3,3’,4,4’-联苯四甲酸二酐的合成  

Synthesis of 3,3’,4,4’-biphenyltetracarboxylic dianhydride

作　　者：张秀红 付裕轩 张恒 王培奇 陈思礼 彭浚峰 ZHANG Xiuhong;FU Yuxuan;ZHANG Heng;WANG Peiqi;CHEN Sili;PENG Junfeng(School of Chemistry,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学化学学院,辽宁大连116024

出　　处：《应用化工》2024年第10期2372-2375,共4页Applied Chemical Industry

摘　　要：3,3’,4,4’-联苯四甲酸二酐是高性能材料聚酰亚胺的前体。采用格氏试剂偶联的方法对3,3’,4,4’-联苯四甲酸二酐的合成进行了研究。首先4-溴邻二甲苯与金属镁反应制备格氏试剂,然后在三氟甲磺酸铁催化下,格氏试剂自身偶联制得3,3’,4,4’-四甲基联苯;3,3’,4,4’-四甲基联苯经氧化、脱水制得3,3’,4,4’-联苯四甲酸二酐。考察了实验中关键因素的影响,确定了偶联最佳反应条件并对反应机理进行了解析。结果表明,偶联反应温度为60℃,反应时间为8 h时,3,3’,4,4’-四甲基联苯的收率达到83%。3,3’,4,4’-联苯四甲酸二酐的收率为78%。机理分析表明格氏试剂在铁催化剂和1,2-二氯乙烷作用下,发生了自偶联反应制备了3,3’,4,4’-四甲基联苯。3,3’,4,4’-Biphenyltetracarboxylic dianhydride is a precursor of high-performance material polyimide.This article adopts the method of Grignard reagent coupling to study the synthesis of 3,3’,4,4’-biphenyltetracarboxylic dianhydride.Firstly,4-bromo-o-xylene reacted with magnesium metal to prepare Grignard reagent.Secondly,under the action of ferric trifluoromethanesulfonate,the Grignard reagent self-coupled to produce 3,3’,4,4’-tetramethyl biphenyl,which was oxidized and then dehydrated to obtain 3,3’,4,4’-biphenyl tetracarboxylic dianhydride.The effects of key factors of the experiments were examined,the optimal reaction conditions of coupling were determined.The reaction mechanism has been analyzed.The results showed that the coupling reaction temperature was 60℃and the reaction time was 8 h,the yield of 3,3’,4,4’-tetramethylbiphenyl reached 83%.The yield of 3,3’,4,4’-biphenyltetracarboxylic dianhydride was 78%.Mechanism analysis shows that Grignard reagent undergoes self coupling reaction with iron catalyst and 1,2-dichloroethane to prepare 3,3’,4,4’-tetramethylbiphenyl.

关 键 词：聚酰亚胺 3 3’ 4 4’-联苯四甲酸二酐 4-溴邻二甲苯 格氏试剂 偶联反应 

分 类 号：TQ245.2[化学工程—有机化工]