Pristine and thermally-rearranged gas separation membranes from novel o-hydroxyl-functionalized spirobifluorene-based polyimides

A novel o-hydroxyl-functionalized spirobifluorene-based diamine monomer, 2,2'-dihydroxyl-9,9'-spirobifluorene-3,3'-diamine (HSBF), was successfully prepared by a universal synthetic method. Two o-hydroxyl-containing polyimides, denoted as 6FDA-HSBF and SPDA-HSBF, were synthesized and characterized. The BET surface areas of 6FDA-HSBF and SPDA-HSBF are 70 and 464 m(2) g(-1), respectively. To date, SPDA-HSBF exhibits the highest CO2 permeability (568 Barrer) among all hydroxyl-containing polyimides. The HSBF-based polyimides exhibited higher CO2/CH4 selectivity than their spirobifluorene (SBF) analogues (42 for 6FDA-HSBF vs. 27 for 6FDA-SBF) due to an increase in their diffusivity selectivity. Polybenzoxazole (PBO) membranes obtained from HSBF-based polyimide precursors by thermal rearrangement showed enhanced permeability but at the cost of significantly decreased selectivity.