5,5′-二硝基-3,3′-联(1,2,4-三唑)草酰肼双阳离子盐的合成、表征与性能预估

Synthesis,Characterization and Performance Prediction of Oxalohydrazidinium 5,5′-dinitro-3,3′-bi(1,2,4-triazolate)

为研究双子型含能离子盐的稳定性和爆轰性能,探究其在含能材料领域的应用前景,以5,5′-二硝基-3,3′-联(1,2,4-三唑)(DNBT)为前体,与草酰肼经酸碱中和反应合成了5,5′-二硝基-3,3′-联(1,2,4-三唑)草酰肼双阳离子盐(DNBOT),成盐收率为80.8%;利用X-射线单晶衍射、红外光谱、核磁共振对产物结构进行表征,通过DSC-TGA同步热分析仪对其热性能进行了分析,采用Gaussian 09程序和EXPLO5爆轰软件对其爆轰性能进行了理论计算并测试了其机械感度。结果表明,化合物5,5′-二硝基-3,3′-联(1,2,4-三唑)草酰肼双阳离子盐的晶体结构属于单斜晶系,晶体密度为1.653g/cm^(3),空间群为P2_(1)/c,晶体结构中含有两个结晶水,脱结晶水后化合物的实测密度为1.701g/cm^(3);在熔点205℃时开始分解,分解峰温为207℃;理论爆速为7620m/s、爆压为21.8GPa、撞击感度大于40J、摩擦感度大于360N,综合性能优于TNT,是一种综合性能较好的新型双子型含能离子化合物,且合成路线简单。

To study the stability and detonation performances of gemini energetic ionic salt,and its application prospect in the field of energetic materials,5,5′-dinitro-3,3′-bi(1,2,4-triazole)was used as the precursor to synthesize oxalohydrazidinium 5,5′-dinitro-3,3′-bi(1,2,4-triazolate)by the acid-base neutralization reaction with oxalyl hydrazide,and the yield is 80.8%.The structure of the product was characterized by single crystal X-ray diffraction,infrared spectroscopy,and nuclear magnetic resonance.Its thermal property was analyzed by DSC-TGA synchronous thermal analyzer.The Gaussian 09 program and EXPLO5 detonation software were used to theoretically calculate detonation performances,and the mechanical sensitivities were also tested.Results show that the crystal structure of oxalohydrazidinium 5,5′-dinitro-3,3′-bi(1,2,4-triazolate)belongs to monoclinic crystal system,space group is P2_(1)/c,with crystal density of 1.653g/cm^(3).The crystal structure contains two crystalline water molecules,and the measured density of the compound after removing the water molecules is 1.701g/cm^(3).It starts to decompose at the melting point of 205℃,and the decomposition peak temperature is 207℃.Its theoretical detonation velocity is 7620m/s,the explosion pressure is 21.8GPa,the impact sensitivity is greater than 40J,and the friction sensitivity is greater than 360N,showing that the comprehensive performance is superior to TNT.It is a novel gemini energetic ionic compound with good comprehensive performance and simple synthetic route.