高纯2,4,6⁃三硝基⁃5⁃乙氧基⁃1,3⁃苯二胺的合成及性能

Synthesis and Properties of High Purity 2,4,6⁃Trinitro⁃5⁃ethoxy⁃1,3⁃phenylenediamine

高纯度2,4,6‑三硝基‑5‑乙氧基‑1,3‑苯二胺(DATNEB)可作为内标物,通过高效液相色谱法对含氯法合成的1,3,5‑三氨基‑2,4,6‑三硝基苯(TATB)的纯度进行精确分析。为研究DATNEB的合成及其含能特性,以苦味酸为原料,经4‑氨基‑1,2,4‑三唑(ATA)氨化,原甲酸三乙酯乙基化两步制得高纯DATNEB,总收率为32.5%,纯度≥99.8%。产物经红外(IR)、核磁(^(1)H NMR、^(13)C NMR)、质谱(MS)以及单晶X‑射线衍射确证结构。对苦味酸双氨基化机理和中间体二氨基苦味酸羟基乙基化机理进行了探讨,且对DATNEB热性能和爆轰性能进行了研究。结果表明,DATNEB为单斜晶系,空间群为P21/c,晶体学参数为:a=1.21261(7)nm,b=0.89654(4)nm,c=1.12310(6)nm,V=1.17675(11)nm3,Z=4,D=1.62 g·cm^(-3)。吸热峰温为193.9℃,放热峰温为236.0℃,具有较好的热稳定性。理论爆速为7.05 km·s^(-1),爆压为21.14 GPa,总体爆轰性能与三硝基甲苯(TNT)相当,但感度远低于TNT和环三亚甲基三硝胺(RDX)。因此合成的高纯DATNEB不仅可作为内标物,用于分析含氯法合成的TATB纯度,还有望作为熔铸炸药的辅助组分。

High purity 2,4,6‑trinitro‑5‑ethoxy‑1,3‑phenylenediamine(DATNEB)can be used as an internal standard in high performance liquid chromatography(HPLC)to accurately analyze the purity of TATB synthesized by the chlorine‑containing method.To study the synthesis and energetic properties of DATNEB,high purity DATNEB was prepared from picric acid by aminating with 4‑amino‑1,2,4‑triazole(ATA)and then ethylating with triethyl orthoformate.The overall yield was 32.5%and the purity was over 99.8%.The structure of the product was characterized by IR,^(1)H NMR,^(13)C NMR,MS and X‑ray single crystal diffraction.The mechanisms of amination and ethylation were discussed,the thermal and detonation properties of DATNEB were also studied.The results show that DATNEB crystallizes in a monoclinic system,space group P21/c with a=1.21261(7)nm,b=0.89654(4)nm,c=1.12310(6)nm,V=1.17675(11)nm3,Z=4,ρ=1.62 g·cm^(-3).DATNEB exhibits an endothermic peak at 193.9℃and exothermic peak at 236.0℃,indicating a good thermal stability.It has a detonation velocity of 7.05 km·s^(-1) and detonation pressure of 21.14 GPa,which is comparable to TNT,while the sensitivityis much lower than that of TNT and RDX.Therefore,the synthesized high‑purity DATNEB can not only be used as an internal standard,but also an auxiliary component of molten‑cast explosives.