Abstract In this work, polynorbornene (PNB) was synthesized via dual-core catalyst successfully and applied in the gas membrane applications. The microstructure and physical properties of resultant PNB were evaluated precisely. FESEM images showed that PNB membrane had a dense and porous microstructure. XRD results indicated that polynorbornene had two sharp peaks at 2θ nearly 10° and 20°. The results of DSC analysis exhibited that with the design of the new synthetic system, the Tg reduced, though both molecular weight, and film-ability of polymer were improved significantly. A molecular weight of over 9 × 105 g/mol was obtained for PNB. The permeability values against CO2 and CH4 were 63.7 and 5.2 (Barrer), respectively, which were comparable with those of reported previously. Additionally, the obtained selectivity was 12.2. DFT-D simulation results showed that O2 molecules have more tendencies to C7H12 than that of other gas molecules and better capability to adsorb onto C7H12.

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