Synthesis of quinacridone by 2,5-bis(aniline) terephthalic acid ring-closing reaction

doi:10.16085/j.issn.1000-6613.2019-1925

Abstract

Abstract:

Quinacridone is an important raw material for pigments, organic solar cells and other materials, and the ring-closing reaction in the synthesis process is still a hot topic. In this paper, 2,5-bis (aniline) terephthalic acid (DATA) was used as the raw material and the quinacridone was synthesized by the ring-closing reaction under the promotion of acid. The orthogonal test was used to examine the effect of the accelerator, feed ratio, heating temperature and reaction time on product yield. The experimental results indicated that with dodecylbenzenesulfonic acid (DBSA) as the accelerator, the factors affecting the yield of quinacridone from primary to secondary were: the type of acid> temperature> time> feeding ratio. Under the conditions of feeding ratio m(DATA)∶m(DBSA)=1∶4.3, reaction temperature 130℃ and reaction time 7h, the yield of the product quinacridone was 92%. Structural characterization of products and intermediates using ¹H NMR, FTIR and UV-vis. The SEM and TG-DSC analysis showed that the morphology of the product was regular and the thermal stability was good. After solvent treatment, the quinacridone was a stable β-crystal form analyzed by XRD.

Key words: quinacridone, 2,5-bis(aniline) terephthalic acid, dodecylbenzenesulfonic acid, closed loop reaction, orthogonal design

摘要：

喹吖啶酮作为颜料、有机太阳能电池等材料的重要原料，其合成过程的闭环反应仍是目前研究的热点。本文以2,5-双(苯胺基)对苯二甲酸（DATA）为原料，在酸促进下进行闭环反应合成喹吖啶酮，通过正交实验考察了促进剂、投料比、加热温度和反应时间对产物收率的影响。实验结果表明，以十二烷基苯磺酸（DBSA）为促进剂，在投料比m(DATA)∶m(DBSA)=1∶4.3、反应温度130℃、反应时间7h的条件下，产物喹吖啶酮收率为92%。由极差R可知，影响喹吖啶酮产率的因素从主到次：酸的种类＞温度＞时间＞投料比。利用¹H NMR、FTIR和UV-vis，对产物和中间产物进行了结构表征；经SEM和TG-DSC热重分析表明产物的形貌规则，热稳定性良好；溶剂处理后，喹吖啶酮经过XRD检测分析为稳定的β-晶型。

关键词: 喹吖啶酮, 2,5-双(苯胺基)对苯二甲酸, 十二烷基苯磺酸, 闭环反应, 正交设计

CLC Number:

TQ25

Xin MA, Gaofei WANG, Ying ZHANG, Liping CHENG, Lixian WANG. Synthesis of quinacridone by 2,5-bis(aniline) terephthalic acid ring-closing reaction[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3750-3756.

马歆, 王高飞, 张莹, 程利平, 王莉贤. 2,5-双(苯胺基)对苯二甲酸闭环反应合成喹吖啶酮[J]. 化工进展, 2020, 39(9): 3750-3756.

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