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 N₂ sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer⁻Emmett⁻Teller (BET) surface area of 396 m² 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 H₂, ~109 for CO₂, and ~25 for O₂) and permselectivities (e.g., αH₂/CH₄ of ~50) that position this polyamide close to the 2008 H₂/CH₄ and H₂/N₂ upper bounds. CO₂⁻CH₄ 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 CH₄ diffusion induced by mixing effects.
Keywords: PIM-polyamides; gas separation; gas sorption; glassy polymers; intrinsic microporosity; mixed-gas permeation; polyamides; triptycene diamine.