Synthesis and Gas-Permeation Characterization of a Novel High-Surface Area Polyamide Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene: Towards Polyamides of Intrinsic Microporosity (PIM-PAs)

A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N bond of the amide group leading to enhanced fractional free volume. Based on N(2) sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer–Emmett–Teller (BET) surface area of 396 m(2) g(−1); to date, this is the highest value reported for a linear polyamide. The aged 6FBBA-TMDAT sample showed moderate pure-gas permeabilities (e.g., 198 barrer for H(2), ~109 for CO(2), and ~25 for O(2)) and permselectivities (e.g., αH(2)/CH(4) of ~50) that position this polyamide close to the 2008 H(2)/CH(4) and H(2)/N(2) upper bounds. CO(2)–CH(4) mixed-gas permeability experiments at 35 °C demonstrated poor plasticization resistance; mixed-gas permselectivity negatively deviated from the pure-gas values likely, due to the enhancement of CH(4) diffusion induced by mixing effects.