两种不同晶型N-甲基-2,4,6-三硝基苯甲胺的制备与性能研究  

Preparation and Performance Study of Two Different Crystal Forms of N-Methyl-2,4,6-trinitromethylamine

作　　者：钟圣 金波 彭汝芳[1,2] ZHONG Sheng;JIN Bo;PENG Ru-fang(State Key Laboratory for Environment-friendly Energy Materials,Southwest University of Science and Technology,Mianyang Sichuan 621010,China;School of Materials Science and Engineering,Southwest University of Science and Technology,Mianyang Sichuan 621010,China)

机构地区：[1]西南科技大学环境友好能源材料国家重点实验室,四川绵阳621010 [2]西南科技大学材料与化学学院,四川绵阳621010

出　　处：《火炸药学报》2022年第6期827-834,共8页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21875192)。

摘　　要：为了寻找一种替代TNT的熔铸液相载体炸药,采用硝化、VNS胺化反应合成N-甲基-2,4,6-三硝基苯甲胺(TNA),并在不同pH环境中重结晶,得到两种不同晶型的TNA(α和β)。通过FT-IR、~1H NMR、13C NMR、SEM以及X射线单晶衍射等方法对获得的α和β两种不同晶型TNA的物相、结构和形貌进行了表征;采用差热分析法(DTA)研究了不同升温速率下α-TNA和β-TNA的熔融和分解过程,并利用Kissinger法和Ozawa法计算了两种晶型的热分解反应动力学参数;通过修正后的氮当量公式,分别计算了α-TNA和β-TNA的爆速、爆压;采用摩擦感度测试和撞击感度测试对α-TNA和β-TNA的安全性能进行了研究。结果表明,α-TNA属于单斜晶系P21/n空间群,β-TNA属于三斜晶系P-1空间群,其密度分别为1.649、1.681g/cm^(3);α-TNA、β-TNA熔点分别为110.98、113.70℃,热分解活化能分别为91.70、94.41kJ/mol;α-TNA、β-TNA爆速、爆压分别为7075、7170m/s和21.37、22.18GPa。α-TNA、β-TNA的摩擦感度、撞击感度均为360N、40J。表明TNA具有良好的热稳定性,爆轰性能与TNT相当,其摩擦感度、撞击感度优于TNT,具有良好的安全性能。In order to find alternative melt-cast liquid phase carrier explosive to TNT,N-methyl-2,4,6-trinitromethylamine(TNA)was synthesized through nitration and VNS amination.Two different crystal forms of TNA(αandβ)were obtained by recrystallization in different pH environments.The structure and morphology of two different crystal forms of TNA were characterized by FT-IR,~1H NMR,13C NMR,SEM,and single crystal X-ray diffraction.The melting and decomposition processes ofα-TNA andβ-TNA at different heating rates were studied by differential thermal analysis(DTA),and the thermal decomposition reaction kinetic parameters of the two crystal forms were calculated by Kissinger and Ozawa methods.The detonation velocity and detonation pressure ofα-TNA andβ-TNA were calculated respectively through the modified nitrogen equivalent formula,and the safety performances were studied by friction and impact sensitivity test.The results show thatα-TNA belongs to monoclinic system,P21/n space group,and the crystal density is 1.649 g/cm^(3);β-TNA belongs to triclinic system,P-1 space group,and the crystal density is 1.681 g/cm^(3).The melting points ofα-TNA andβ-TNA are 110.98℃and 113.70℃,respectively;the thermal decomposition activation energies are 91.70 kJ/mol and 94.41 kJ/mol,respectively.The detonation velocity and detonation pressure ofα-TNA andβ-TNA are 7075 m/s,7170 m/s and 21.37 GPa,22.18 GPa.The friction and impact sensitivity of bothα-TNA andβ-TNA are 360 N and 40 J.It shows that TNA has good thermal stability and good safety performance.Its detonation performance is comparable to that of TNT,and friction and impact sensitivity are lower than that of TNT.

关 键 词：有机化学 N-甲基-2 4 6-三硝基苯甲胺 TNA 晶型 热稳定性能 安全性能 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O625.6[理学—有机化学]