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A highly gas permeable polymer with exceptional size selectivity is prepared by fusing triptycene units together via a polymerization reaction involving Tröger's base formation. The extreme rigidity of this polymer of intrinsic microporosity (PIM‐Trip‐TB) facilitates gas permeability data that lie well above the benchmark 2008 Robeson upper bounds for the important O2/N2 and H2/N2 gas pairs.
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