季铵型多孔超交联离子聚合物催化二氧化碳环加成合成环状碳酸酯

Quaternary ammonium-based porous hypercrosslinked ionic polymer for cycloaddition of carbon dioxide into cyclic carbonates

以双(三苯基膦)氯化铵为单体,通过傅-克烷基化反应制备一种季铵型多孔超交联离子聚合物(QA-PHIP)。采用傅里叶变换红外光谱、扫描电镜和N 2吸附-脱附等对QA-PHIP进行表征。结果表明,QA-PHIP的比表面积为903.7 m^(2)·g^(-1),在0.1 MPa和0℃条件下CO_(2)的吸附量为52.1 cm^(3)·g^(-1)。将QA-PHIP应用于催化CO_(2)与环氧化物合成环状碳酸酯的反应,考察反应温度和催化剂用量等因素对催化性能的影响。QA-PHIP表现出良好的催化性能,在120℃和1.0 MPa条件下反应12 h,可获得99.6%的环氧氯丙烷转化率和97.3%的氯甲基二氧杂戊环酮收率。QA-PHIP表现出良好的底物扩展性和重复使用性。

A quaternary ammonium-based porous hypercrosslinked ionic polymer(QA-PHIP)was prepared through Friedel-Cratfs alkylation using biphenyl phosphine ammonium chloride as monomer.QA-PHIP was characterized by various techniques such as Fourier transform infrared spectroscopy,scanning electron microscopy and nitrogen adsorption-desorption measurement.The results showed that the specific surface area of QA-PHIP was 903.7 m^(2)·g^(-1),and the CO_(2)adsorption capacity was 52.1 cm^(3)·g^(-1)at 0.1 MPa and 0℃.Furthermore,QA-PHIP was applied to catalyze the synthesis of cyclic carbonates from CO_(2)and epoxide,and the effects of parameters such as reaction temperature and catalyst dosage on the catalytic performance were systematically investigated.QA-PHIP displayed good catalytic performance of 99.6%conversion of epichlorohydrin and 97.3%yield of chloromethyldioxane at 120℃and 1.0 MPa for 12 h.Moreover,QA-PHIP exhibited good substrate expansibility and reusability.