Cross-linking of Polymer of Intrinsic Microporosity (PIM-1) via nitrene reaction and its effect on gas transport property

• Synthesis and characterization of PEG functionalized biazide successfully.
• PIM-1 membrane were cross-linked with PEG biazide via nitrene reaction.
• Cross-linked PIM-1 membranes were characterized by FTIR, TGA-FTIR and gel content analysis.
• Cross-linked PIM-1 membranes showed enhancement in CO2/N2, CO2/CH4 and C3H6/C3H8 gas separation.
• Cross-linked PIM-1 membrane suppressed plasticization under high CO2 pressure.

Polymer of Intrinsic Microporosity (i.e. PIM-1) has been crosslinked thermally via nitrene reaction using polyethylene glycol biazide (PEG-biazide) as a crosslinker. The crosslinking temperature was optimized using TGA coupled with FT-IR spectroscopy. The dense membranes containing different ratios of PIM-1 to PEG-biazide were cast from chloroform solution. Crosslinking of PIM-1 renders it insoluble even in excellent solvents for the uncrosslinked polymer. The resulting crosslinked membranes were characterized by FT-IR spectroscopy, TGA and gel content analysis. The influence of crosslinker content on the gas transport properties of PIM-1, its density and fractional free volume (FFV) were investigated. Compared to the pure PIM-1 membrane, the crosslinked PIM-1 membranes showed better gas separation performance especially for CO2/N2, CO2/CH4 and propylene/propane (C3H6/C3H8) gas pairs and as well as suppressed penetrant-induced plasticization under high CO2 pressure.

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