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2,4-二硝基苯甲醚的连续流动制备及反应动力学
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1.北京理工大学 材料学院, 北京 100081;2.湖北东方化工有限公司, 湖北 襄阳 441022

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Continuous Flow Preparation and Reaction Kinetics of 2,4-dinitroanisole
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1.School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China;2.Hubei Dongfang Chemical Industry Co., Ltd, Hubei 441022, China

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    摘要:

    2,4-二硝基苯甲醚(DNAN)是一种替代2,4,6-三硝基甲苯(TNT)并已获得应用的新型钝感熔铸载体炸药。间歇釜式制备DNAN工艺存在反应时间长、在制量大及副产物多等问题,亟需开展新型制备工艺研究。基于此,以2,4-二硝基氯苯(2,4-DNCB)为原料、在甲醇和氢氧化钠溶剂体系中,开展连续流动化制备DNAN工艺及反应动力学研究;对反应机理进行了过渡态计算,并使用连续流动合成设备,进行了反应动力学实验。动力学研究结果显示,2,4-DNCB的醚化反应为二级反应,反应速率与2,4-DNCB和氢氧化钠的浓度乘积成正比,活化能为73.950 kJ∙mol-1,指前因子A0=7.991×1010 L∙mol-1∙s-1。通过正交试验系统考察了反应温度、停留时间、摩尔比等工艺参数对DNAN的纯度和收率的影响,得到较优工艺条件为:反应温度90 ℃,停留时间1 min,物料摩尔比1.6∶1。DNAN的收率可达93.7%,纯度为99.99%以上。

    Abstract:

    2,4-Dinitroanisole (DNAN) has emerged as a novel insensitive melt-cast carrier explosive, serving as a practical and effective replacement for TNT in various applications. However, the conventional batch reactor synthesis method is plagued by several limitations, including prolonged reaction duration, excessive in-process inventory, and significant generation of byproducts, which collectively restrict its safe and efficient large-scale production. Consequently, developing advanced preparation processes has become imperative. This study investigates the synthesis of DNAN employing a reaction system comprising 2,4-dinitrochlorobenzene (2,4-DNCB), methanol, and sodium hydroxide, with a particular focus on continuous flow technology and reaction kinetics. Through mechanistic simulations, a kinetic reaction model was successfully established. The experimental kinetic results indicate that the etherification of 2,4-DNCB follows second-order reaction kinetics, where the reaction rate is proportional to the product of the concentrations of 2,4-DNCB and NaOH. Key kinetic parameters were determined as follows: Activation energy (Ea): 73.950 kJ·mol-1. Pre-exponential factor (A0): 7.991×1010 L·mol-1·s-1.The effects of critical process variables—namely, reaction temperature, residence time, and molar ratio of reactants—on the product purity and yield were systematically investigated. The optimal reaction conditions were identified as: Reaction temperature: 90 ℃. Residence time: 1 min. Molar ratio (2,4-DNCB∶NaOH): 1.6∶1. Under these optimized conditions, DNAN was obtained with a yield of 93.7% and a purity exceeding 99.99%. This research provides a robust theoretical foundation and practical methodology for the continuous and efficient production of DNAN.

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引用本文

朱旭,张文瑾,陈军,等.2,4-二硝基苯甲醚的连续流动制备及反应动力学[J].含能材料, 2025, 33(12):1377-1384. DOI:10.11943/CJEM2025206.
ZHU Xu, ZHANG Wenjin, CHEN Jun, et al. Continuous Flow Preparation and Reaction Kinetics of 2,4-dinitroanisole[J]. Chinese Journal of Energetic Materials, 2025, 33(12):1377-1384. DOI:10.11943/CJEM2025206.

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历史
  • 收稿日期: 2025-09-19
  • 最后修改日期: 2025-12-06
  • 录用日期: 2025-11-27
  • 在线发布日期: 2025-12-09
  • 出版日期: 2025-12-25