Effect of pendant ester groups on gas transport property of 6FDA-BAPP/6FAP copolyimide membrane

Despite the various methods that have been developed, controlling the microstructure of polyimide membranes to achieve excellent separation performance based on target gases remains a challenge. One such method involves rearranging polyimides containing ortho-hydroxyl groups into polybenzoxazoles at temperatures above 400 °C, which can effectively distort the backbones and improve gas diffusion. However, this approach is limited by the extremely high conversion temperatures required and low conversion degrees achieved. The esterification process of the polyimide, which contains ortho-hydroxyl groups to the imide ring, represents a simple and effective approach to enhance the membrane's competitiveness in gas separation without undergoing thermal rearrangement at high temperatures. The polyimide was prepared by the polycondensation of 4,4'-(Hexafluoro isopropylidene) diphthalic anhydride (6FDA), 2,2-double (4,4-amino phenoxy) propane (BAPP), and 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (6FAP). Microstructures and gas transport coefficients were analyzed when the esterification of 6FDA-BAPP/6FAP was conducted using acetic anhydride and caproic anhydride. In CO2/N2 separation, a-6FDA-BAPP/6FAP exhibits CO2 permeability of 1279.41 ± 66.93 Barrer and perm-selectivity of 40.80 ± 2.27, owing to the significantly improved affinity to CO2. The membrane of c-6FDA-BAPP/6FAP exhibit the further improved CO2 permeability and deteriorated perm-selectivity, due to a leveling effect on the diffusion of CO2 and N2 caused by the pendant caproates with longer alkyl chains. The results confirmed that the gas separation performance of polyimide membrane containing ortho-hydroxyl groups is sensitive to the pendant group. [Display omitted] •Esterification of the polyimides containing hydroxyl groups at ortho position of imide rings enhance CO2/N2 separation.•The esterification effectively enhanced CO2 solubility, resulting in an excellent CO2/N2 separation performance surpass 2008 upper bound.•Longer alkyl chain in the pendant ester groups exhibit a leveling effect on CO2 and N2 transport.