3,4-二氨基-5-(3,4-二氨基-1,2,4-三唑-5-基)-1,2,4-三唑及其含能离子盐的合成及性能

Synthesis and Properties of 3,4-Diamino-5-(3,4-diamino-1,2,4-triazol-5-yl)-1,2,4-triazole and Its Energetic Salts

以含能化合物3,4‑二氨基‑5‑(3,4‑二氨基‑1,2,4‑三唑‑5‑基)‑1,2,4‑三唑(化合物1)为有机碱,分别与高氯酸和硝酸进行中和反应,合成了两种具有高热稳定性的含能离子盐:3,4‑二氨基‑5‑(3,4‑二氨基‑1,2,4‑三唑‑5‑基)‑1,2,4‑三唑高氯酸盐(化合物2),3,4‑二氨基‑5‑(3,4‑二氨基‑1,2,4‑三唑‑5‑基)‑1,2,4‑三唑硝酸盐(化合物3)。首次培养了化合物2和3的单晶,并采用单晶X射线衍射进行晶体结构解析;化合物2的晶体结构中,每个阳离子和12个相邻的高氯酸根通过氢键作用相互连接,阳离子形成层状堆积,高氯酸根阴离子镶嵌在层与层之间;化合物3的晶体结构中,每个阳离子和10个相邻的硝酸根通过氢键作用相互连接,从而构筑化合物3的层状堆积结构。采用差示扫描量热仪(DSC)和热重分析仪(TG)研究了化合物2和3的热稳定性,化合物2和3具有超高的热稳定性,其热分解温度分别为338.3℃和289.8℃。此外,化合物2的理论爆速和比冲分别为8308 m·s^(-1)和250.3 s,表现出优异的能量特征;化合物3具有优异的感度特性,其撞击感度和摩擦感度分别高于20 J和360 N。

Herein,two energetic salts,3,4‑diamino‑5‑(3,4‑diamino‑1,2,4‑triazol‑5‑yl)‑1,2,4‑triazolium perchlorate(2)and 3,4‑diamino‑5‑(3,4‑diamino‑1,2,4‑triazole‑5‑yl)‑1,2,4‑triazolium nitrate(3),were prepared by neutralization reaction of 3,4‑diamino‑5‑(3,4‑diamino‑1,2,4‑triazol‑5‑yl)‑1,2,4‑triazole(1)with perchloric acid and nitric acid,respectively.The suitable single crystals of 2 and 3 were obtained and the crystal structures were measured by single crystal X‑ray diffraction analysis.In the crystal structure of 2,each cation interacted with 12 adjacent perchlorates anions through hydrogen bonding.Layer structures were formed by the cations of protonated 1.Perchlorate anions were embedded into two nearby layers.In the crystal structure of 3,each cation interacted with 10 nearby nitrates through hydrogen bonding.Layer structures were built by the cations and nitrates.The thermal stabilities of 2 and 3 were measured by differential scanning calorimeter(DSC)and thermogravimetric analyzer(TG).Compounds 2 and 3 had ultra‑high thermal stabilities,and their thermal decomposition temperatures were 338.3℃and 289.8℃,respectively.In addition,the calculated detonation velocity and specific impulse of 2 were 8308 m·s^(-1) and 250.3 s,respectively,indicating 3 shows excellent energetic properties.Compound 3 had excellent mechanical sensitivity.The values of impact sensitivity and friction sensitivity were higher than 20 J and 360 N,respectively.