The synthesis and gas permeation properties of two 6FDA-dianhydride-based polyimides prepared from 2,6-diaminotriptycene (6FDA-DAT1) and its extended iptycene analog (6FDA-DAT2) are reported. The additional benzene ring on the extended triptycene moiety in 6FDA-DAT2 increases the free volume over 6FDA-DAT1 and reduces the chain packing efficiency. The BET surface area based on nitrogen adsorption in 6FDA-DAT2 (450 m(2) g(-1)) is similar to 40% greater than that of 6FDA-DAT1 (320 m(2) g(-1)). 6FDA-DAT1 shows a CO2 permeability of 120 Barer and CO2/CH4 selectivity of 38, whereas 6FDA-DAT2 exhibits a 75% increase in CO2 permeability to 210 Barrer coupled with a moderate decrease in selectivity (CO2/CH4=30). Interestingly, minimal physical aging was observed over 150 days for both polymers and attributed to the high internal free volume of the shape-persistent iptycene geometries. The aged polyimides maintained CO2/CH4 selectivities of 25-35 along with high CO2 permeabilities of 90-120 Barrer up to CO2 partial pressures of 10 bar in an aggressive 50:50 CO2:CH4 mixed-gas feed, suggesting potential application in membranes for natural gas sweetening. (C) 2015 Elsevier B.V. All rights reserved.