Molecular design of free volume structure in thermally rearranged polybenzoxazole membranes for gas separation studied by positron annihilation

Abstract

AbstractIn this work, 2,2‐bis(3‐amino‐4‐hydroxyphenyl) hexafluoropropane (APAF) was used as the fixed diamine monomer, and 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), 3,3′,4,4′‐biphenyltetracarboxylic diandhydride (BPDA) and pyromellitic dianhydride (PMDA) were selected as four different dianhydride monomers, respectively, to prepare the thermally rearranged polybenzoxazole (TR‐PBO) gas separation membranes with different structures via a thermal rearrangement reaction at 450°C. The microstructure of TR‐PBO membranes was investigated using X‐ray diffraction and positron annihilation spectroscopy. All the TR‐PBO membranes exhibit bimodal free volume structure, containing ultramicropores (<0.7 nm) and micropores (<2 nm) with size of 3.6–4.6 and 7.6–8.4 Å, respectively. As the steric hindrance of the bridging groups in the dianhydride monomers increases, the radius and number of pores in the membranes increases, leading to an increase in fractional free volume (FFV). The pure gas permeation test shows a positive correlation between gas permeability and FFV in the TR‐PBO membranes, indicating that an increase in FFV is favorable for the diffusion of gas molecules. Particularly, the ultramicropores play a decisive role on the gas selectivity. All the TR‐PBO membranes exhibit excellent gas permeaselectivity. Among them, the H2/CH4 separation performance of APAF‐6FDA and APAF‐ODPA membranes approaches the 2008 Robeson upper bound, which is due to the high number of both micropores and ultramicropores. Our results demonstrate that the free volume structure of polymer membranes can be designed by selecting monomers with different structures and utilizing thermal rearrangement reactions, allowing for the preparation of gas separation membranes with high permeability and selectivity.