Two intrinsically microporous polyimides were obtained by high-temperature, one-pot poly-condensation reaction of novel triptycene-based dianhydrides containing dimethyl- or diisopropyl-bridgehead groups with a commercially available highly sterically hindered 3,3 '-dimethylnaphthidine (DMN) diamine monomer. The dimethyl bridgehead groups in the triptycene building block provided the DMN-based polyimide (TDA1-DMN) with larger surface area (760 m(2) g(-1)) than the diisopropyl-based polyimide (TDA1-DMN) (680 m(2) g(-1)), greater fraction of ultramicroporosity, as observed from N-2 and CO2 NLDFT adsorption analysis, and higher gas permeability and selectivity. Wide-angle X-ray diffraction (WAXD) measurements demonstrated that TDA1-DMN and TDAi3-DMN exhibited a bimodal pore size distribution, where TDA1-DMN showed smaller d-spacing values and broader intensity peaks. Both TDADMN-based polyimides showed very high gas permeabilities with moderate selectivities. For example, fresh TDA1-DMN exhibited an O-2 permeability of 783 Barrer coupled with an O-2/N-2 selectivity of 4.3 and H-2 permeability of 3050 Barrer with H-2/N-2 selectivity of 16.7, values that surpassed the 2008 Robeson permeability/selectivity upper bounds. Physical aging of the TDA-DMN polyimide films over a period of 250 days showed relatively small changes in permeability (similar to 20%) and selectivity (similar to 5%). (C) 2016 Elsevier Ltd. All rights reserved.