间苯三酚法合成TATB产品中副产物的鉴定及性能表征

Identification and Performance Characterization of By-products in TATB Synthesized by Phloroglucinol Method

为研究间苯三酚法合成无氯TATB副产物对TATB性能的影响,采用柱层析法将TATB中含有的微量副产物进行了有效分离,结合红外光谱、质谱及核磁对分离得到的副产物进行定性分析;通过差示扫描量热法、热失重法研究TATB及副产物的热分解性能;基于密度泛函数理论计算了TATB及副产物的部分爆轰性能参数。结果表明,TATB中含有的副产物为1-氨基-3,5-二乙氧基-2,4,6-三硝基苯(AETB)和1,3-二氨基-5-乙氧基-2,4,6-三硝基苯(EDATB);副产物的热分解性能与TATB间存在一定差异,TATB及副产物均只有一个热失重过程,但副产物失重过程的起始温度及速率远低于TATB;在相同升温速率下,AETB和EDATB的放热分解峰温分别比TATB低109.2℃和121.4℃;TATB仅在较高温度下存在一个放热分解的过程,副产物EDATB和AETB在较低温度下均存在明显的吸热熔化现象,温度继续上升到一定值后逐渐发生放热分解,副产物的热安定性远低于TATB;由密度泛函理论计算获得副产物的爆热值与TATB十分接近,但是密度、爆速及爆压值均低于TATB。

To study the effect of by-products on the properties of chlorine-free TATB synthesized by phloroglucinol method,column chromatography was used to effectively separate the trace by-products contained in TATB.The by-products were qualitatively analyzed by FTIR,NMR and MS.Thermal decomposition properties of TATB and by-products were studied by differential scanning calorimetry and thermogravimetry;Based on the density functional theory,some detonation performance parameters of TATB and by-products were calculated.The results show that the by-products in TATB are 1-amino-3,5-diethoxy-2,4,6-trinitrobenzene(AETB)and 1,3-diamino-5-ethoxy-2,4,6-trinitrobenzene(EDATB).There are some differences between the thermal decomposition properties of by-products and TATB.Both TATB and by-products have only one thermogravimetric process,but the initial temperature and rate of the by-product mass loss process are much lower than that of TATB.At the same heating rate,the exothermic decomposition peak temperatures of AETB and EDATB are 109.2℃and 121.4℃lower than those of TATB,respectively.TATB only has one exothermic decomposition process at higher temperatures.EDATB and AETB have obvious endothermic melting phenomena at lower temperatures,and the exothermic decomposition gradually occurs when the temperature continues to rise to a certain value,and the thermal stability of the by-products is much lower than that of TATB.The detonation heat values of the by-products calculated by density functional theory(DFT)are very close to that of TATB,but the values of density,detonation velocity and detonation pressure are all lower than those of TATB.