Gas transport properties of polyimide membranes based on triphenylamine unit

A series of polyimide (PI) membranes were prepared based on three triphenylamine-based diamines, namely 4,4′-diaminotriphenylamine, 4,4′-diamino-3′′,5′′-dimethyltriphenylamine, and 4,4′-diamino-3′′,5′′-ditrifluoromethyltriphenylamine, via thermal imidization procedure. The PI membranes displayed good thermal properties, with glass transition temperatures of 279–341°C and 5% weight loss temperatures above 515°C under a nitrogen atmosphere. The gas permeation properties of the membranes were investigated and interpreted from the viewpoint of the PI backbone structure. The gas permeation coefficients increased as the substituent pendant groups at the 3′′,5′′ positions of the triphenylamine varied from –H to –CH₃ and –CF₃, and the permselectivity of gas pairs (including hydrogen/nitrogen (N₂), oxygen/N₂, carbon dioxide (CO₂)/N₂, and CO₂/methane) decreased in this order. The diffusion coefficients and solubility coefficients were calculated, and the results revealed the variation of the substituted triphenylamine units principally influenced the diffusion coefficients, indicating that the substituted triphenylamine affected the gas transport properties by “diffusivity-controlled” modification.