C.I.颜料红177中间体的制备工艺改进  

An Efficient Method for Improved Preparation of C.I.Pigment Red 177 Intermediate

作　　者：张天永[1,2] 任忠静 李彬 姜爽[1] 史继星[1] 石志强 吕东军 ZHANG Tianyong;Ren Zhongjing;LI Bin;JIANG Shuang;SHI Jixing;SHI Zhiqiang;Lü Dongjun(Tianjin Key Laboratory of Applied Catalysis Science and Technology,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300354,China;Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300072,China;Department of Chemical Engineering,Renai College,Tianjin University,Tianjin 301636,China;Yuhong Pigment Co.Ltd,Dezhou,Shandong 253000,China;Shangdong Engineering Technology Research Center for the Whole Process Control of Organic Pigment′s Cleaner Production,Dezhou,Shandong 253000,China)

机构地区：[1]天津大学化工学院,天津市应用催化科学与工程重点实验室,天津300354 [2]天津化学化工协同创新中心,天津300072 [3]天津大学仁爱学院化工系,天津301636 [4]宇虹颜料股份有限公司,山东德州253000 [5]山东省有机颜料清洁生产全过程控制工程技术研究中心,山东德州253000

出　　处：《应用化学》2020年第4期433-439,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21908161);天津市科技创新平台计划(14TXGCCX00017);天津市自然科学基金(16JCYBJC20800)资助。

摘　　要：本文较为系统地研究了铜粉催化剂加入方式对C.I.颜料红177中间体4,4′-二氨基-1,1′-二蒽醌-3,3′-二磺酸(DAS)合成过程中的乌尔曼偶联反应速率的影响规律。研究结果表明,在55℃较佳反应温度下,先加入与溴氨酸钠质量比为2∶5的铜粉,反应一段时间后再加入与溴氨酸钠的质量比为1∶5的铜粉,与一次性加入与溴氨酸钠的质量比为3∶5的铜粉相比较,综合反应时间可节省2~3 h。另外,对于DAS中混有的铜盐,采取在制备过程中加入柠檬酸的方法予以去除,此举可提高DAS的纯度。当铜粉与柠檬酸的质量比为6∶1时,可使DAS中铜盐的含量小于0.001%。此外还探究了蒸馏后滤液的剩余量对DAS收率的影响,结果表明,滤液的剩余量在20 mL时,DAS的收率在95%以上。基于本文的研究结果提出,欲进一步提高该反应的收率,需要寻找更高效的催化剂。The effect of batch addition of the catalyst(copper powder)on the reaction rate during the synthesis of 4,4′-diamino-1,1′-dianthraquinone-3,3′-disulfonic acid(DAS)was investigated systematically.The results indicate that 55℃is the preferred reaction temperature.Copper powder and sodium bromate with a mass ratio of of 2∶5 are first added,and the second portion of catalyst with a mass ratio of 1∶5 copper powder to sodium bromate is then added during the reaction.The reaction time could be saved for 2~3 h compared to adding copper powder at one time(the mass ratio of copper powder to sodium bromate is 3∶5).The copper salt mixed in DAS could be removed efficiently by addition of citric acid during the preparation process,which can improve the purity of DAS.When the mass ratio of copper powder to citric acid is 6∶1,the content of copper salt in DAS is less than 0.001%.In addition,the influence of the residual amount of the filtrate after distillation on the yield of DAS is also explored and the yield of DAS is above 95%when the remaining amount of filtrate is 20 mL.The results of this study also indicate that to further improve the yield of the reaction,more efficient catalyst is needed.

关 键 词：C.I.颜料红177中间体 催化剂 铜粉 柠檬酸 

分 类 号：O625.6[理学—有机化学]