Gas sorption and transport in polyarylates: effect of substituent symmetry and polarity

Abstract

The gas sorption properties of polyarylates based on bisphenol-A possessing symmetric/asymmetric substitution by nonpolar -CH₃ group and symmetrically linked terephthalic acid were examined. The effects of substitution of polar bromine on terephalic acid moiety of polyarylate based on asymmetrically substituted bisphenol were also studied for physical, sorption and transport properties. The estimation of dual mode sorption parameters, solubility and diffusion coefficient revealed that nature of the substituent and substitution type plays a crucial role in depicting permeation properties. An asymmetric substitution by -CH₃ group increased solubility coefficient of pure gases (N₂, O₂, CH₄ and CO₂) up to 27% and symmetric substitution increased the same up to 106%. This was coupled with 7-35% increase in solubility selectivity in both cases of substitution, which ascertained the usefulness of methyl group substitution in polyarylates based on terephalic acid. The pressure dependency of solubility coefficients and solubility selectivity was also investigated for these polyarylates. The sorption and transport properties of these polyarylates correlated well with physical properties of polyarylates and gases studied. The sorption/desorption kinetics of symmetrically substituted TMBisA-T was performed in order to deduce time dependent sorption behavior and to evaluate diffusivity coefficient. The apparent diffusion coefficients from sorption kinetics, desorption kinetics and from steady-states permeation-sorption were compared. The diffusion coefficients of CH₄ and N₂ deduced by these methods correlated well with each other.