1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is an essential insensitive energetic material. The alkylation of 1,3,5-trihydroxy-2,4,6-trinitrobenzene (Trinitrophloroglucinol, TNPG), which yields 1,3,5-triethoxy-2,4,6-trinitrobenzene (TETNB), is a pivotal step for the synthesis of TATB. The conventional synthetic process has suffered from long reaction time (∼165 min), intricate procedures, and intensive evaporation of a large number of volatile by-products, which increases the risk of spill and eruption of the reaction system, and necessitates in situ continuous gas–liquid separation. A new process for continuous alkylation in microreactors was proposed in this study. Firstly, a parametric investigation in the batch reactor was performed to explore the effects of various process parameters on the yields, resulting in the optimal experimental conditions, i.e., no reflux condensation, triethyl orthoformate (TEOF) as alkylation reagent, molar ratio of 12, reaction temperature of 120 °C and reaction time of 40 min. Subsequent continuous synthesis in microreactors was conducted, which realized the convenient process operation and no need of gas–liquid separation, leading to substantial improvement in the reaction efficiency and safety. Remarkably, within a packed microreactor, under the reaction temperature of 130 °C and residence time of 3 min, 99.24 % in the yield of TETNB was achieved. Comparing with conventional batch reactors, the required reaction time was reduced to approximately 1/50. Taking the advantages of precise control of temperature and reaction time in the microreactors, the kinetics of alkylation reaction were determined. This innovative approach of continuous synthesis can provide an efficient and alternative route for the synthesis of TATB, as well as other energetic materials and similar processes.

中文翻译：

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1,3,5-三羟基-2,4,6-三硝基苯在微反应器中的连续烷基化：过程强化和反应动力学


1,3,5-三氨基-2,4,6-三硝基苯（TATB）是一种重要的不敏感含能材料。 1,3,5-三羟基-2,4,6-三硝基苯（三硝基三硝基苯三酚，TNPG）的烷基化生成 1,3,5-三乙氧基-2,4,6-三硝基苯 (TETNB)，是TATB的合成。传统的合成工艺反应时间长（~165 min），程序复杂，大量挥发性副产物强烈蒸发，增加了反应体系溢出和喷发的风险，需要原位连续合成。气液分离。本研究提出了一种在微反应器中连续烷基化的新工艺。首先，在间歇式反应器中进行参数研究，探讨各种工艺参数对收率的影响，得出最佳实验条件为：无回流冷凝，原甲酸三乙酯（TEOF）为烷基化试剂，摩尔比为12，反应温度120℃，反应时间40分钟。随后在微反应器中进行连续合成，实现了工艺操作便捷且无需气液分离，反应效率和安全性大幅提高。值得注意的是，在填充的微反应器中，在130℃的反应温度和3分钟的停留时间下，TETNB的收率达到了99.24%。与传统间歇式反应器相比，所需反应时间减少至约1/50。利用微反应器中精确控制温度和反应时间的优点，确定了烷基化反应的动力学。 这种连续合成的创新方法可以为TATB以及其他含能材料和类似工艺的合成提供有效的替代路线。