Synthesis and characterization of triptycene-based polyimides with tunable high fractional free volume for gas separation membranes

Robust polymer membranes that are highly permeable and selective are desired for energy efficient gas separation processes. In this study, a series of rigid, bulky triptycene-based diamine monomers were designed, synthesized, and subsequently incorporated into the backbone of polyimides via polycondensation with 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) to obtain a series of polyimide membranes with high fractional free volume. These triptycene-containing polyimides with systematic variations in their chemical structure demonstrate the viability of the 'tunable' fractional free volume by introducing various substituents onto the polymer backbone. All the polyimides synthesized exhibited film-forming high molecular weight, high solubility, and excellent thermal properties, with glass transition temperatures ranging from 280 °C to 300 °C and thermal stability up to 500 °C. Compared to other classes of glassy polymers, these triptycene-polyimides had high combinations of permeability and selectivity, suggesting that a favorable free volume size distribution in these triptycene polyimides was induced by the unique chain packing mechanism of triptycene units. The correlation between gas transport properties and the polymer chemical structure was also investigated. Altering the size of the substituents neighboring the triptycene units provides greater opportunity to fine-tune the fractional free volume and free volume size distribution in the polymer, which in turn can change the transport properties effectively to meet various separation needs. It is expected that additional design modifications made by exploiting the chemistry versatility of the triptycene moiety and by selectively adding other components may improve these membranes to break the gas permeability-selectivity trade-off barrier. This journal is