Cu(DMe-H_2 biim)(OAc)_2催化甲醇氧化羰基化合成碳酸二甲酯  

Synthesis of Dimethyl Carbonate from Oxidative Carbonylation of Methanol Catalyzed by Cu(DMe-H_2 biim)(OAc)_2

作　　者：肖艳华[1] 雷汉民 黄丽明[1] 吴元欣[1] 王公应[2] 杜治平[1,2] 

机构地区：[1]绿色化工过程教育部重点实验室武汉工程大学,湖北武汉430074 [2]中国科学院成都有机化学研究所,四川成都610041

出　　处：《精细化工》2016年第4期419-424,共6页Fine Chemicals

基　　金：国家自然科学基金(21276201);湖北省协同创新项目(010846)~~

摘　　要：以Cu(OAc)2为铜源,2,2'-联咪唑(H2biim)、1,1'-二亚甲基-2,2'-联咪唑(DMe-H2biim)和1,1'-邻二甲苯-2,2'-联咪唑(Oxy-H2biim)为配体,研究了其在甲醇氧化羰基化合成碳酸二甲酯(DMC)反应中的催化性能,并采用FTIR、TG和CO-TPR对Cu(DMe-H2biim)(OAc)2进行了表征。结果表明,DMe-H2biim中亚甲基的给电子效应使其比H2biim和Oxy-H2biim能更好地促进DMC的合成,且配合物Cu(DMe-H2biim)(OAc)2比等物质的量的Cu(OAc)2和DMe-H2biim混合物具有更高的催化活性。在Cu(DMe-H2biim)(OAc)2为催化剂,反应时间为4h,反应温度为110℃,催化剂浓度为0.014 mol/L的条件下,DMC的转化数(TON)为20.4,DMC选择性为95.8%。Catalytic performances of copper complexes,which were synthesized from Cu（OAc）2as a copper source and 2,2＇-biimidazole（H2biim）,1,1＇-dimethylene-2,2＇-biimidazole（DMe-H2biim） or1,1＇-ο-xylylene-2,2＇-biimidazole（Oxy-H2biim） as a ligand,were investigated in oxidative carbonylation of methanol to dimethyl carbonate（DMC）,and Cu（DMe-H2biim）（OAc）2was characterized by infrared spectroscopy,thermogravimetric analysis and CO temperature-programmed reduction.It was found that DMe-H2 biim exhibited higher performance for DMC synthesis than H2 biim and Oxy-H2 biim due to the electron-donating effect of the methylene group,and the catalytic activity of Cu（DMe-H2biim）（OAc）2was higher than that of the equimolar mixture of Cu（OAc）2and DMeH2 biim.The turnover number and the selectivity of DMC reached 20.4 and 95.8%,respectively,under the optimum conditions of Cu（DMe-H2biim）（OAc）2as the catalyst,reaction time 4 h,reaction temperature 110 ℃ and the concentration of the catalyst 0.014 mol / L.

关 键 词：碳酸二甲酯 氧化羰基化 联咪唑 铜配合物 催化技术 

分 类 号：TQ203.2[化学工程—有机化工]