树状化核桃壳基催化剂的制备及其催化CO_(2)与胺的甲酰化反应  

Preparation of Imidazole Salt Dendrimers Functionalized Walnut Shell Powder-based Catalysts and Application in N-formylation of CO_(2)

作　　者：赖石林 陆颖琪 张辉 高利柱[1] 熊兴泉 LAI Shi-lin;LU Ying-qi;ZHANG Hui;GAO Li-zhu;XIONG Xing-quan(College of Materials Science and Engineering,Huaqiao University,Xiamen 361021,China;Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201204,China)

机构地区：[1]华侨大学材料科学与工程学院,厦门361021 [2]中国科学院上海高等研究院,上海201204

出　　处：《高分子通报》2024年第10期1459-1469,共11页Polymer Bulletin

基　　金：福建省“高校新世纪优秀人才支持计划”;“华侨大学中青年教师科研提升资助计划”(项目号ZQN-YX103);福建省自然科学基金(基金号2021J01294)。

摘　　要：以林产工业废弃物核桃壳粉(WS)为原料,通过对其进行多步化学改性,分别制备出外围被不同代数咪唑盐(IM)树状分子(WS-Gn-FeCl_(3)(n=1,2,3))功能化的催化剂载体(Gn-IM(n=1,2,3)),然后将该系列载体分别负载FeCl_(3),制备出核桃壳粉基异相催化剂WS-Gn-FeCl_(3)(n=1,2,3)。通过采用傅里叶红外(FTIR)、热重分析(TG)、元素分析(EA)等对WS-Gn-FeCl_(3)(n=1,2,3)进行了表征分析。将所得催化剂应用于有机胺的甲酰化反应,结果表明树状分子代数对催化剂的催化活性有着重要影响,第三代催化剂WS-G3-FeCl_(3)显示出最高催化活性。以WS-G3-FeCl_(3)为催化剂催化有机胺与CO_(2)之间的甲酰化反应,在100℃以及CO_(2)氛围中(1.0 MPa)反应1 h,即可高效合成出甲酰胺类化合物,且WS-G3-FeCl_(3)容易回收与重复使用,该催化剂在重复使用10次后活性没有明显的降低。Walnut shell(WS)powder,a kind of industrial waste of forest products,was used as raw material to prepare WS-based supports WS-Gn-IM(n=1,2,3)functionalized with imidazole salt dendrimers by multi-step chemical modification,and then the WS-based heterogeneous catalysts WS-Gn-FeCl_(3)(n=1,2,3)were obtained by complexing WS-Gn-IM(n=1,2,3)with FeCl_(3).WS-Gn-FeCl_(3)(n=1,2,3)were characterized by various characterization methods,such as Fourier-transform infrared(FTIR)spectroscopy,thermogravimetric analysis(TGA)and elemental analysis.In addition,WS-Gn-FeCl_(3)(n=1,2,3)were used in the catalytic N-formylation reaction with CO_(2).The results showed that the generation of imidazole salt dendrimers had an important influence on the catalytic activity of the catalysts,and WS-G3-FeCl_(3)showed the highest catalytic activity.Using WS-G3-FeCl_(3)to catalyze the N-formylation reaction between organic amines and CO_(2)(1.0 MPa),formamide compounds can be efficiently synthesized at a temperature of 100℃for 1 h.WS-G3-FeCl_(3)could be easily recovered and reused at least 10 times without a significant reduction in activity.

关 键 词：核桃壳粉 树状分子 CO_(2) 甲酰胺 异相催化 

分 类 号：O621.251[理学—有机化学] O643.36[理学—化学]