HAB-6FDA polyimide was synthesized from 3,3'-dihydroxy-4,4'-diamino-biphenyl (HAB) and 2,2'-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) by a two-step polycondensation method with chemical imidization. This polyimide was used as the precursor to prepare thermally rearranged (TR) polymers. The rearrangement reaction was performed at temperatures from 350 to 450 degrees C. Based on mass loss during the TR process, TR conversion levels as high as 76% were observed. CO2 permeability increased from 12 Barrer in the precursor polyimide (HAB-6FDA) to 410 Barrer in the TR polymer prepared at 450 degrees C, while pure gas CO2/CH4 selectivity decreased from 42 to 24. Both diffusivity and solubility increased following the rearrangement process, but the change in gas diffusivity was the largest contribution to the increase in permeability. From the polyimide to the sample heated at 450 for 30 min, CO2 diffusivity increased by approximately a factor of 20 while solubility increased by a factor of 1.7. Similar changes were observed for other gases. Fractional free volume increased from 15% in the polyimide precursor to 20% in the TR polymer rearranged at 450 degrees C. The HAB-6FDA TR polymers exhibited higher CO2 permeability than other classes of polymers with similar free volume, suggesting a free volume distribution in these TR polymers that favors high permeability. (C) 2012 Elsevier B.V. All rights reserved.