The design and synthesis of porous materials with novel structures and functional groups to prepare mixed matrix membranes (MMMs) is an effective way to break through trade-off effect of membrane technology. Here, hyper crosslinked polymers containing amino groups (HCPs-NH 2 ) with philic-CO 2 frame were successfully prepared for the fabrication of polyimide (PI)/HCPs-NH 2 MMMs. The separation performance of pure gas is studied in order to explore NH 2 groups facilitating CO 2 diffusion and transmission and enhancing CO 2 permeability. Consequently, the permeability of the PI/HCPs-NH 2 MMMs toward CO 2 and O 2 are 77.56 Barrer and 17.91 Barrer versus pure PI film toward CO 2 and O 2 (62.42 Barrer and 13.85 Barrer). The selectivity for CO 2 /CH 4 and O 2 /N 2 pairs is 24.44 and 4.01, and the selectivity of pure PI film toward CO 2 /CH 4 and O 2 /N 2 pairs is 20.76 and 3.29, respectively. The permeability and selectivity of PI/HCPs-NH 2 MMMs are higher than pure PI film breaking through the trade-off effect. Moreover, the PI/HCPs-NH 2 MMMs show better separation performance on the CO 2 /CH 4 pair than the O 2 /N 2 pair, indicating HCPs-NH 2 with philic-CO 2 frame plays a very important role in promoting CO 2 permeability. Thus, the PI/HCPs-NH 2 MMMs have potential applications in the field of natural gas purification.

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