双(1,2,4-三唑基)三氮烯含能离子化合物的合成及其性能研究  

Synthesis and Properties of Bis(1,2,4-triazolyl)triazene Energetic Ionic Compounds

作　　者：蒋绣俄 杜慧英 朱娟 李彬 屈智慧 伍波 马丛明 JIANG Xiu-e;DU Hui-ying;ZHU Juan;LI bin;QU Zhi-hui;WU Bo;MA Cong-ming(State key Laboratory of Environment-friendly Energy Materials,Southwest University of Science and Technology,Mianyang Sichuan 621010,China;Luzhou North Chemical Industries Co.Ltd.,Luzhou Sichuan 646003,China;College of Safety Science and Engineering,Nanjing Tech University,Nanjing 211800,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]泸州北方化学工业有限公司,四川泸州646003 [3]南京工业大学安全科学与工程学院,江苏南京211800

出　　处：《火炸药学报》2021年第5期595-601,共7页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21905236)。

摘　　要：以3-氨基-1,2,4-三氮唑(1)为原料,通过重氮-N-偶联反应得到了具有三氮烯(—N=N—NH—)结构的双(1,2,4-三唑基)三氮烯(2);利用其酸性,设计并合成了基于该阴离子的5种离子型含能化合物;利用X-射线单晶衍射分析、傅里叶变换红外光谱(FT-IR)、核磁共振谱(^(1)H NMR、^(13)C NMR)、差示扫描量热仪-热失重(DSC-TG)联用等手段对所合成的化合物进行了结构表征和理化性能测试,并利用Kamlet-Jacobs方程预测了其爆轰性能。结果表明,中性化合物2以及4种含能离子化合物的热分解温度范围为164.73~210.97℃,其中羟胺盐的热分解温度为210.97℃,热稳定性较好;正生成焓范围为509.98~937.22kJ/mol;其中三氮烯钠盐(3)为正交晶系,空间群为Pccn,晶体密度为1.548g/cm^(3);5种化合物实测感度较低,其撞击感度特性落高(H_(50))在46.2~105.1cm之间,均优于RDX(H_(50)=46.1cm),其中中性化合物2的感度(H_(50)=105.1cm)与TNT(H_(50)=102.0cm)相近;5种化合物理论爆速为6406~7348m/s、爆压为16.6.0~21.9GPa。Bis(1,2,4-triazolyl)triazene(2)with triazene bridge(—N=N—NH—)was synthesized from 3-amino-1,2,4-triazole(1)via diazonium-N-coupling reaction.Five energetic ionic derivatives(3-7)of compound 2 were designed and synthesized by taking advantage of its acidity.The resulting compounds were characterized by single crystal X-ray diffraction analysis,Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(^(1)H NMR,^(13)C NMR),while their thermal stabilities were investigated by differential scanning calorimeter-thermalgravimetric(DSC-TG)united device.The impact sensitivity was measured according to GJB772A-97 method,and their detonation parameters were predicted based on isodesmic reactions and Kamlet-Jacobs equation.The results show that the thermal decomposition temperature of compound 2 and the four energetic ionic compounds range from 164.73 to 210.97℃,among which the hydroxylamine salt exhibits good thermal stability with decomposition temperature of 210.97℃;the range of positive enthalpy of formation is 509.98 to 937.22kJ/mol.Among them,the triazene sodium salt(3)belongs to an orthorhombic crystal system with space group of Pccn,and the crystal density is 1.548g/cm^(3).The measured sensitivities of the five compounds are relatively low with the H_(50) value range from 46.2—105.1cm,which are less sensitive than that of RDX(H_(50)=46.1cm),and the sensitivity of compound 2(H_(50)=105.1cm)is similar to that of TNT(H_(50)=102.0cm).These compounds exhibit modest detonation performances with detonation velosity of 6406—7348m/s and detonation pressure of 16.6.0—21.9GPa.

关 键 词：有机化学 含能离子化合物 双(1 2 4-三唑基)三氮烯 晶体结构 热分解 撞击感度 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]