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Steric hindrance effects of diverse substituents in spirobisindane-based polyimides for gas separation
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DOI：10.1016/j.seppur.2026.139624.png)
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Abstract
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Development of polymer membranes that combine high processability with superior gas permselectivity remains a critical challenge. In this work, a series of spirobisindane-based polyimides bearing diverse substituents (SPIRO-PIs) were synthesized by polymerization with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Substituents including H, -CF3, and -CH3 were introduced to disrupt chain packing, reduce packing efficiency and systematically tuning the fractional free volume (FFV) and gas separation properties of the resulting polyimides. The obtained SPIRO-PIs exhibited excellent solubility in common organic solvents and good processability. Gas separation measurements showed that SPIRO-CH3-6FDA exhibits a CO2 permeability of 578 Barrer and a CO2/CH4 selectivity of 17.4, while SPIRO-CF3-6FDA exhibits a CO2 permeability of 428 Barrer and a CO2/CH4 selectivity of 22.9. Furthermore, SPIRO-CH3-6FDA displays a high BET surface area of 629 m2 g−1, mainly attributed to the enhanced steric hindrance induced by methyl substituents. These SPIRO-PIs also demonstrated excellent mechanical strength and outstanding thermal stability, highlighting their potential as promising candidates for high-performance gas separation membranes.
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