Facile Synthesis of Binuclear Imidazole-Based Poly(ionic liquid) via Monomer Self-Polymerization: Unlocking High-Efficiency CO2 Conversion to Cyclic Carbonate

Strategic utilization of carbon dioxide as both a carbon mitigation tool and a sustainable C1 feedstock represents a pivotal pathway toward green chemistry. Although poly(ionic liquid)s (PILs) exhibit promise in CO2conversion, conventional divinylbenzene (DVB) cross-linked architectures are limited by reduced ionic density and limited accessibility of active sites. Herein, we reported a binuclear imidazolium-functionalized PIL catalyst (P-BVIMCl), synthesized through a simple self-polymerization process, derived from rationally designed ionic liquid monomers formed by quaternization of 1,4-bis(chloromethyl)benzene with N-vinylimidazole. The dual active sites in P-BVIMCl-quaternary ammonium cation (N+) and nucleophilic chloride anion (Cl−) synergistically enhanced CO2adsorption/activation and epoxide ring-opening. Under optimal catalyst preparation conditions (100 °C, 24 h, water/ethanol = 1:3 (v/v), 10 wt% AIBN initiator) and reaction conditions (100 °C, 2.0 MPa CO2, 10 mmol epichlorohydrin, 6.7 wt% catalyst loading, 3.0 h), P-BVIMCl catalyzed the synthesis of glycerol carbonate (GLC) with a yield of up to 93.4% and selectivity of 99.6%, maintaining activity close to 90% after five cycles. Systematic characterization and density functional theory (DFT) calculations confirmed the synergistic activation mechanism. This work established a paradigm for constructing high-ionic-density catalysts through molecular engineering, advancing the development of high-performance PILs for industrial CO2valorization.