Membrane-based helium recovery from natural gas faces a major challenge due to membrane plasticization, which increases permeances but reduces selectivities. Thermal crosslinking has emerged as a promising approach to enhance the plasticization resistance of membranes by restricting segmental mobility and creating well-defined microporosity for gas separation. Herein, we develop novel dual thermally crosslinked asymmetric hollow fiber membranes (HFMs) using a 4,4′-diamino-2,2′-biphenyldicarboxylic acid-containing copolyimide. Decarboxylation-based dual crosslinking is achieved through heat treatment at various temperatures, resulting in the generation of C–C covalent bonds. The interchain distance increases from 5.33 to 5.76 Å, and the hierarchical pore size distributions exhibit ultra-micropore size between 5.6 and 6.8 Å as well as micropore size between 7.0 and 9.5 Å. Notably, the formation of stable C–C covalent bonds through dual crosslinking and the existence of bulky −CF3 groups in the 2,2′-bis(trifluoromethyl)-4,4′-biphenyldiamine moiety prevent substructure collapse by enhancing the chain rigidity and rotational barrier. Gas transport properties of the crosslinked HFMs are effectively tuned by adjusting the heat treatment temperatures. Particularly, the PI-TFMB-HF@400 membrane exhibits a He permeance of 25 GPU and He/CH4 selectivity of 269. Additionally, the crosslinked HFMs exhibit enhanced plasticization resistance. The PI-TFMB-HF@400 membrane, for instance, shows only a 24 % decrease in mixed-gas CO2/CH4 selectivity and an 80 % increase in mixed-gas [He/(CO2 + CH4)] selectivity when exposed to a high-pressure (40 bar) ternary mixed-gas feed of He/CO2/CH4 (0.3/49.7/50, v/v/v), and the mixed-gas [He/(CO2 + CH4)] selectivity increases with temperature. The dual thermally crosslinked HFMs in this study demonstrate the potential for helium recovery from aggressive natural gas.
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