Hypercrosslinked Ionic Polymers with High Ionic Content for Efficient Conversion of Carbon Dioxide into Cyclic Carbonates

The effective conversion of carbon dioxide (CO2) into cyclic carbonates requires porous materials with high ionic content and large specific surface area. Herein, we developed a new systematic post-synthetic modification strategy for synthesizing imidazolium-based hypercrosslinked ionic polymers (HIPs) with high ionic content (up to 2.1 mmol g(-1)) and large specific surface area (385 m(2) g(-1)) from porous hypercrosslinked polymers (HCPs) through addition reaction and quaternization. The obtained HIPs were efficient in CO2 capture and conversion. Under the synergistic effect of high ionic content, large specific surface area, and plentiful micro/mesoporosity, the metal-free catalyst [HCP-CH2-Im][Cl]-1 exhibited quantitative selectivities, high catalytic yields, and good substrate compatibility for the conversion of CO2 into cyclic carbonates at atmospheric pressure (0.1 MPa) in a shorter reaction time in the absence of cocatalysts, solvents, and additives. High catalytic yields (styrene oxide, 120 degrees C, 8 h, 94% yield; 100 degrees C, 20 h, 93% yield) can be achieved by appropriately extending the reaction times at low temperature, and the reaction times are shorter than other porous materials under the same conditions. This work provides a new strategy for synthesizing an efficient metal-free heterogeneous catalyst with high ionic content and a large specific surface area from HCPs for the conversion of CO2 into cyclic carbonates. It also demonstrates that the ionic content and specific surface area must be coordinated to obtain high catalytic activity for CO2 cycloaddition reaction.