N^1-(2,2,2-三硝基乙基)-1,5-二氨基四唑的合成工艺改进与热性能

Synthesis process improvement and thermal properties of N^1-(2,2,2-trinitroethyl)-1,5-diamino-1H-tetrazole

改进了含能化合物 N1-(2,2,2-三硝基乙基)-1,5-二氨基四唑(TTD)的合成工艺。以二氨基胍盐酸盐为原料,经重氮化反应合成出 1,5-二氨基四唑(DAT),然后与 2,2,2-三硝基乙醇(TNE)发生曼尼希缩合反应得到 TTD,并采用红外光谱、核磁共振、元素分析等鉴定了其结构;优化了缩合反应条件,确定适宜反应条件为:选用物料 DAT 与 TNE 的质量比 1:2.0,反应介质水/乙醇的质量比 1:0.3,温度 30 ℃,时间 1 h。利用差示扫描量热法(DSC)、热失重法(TG)对 TTD进行了热分解研究,并结合 Kissinger 法和 Ozawa 法及相关方程计算了 TTD 的热动力学参数、热爆炸临界温度,得到TTD 的活化能和指前因子分别为:73.65 kJ mol 1,21.15 s 1;并计算得到热爆炸临界温度为 401.34 K。

An improved synthetic process was developed for N1-(2,2,2-trinitroethyl)-1,5-diamino- 1H-tetrazole (TTD). TTD was prepared via diazotization and mannich condensation using diaminoguanidinium and trinitroethanol (TNE) as raw materials, and its structure was identified by IR, 1HNMR and elemental analysis. The optimized reaction condition of TTD was found as: the mass ratio of TTD to TNE = 1:2.0, the mass ratio of water to ethanol = 1:0.3, reaction temperature = 30 ℃ and reaction time = 1 h. The thermal decomposition properties of TTD were studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). Its thermal decomposition kinetic parameters and thermodynamic parameters were calculated by Kissinger and Ozawa methods. The activation energy of TTD was 73.65 kJ mol 1, the pre-exponential factor was 21.15 s 1 and the critical temperatures of thermal explosion (Tp) was 401.34 K.