文献类型：期刊文献

中文题名：双功能Mn基催化剂在二氧化碳和环氧化物环加成反应中的应用

英文题名：Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides

作者：张湘南[1];马宏方[1];钱炜鑫[1];张海涛[1];应卫勇[1]

机构：[1]华东理工大学化工学院大型工业反应器工程教育部工程研究中心化学工程联合国家重点实验室,上海200237

年份：2025

卷号：50

期号：1

起止页码：20

中文期刊名：低碳化学与化工

外文期刊名：Low-Carbon Chemistry and Chemical Engineering

收录：;北大核心:【北大核心2023】；

基金：国家自然科学基金(22178113);中央高校基本科研业务费专项资金(JKA01231712)。

语种：中文

中文关键词：环状碳酸酯;双功能Mn基催化剂;二氧化碳;环氧化物;环加成反应

外文关键词：cyclic carbonates;bifunctional Mn-based catalysts;carbon dioxide;epoxides;cycloaddition reaction

摘要：二氧化碳(CO_(2))和环氧化物环加成反应是目前合成环状碳酸酯的有效方法之一。催化剂对活化该反应中的CO_(2)和环氧化物具有重要意义。以2,2’-联吡啶及其衍生物为配体,Mn(CO)_(5)Br为金属源,乙醚为溶剂制备了一系列双功能Mn基催化剂L_(n)Mn(CO)_(3)Br(n=1~6)。通过^(1)H NMR、^(13)C NMR、HR-MS和FT-IR等对L_(n)Mn(CO)_(3)Br的化学结构、相对分子质量和化学基团等进行了表征。研究了L_(n)Mn(CO)_(3)Br在CO_(2)和环氧氯丙烷环加成反应中的催化性能,及L_(1)Mn(CO)_(3)Br对一系列环氧化物底物的适应性。结果表明,L_(n)Mn(CO)_(3)Br中给电子基团(甲氧基、叔丁基和甲基)的给电子性能和吡啶环上甲基的位置均对其催化性能有影响;对于CO_(2)和环氧氯丙烷环加成反应,在L_(1)Mn(CO)_(3)Br投加量(物质的量分数)为0.05%、反应温度为125℃和反应压力为3.0 MPa的条件下反应1 h,L_(1)Mn(CO)_(3)Br的环氧氯丙烷转化率和催化剂转换频率分别为42%和840 h^(-1);L_(1)Mn(CO)_(3)Br对多种环氧化物作底物的环加成反应具有适应性,且底物的空间位阻效应对其催化性能有较大影响。
The cycloaddition reaction of carbon dioxide(CO_(2))and epoxides is an effective method to synthesize cyclic carbonates.Catalysts are important for the activation of CO_(2)and epoxides in the reaction.A series of bifunctional Mn-based catalysts L_(n)Mn(CO)_(3)Br(n=1~6)were prepared by 2,2’-bipyridine with its derivatives as the ligands,Mn(CO)5Br as the metal source and ethyl ether as the solvent.The chemical structures,molecular weights and chemical groups of L_(n)Mn(CO)_(3)Br were characterized by ^(1)H NMR,^(13)C NMR,HR-MS and FT-IR,etc.The catalytic performances of L_(n)Mn(CO)_(3)Br in the cycloaddition reaction of CO_(2)and epichlorohydrin and the adaptability of L_(1)Mn(CO)_(3)Br to a series of epoxide substrates were studied.The results show that the electron donating properties of electron donating groups(methoxy group,tertiary butyl and methyl group)in L_(n)Mn(CO)_(3)Br and the positions of methyl group on the pyridine ring have influences on their catalytic performances.For the cycloaddition reaction of CO_(2)and epiglorohydrin,under the conditions of L_(1)Mn(CO)_(3)Br dosage(mole fraction)of 0.05%,reaction temperature of 125℃and reaction pressure of 3.0 MPa for 1 h,the epiglorohydrin conversion rate and catalyst turnover frequency of L_(1)Mn(CO)_(3)Br are 42%and 840 h^(-1),respectively.L_(1)Mn(CO)_(3)Br has adaptability to the cycloaddition reaction of several epoxides.And the steric hindrance effects of the substrates have great influences on catalytic performance of L_(1)Mn(CO_(3))Br.