聚酰亚胺单体2,3,3′,4′-联苯四甲酸二酐的合成及表征  

Synthesis and characterization of polyimide monomer 2,3,3′,4′-biphenyl tetracarboxylic dianhydride

作　　者：梅昊 邓刚 万力 陈斯淮 袁军 贾丽慧 MEI Hao;DENG Gang;WAN Li;CHEN Sihuai;YUAN Jun;JIA Lihui(School of Chemistry and Environmental Engineering,Wuhan Institute of Technology,Wuhan 430205,China)

机构地区：[1]武汉工程大学化学与环境工程学院,湖北武汉430205

出　　处：《武汉工程大学学报》2025年第1期14-20,共7页Journal of Wuhan Institute of Technology

摘　　要：以3-氯-邻苯二甲酸酐和4-氯-邻苯二甲酸酐为原料,经酯化、偶联、水解、脱水4步反应,制备出此前报道较少的聚酰亚胺重要单体2,3,3′,4′-联苯四甲酸二酐(a-BPDA)。交叉偶联反应是合成a-BPDA最关键的反应。以三苯基膦和氯化镍为催化剂,解决了常用催化剂必须新鲜制备和易失活的问题,简化了合成工序。通过单因素实验对合成工艺进行优化,优化后的最佳偶联条件为:n(无水氯化镍)∶n(三苯基膦)∶n(3-氯邻苯二甲酸二甲酯)∶n(4-氯邻苯二甲酸二甲酯)∶n(锌粉)=0.08∶0.48∶1.00∶1.00∶3.20,在100℃下反应1 h。优化后的工艺操作简单,反应条件温和,总收率高达75.57%,使该产品的工业化生产成为可能。We used 3 chloro phthalic anhydride and 4 chloro phthalic anhydride as raw materials to prepare 2,3,3′,4′biphenyltetracarboxylic acid dianhydride(a-BPDA),an important polyimide monomer which had been rarely reported before,through a four-step process including esterification,coupling,hydrolysis and dehydration.Since the cross-coupling reaction is the most crucial reaction for the synthesis of a-BPDA,we used triphenylphosphine and nickel chloride as catalysts,which overcame the drawbacks of the commonly used catalysts that have to be freshly prepared and are prone to deactivation.The synthetic process was explored by one-way experiments and optimized.The optimal coupling conditions were as follows∶n(anhydrous nickel chloride)∶n(triphenylphosphine)∶n(dimethyl 3-chlorophthalate)∶n(dimethyl 4-chlorophthalate)∶n(zinc powder)=0.08∶0.48∶1.00∶1.00∶3.20.The reaction was carried out at 100℃for 1 h,giving a high overall yield of 75.57%.The simplified synthesis,mild reaction condition and high yield provide the possibility of industrial production of a-BPDA.

关 键 词：聚酰亚胺单体 2 3 3′ 4′-联苯四甲酸二酐 交叉偶联反应 

分 类 号：O625[理学—有机化学]