季铵盐离子液体功能化金属-有机骨架材料温和条件下催化CO2环加成反应

Metal-organic framework material functionalized by quaternary ammonium salt ionic liquid for the cycloaddition of CO under mild conditions

将季铵盐离子液体4-(苯甲酸)三乙胺溴(QAIL)固载于金属-有机骨架材料MIL-101中,得到一种兼具酸碱活性位点的新型功能化金属-有机骨架材料FMOF-QAIL,并用于温和条件下催化转化CO2与环氧氯丙烷(ECH)的环加成反应。季铵盐离子液体不仅作为Lewis碱性位点对CO2具有强吸附能力,与催化剂中的Lewis酸性位点实现对环氧化物协同催化,同时还提供卤素反离子作为亲核试剂参与环加成反应。在反应温度70℃、CO2压力0.1 MPa下,无需溶剂和助催化剂,产物氯丙烯碳酸酯(CPC)的产率和选择性分别高达95%和99%。

The quaternary ammonium salt ionic liquid 4-(benzoic acid)triethylamine bromide(QAIL)was immobilized in the metal-organic framework material MIL-101,and a new functional metal-organic framework named FMOF-QAIL with acid-base active sites was obtained and used for catalytic conversion of epichlorohydrin(ECH)and CO2 into cyclic addition under mild conditions.As Lewis basic sites,Quaternary ammonium ionic liquids not only have strong adsorption capacity for CO2 and synergistically catalyze epoxides with Lewis acid sites in the catalyst,but also provide halogen counter ions as nucleophiles to participate in cycloaddition.At 70°C,CO2 pressure of 0.1 MPa,without solvent or cocatalyst,the yield and selectivity of chloropropylene carbonate(CPC)are as high as 95%and 99%,respectively.