Synthesis of Highly Gas-Permeable Polyimides of Intrinsic Microporosity Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene

[Image: see text] A simple synthetic route to a novel sterically hindered triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diaminotriptycene (TMDAT), and its use in the preparation of high molecular weight polyimides of intrinsic microporosity (PIM-PIs) are reported. The organosoluble TMDAT-derived polyimides displayed high Brunauer–Emmett–Teller surface areas ranging between 610 and 850 m(2) g(–1) and demonstrated excellent thermal stability of up to 510 °C. Introduction of the rigid three-dimensional paddlewheel triptycene framework and the tetramethyl-induced restriction of the imide bond rotation resulted in highly permeable polyimides with moderate gas-pair selectivity. The best performing polyimide made from TMDAT and a triptycene-based dianhydride showed gas transport properties located between the 2008 and 2015 polymer permeability/selectivity trade-off curves with H(2) and O(2) permeabilities of 2858 and 575 barrer combined with H(2)/N(2) and O(2)/N(2) selectivities of 24 and 4.8, respectively, after 200 days of physical aging.