几种新型^(3)LCuCl配合物的合成及其对甲醇氧化羰基化反应催化性能研究  

The synthesis of novel ^(3)LCuCl complexes and their catalytic properties in oxidative carbonylation of methanol

作　　者：王云飞 刘昌盛 杨喜庆 胡泉源[1] WANG Yunfei;LIU Changsheng;YANG Xiqing;HU Quanyuan(School of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China)

机构地区：[1]湖北大学化学化工学院,湖北武汉430062

出　　处：《湖北大学学报（自然科学版）》2022年第4期436-441,共6页Journal of Hubei University：Natural Science

摘　　要：甲醇液相氧化羰基化合成碳酸二甲酯是一碳化学研究的重要应用领域之一,其核心工作是反应催化剂的开发和使用.本项工作从仿生催化的角度进行催化剂结构设计,合成三种结构新颖的氯化亚铜的配合物,分别具有N-N-N、N-O-N和N-S-N新型配体,并用于甲醇液相氧化羰基化催化反应,在工业生产的反应条件(120℃/2.4 MPa)下研究了它们在合成碳酸二甲酯反应中的催化性能.5 h后的实验结果显示,N-O-N型配合物对碳酸二甲酯的时空转化率高于81 g·DMC/(g·cat·h),但选择性低于90%.N-N-N型配合物对碳酸二甲酯的催化选择性在94%以上,但时空转化率只有37.5 g·DMC/(g·cat·h).N-S-N型配合物综合催化效果不佳.实验结果说明杂原子和金属离子的配位能力过强对催化性能不利,如何在选择性与时空转化率之间取得较好的平衡需要进一步探讨.Oxidative carbonylation of methanol for preparation of dimethyl carbonate(DMC)is one of the important research topics in C1-Chemistry.The core work is the development and use of catalysts.From the perspective of biomimetic catalysis,three novel complexes of cuprous chloride were designed and synthesized,which containing N-N-N,N-O-N and N-S-N tridentate ligand respectively.The complexes were applied to oxidative carbonylation of methanol and their catalytic properties were studied under manufactural conditions at 120℃and 2.4 MPa.The experimental results,after 5 h,showed that the space-time conversion rate of DMC for N-O-N-type complex was above 81 g·DMC/(g·cat·h)with a selectivity value lower than 90%.The catalytic selectivity of DMC for N-N-N-type complex was over 94%,while the value of its space-time conversion rate was merely 37.5 g·DMC/(g·cat·h).The comprehensive catalytic activity for N-S-N-type complex was unsatisfactory.We find that the catalytic performance is unfavorable when too strong coordination existing between heteroatoms and cuprous ion.How to achieve a better balance between selectivity and space-time conversion needs to be further discussed.

关 键 词：碳酸二甲酯 氯化亚铜配合物 氧化羰基化 催化反应 

分 类 号：O626.26[理学—有机化学]