5,6-二氨基呋咱并[3,4-b]吡嗪-4,7-二氧化物(DAFPO)的合成、结构及性能

Synthesis,Structure and Properties of 5,6-Diaminofurazano[3,4-b]pyrazine-4,7-dioxide

新型高能不敏感含能材料的合成对于武器装备能量水平和安全性的提升有重要意义。以5,6-二氨基呋咱并[3,4-b]吡嗪为原料,经氧化反应首次合成了5,6-二氨基呋咱并[3,4-b]吡嗪-4,7-二氧化物(DAFPO),用核磁共振(氢谱、碳谱、氮谱)、红外光谱和元素分析对其进行了表征。以乙酸乙酿为溶剂使用缓慢蒸发法获得了DAFPO-2H_2O的单晶,利用X-射线单晶衍射和Hirshfeld表面分析完成了结构解析和分子间相互作用研究。结果表明,DAFPO·2H2O属正交晶系,Pna21空间群,296 K下晶体密度1.806 g·cm^-3,分子间存在较强的O…H和N…H氢键作用。使用差示扫描量热法(DSC)和热失重法(TG/DTG)进行热分析,结果显示其热分解峰温为131.8℃。基于原子化反应利用Gaussian 09计算DAFPO的固相生成热为753.5 kJ·mol^-1,由气体膨胀置换法测得其密度1.86 g·cm^-3,使用EXPLO5预测其理论爆速和理论爆压分别为8836 m·s^-1和36.0 GPa,采用BAM标准方法测得其撞击感度大于40 J,摩擦感度大于360 N。性能研究结果表明,DAFPO是一种兼具较高能量水平和优良安全性能的新型不敏感含能材料。

The synthesis of novel high energy low sensitivity materials is important for improving of energy level and safety performance of weapons.5,6-Diaminofurazano[3,4-b]pyrazine-4,7-dioxide(DAFPO)was firstly synthesized by oxidation reaction using 5,6-diaminofurazano[3,4-b]pyrazine as raw material.Its structure was characterized by nuclear magnetic resonance(^1 H,^13C and ^14N spectrum),infrared spectroscopy and element analysis.The single crystal of DAFPO·2 H2O was cultivated from ethyl acetate.Its crystal structure was determined by X-ray single-crystal diffraction,and the intermolecular interactions were investigated by Hirshfeld surface analysis.DAFPO·2 H2O belongs to orthorhombic system,space group Pna21,the crystal density is 1.806 g·cm^-3 at 296 K.The crystal is stabilized by strong O…H and N…H hydrogen bonds interactions existed in different molecules.The thermal behavior of DAFPO was studied by DSC and TG/DTG method,giving decomposition temperature at 131.8℃.Based on atomization reaction and Gaussian 09 software,the calculated solid heats of formation of DAFPO is 753.5 kJ·mol^-1.Its density is 1.86 g·cm^-3 by gas expansion replacement method.The calculated detonation velocity and detonation pressure predicted by EXPLO5 code are 8836 m·s^-1 and 36.0 GPa,respectively.According to standard BAM method,the impact sensitivity is above 40 J,and the friction sensitivity is above 360 N.It is found that DAFPO is a novel low sensitivity energetic material with high energy level and good safety performance.