In the present work, we report highly permeable polymer nanocomposites applied to natural gas purification. Using a polymer of intrinsic microporosity (PIM), which contains ethanoanthracene (EA) and Tröger base (TB) units as control material (PIM-EA(Me2)-TB), we design and synthesize a version of this PIM without methyl side chains, PIM-EA(H2)-TB. Nanocomposites are made by combining PIM-EA(H2)-TB with 10 wt. % of porous aromatic framework-1 (PAF-1) nanoparticles (which is a self-assembled microporous polymer with repeating units comprising aromatic carbon rings arranged in a tetrahedron). 13C solid state nuclear magnetic resonance (NMR) spectra and the cross-sectional scanning electron microscope (SEM) demonstrated that incorporation of PAF-1 into PIM-EA(H2)-TB yields a phase separated system. Small angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) were used to characterize the presence of PAF-1 impact on the spacing between PIM-EA(H2)-TB chains, suggesting that PAF-1 drastically enhances d-spacing in PIM-EA(H2)-TB. Pure gas permeability for CO2 and CH4 was measured as a function of upstream pressure at 35 . Incorporation of PAF-1 substantially increases pure CO2 permeability of PIM-EA(H2)-TB, but decreases pure CO2/CH4 selectivity, presumably attributed to free volume increase imparted by PAF-1 in PIM-EA(H2)-TB matrix. Permeation of mixtures of CO2 and CH4 (50:50 mol. %) are presented alongside the measurements of pure components to characterize the performance of these materials under simulated natural gas conditions.
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