. In this work, we revisit the partition coefficient issue and provide some new data at lower temperatures. At temperatures near the glass-transition temperature, the modification of the capillary column model proposed by Vrentas et al. (Macromolecules 1993, 26, 6670) was used for the infinite dilution region. The diffusion data correlated well with the Vrentas-Duda free-volume model.