Poly(ionic liquid) materials tailored by carboxyl groups for the gas phase-conversion of epoxide and CO2 into cyclic carbonates

Carbon dioxide (CO2) is an important C1 resource, and the preparation of cyclocarbonate by catalyzing CO2 and epoxides is a nature-friendly route to utilize. In this study, polymer ionic liquid materials (PILMs) were prepared by copolymerizing the vinylimidazole-based ionic liquids (ILs) as monomer with carbonyl-rich copolymer monomer methyl methacrylate (MMA) and crosslinking agent ethylene glycol dimethacrylate (EGDMA), to enhance the affinity of PILMs for CO2 and PO. Then, epoxides and CO2 were converted to cyclic carbonates using PILMs by the gas-liquid reaction (GLR) and the gas phase-conversion progress (GCP). Amongst those polymer ionic liquid materials, the PILM containing carboxypropyl group (PILM-VCPImBr) exhibited the performance with the propylene carbonate (PC) yield of 96.7% (at 130 °C, 3 MPa CO2, reaction time 3 h) by GLR. And the yield of PC reached 94.2% (at 130 °C, 2 MPa CO2, reaction time 3 h) by GCP, which was the same as that of GLR. The excellent catalytic activity can be attributed to the fact that the PILMs fully dispersed the active sites and were rich in pores, which could effectively catalyze propylene oxide (PO) and CO2 to generate PC. Finally, 1H NMR spectra showed that VCPImBr and PO formed strong hydrogen bonds to participate the ring-opening process of epoxides, and a possible catalytic mechanism of H-bond synergistic effect was proposed. This article provides a novel strategy for designing both stable and nature-friendly catalysts in the CO2 transformation, and proposes a new method for cyclic carbonate conversion.