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以R-phen(R=5-NH_2、5-CH_3、5-H、5-Cl、5-NO_2,2-CH_3、4-CH_3、2,9-dimethyl、4,7-dimethyl、5,6-dimethyl;phen=1,10-邻菲啰啉)和溴化铜为原料,通过沉淀反应制备了铜配合物Cu(R-phen)Br_2。在甲醇氧化羰基化反应中,以Cu(OCH_3)_2和卤化亚铜/卤化铜为催化剂考察了卤素离子的作用机理,以Cu(R-phen)Br_2为催化剂探究了催化剂的构效关系,以及工艺条件对甲醇氧化羰基化反应的影响。结果表明:卤素离子主要起桥联作用,其催化活性顺序为交界碱Br->硬碱Cl->软碱I-;Cu(R-phen)Br_2中,催化活性顺序为Cu(5-NO_2-phen)Br_2Cu(4-CH_3-phen)Br_2>Cu(2-CH_3-phen)Br_2,且比相应的含双甲基phen的Cu配合物的催化活性高。以Cu(5-CH_3-phen)Br_2催化甲醇氧化羰基化的优化工艺条件为:总压力4 MPa、CO与O_2的分压比为19∶1、反应时间4 h、反应温度130℃、催化剂浓度0.0110 mol/L(以甲醇体积计)。在此条件下,碳酸二甲酯(DMC)的TON[n(DMC)/n(Cu)]值为67.2,DMC的选择性为96.9%。
In order to improve the stability of the system, R-phen (R = 5-NH_2,5-CH_3,5-H, 5-Cl, 5-NO_2, 2-CH_3,4-CH_3,2,9-dimethyl, phenanthroline) and copper bromide as raw materials, a copper complex Cu (R-phen) Br 2 was prepared by precipitation reaction. In the oxidative carbonylation of methanol, the mechanism of action of halogen ions was investigated using Cu (OCH 3) 2 and cuprous halide / copper halides as catalyst. The structure-activity relationship of the catalysts was investigated using Cu (R-phen) Br 2 as catalyst Effect of Technological Conditions on Oxidative Carbonylation of Methanol. The results showed that the main activity of bridging was halide ion. The order of catalytic activity was Cu (R-phen) Br2 and Cu (R-phen) (phen) Br_2 Cu (4-CH_3-phen) high. The optimum conditions for the oxidative carbonylation of methanol with Cu (5-CH_3-phen) Br_2 were: total pressure 4 MPa, partial pressure ratio of CO to O_2 19:1, reaction time 4 h, reaction temperature 130 ℃, catalyst concentration 0.0110 mol / L (based on methanol volume). Under these conditions, the TON [n (DMC) / n (Cu)] value of DMC was 67.2 and the selectivity of DMC was 96.9%.