4-硝基-2-(1-硝基-1,2,4--三唑-3-基)-1,2,3-三唑的合成、热性能及量子化学研究

摘要

Using 3-amino-1,2,4-triazole as starting material,a new energetic compound,4-nitro-2-(1-nitro-1,2,4-triazole-3-yl)-1,2,3-triazole(DNDTz),was synthesized via diazotisation,substitution,intramolecular cyclic condensation and nitration with a yield of 25.02％.The structure of intermediates and target product was confirmed by IR,1 HNMR,13C NMR,mass spectrum and elemental analysis.The thermal behavior of DNDTz was studied by using differential scanning calorimetry (DSC) and thermogravimetry (TG).The results show that DNDTz is directly decomposed in solid without changing into liquid by heating.The exothermic decomposition peak temperature of DNDTz is 160.8 ℃.Its thermal decomposition process can be divided into three stages with mass loss of 13.50％,52.39 ％ and 27.15 ％,respectively.The optimized geometry of DNDTz were performed by the B3PW91/6-31G(d,p) method.The stable structure,bond order,thermodynamic properties and the temperatures dependence on thermodynamic parameters of DNDTz were obtained.The crystal density of DNDTz obtained by Monte-Carlo and Politzer's correlation is 1.812 g/cm3.The detonation velocity of DNDTz predicted by VLW formula is 8.604 km/s.%以3-氨基-1,2,4-三唑为原料,经过重氮化、取代、分子内缩合、硝化反应合成4-硝基-2-(1-硝基-1,2,4-三唑-3-基)-1,2,3-三唑(DNDTz),总收率为25.02％.采用红外光谱、1H NMR、13C NMR、质谱及元素分析对中间体及目标产物的结构进行了表征;采用DSC、TG研究了DNDTz的热行为,得到DNDTz放热分解峰为160.8℃,热分解过程分为三个阶段,质量损失分别为13.5％、52.39％、27.15％.结果表明,DNDTz没有熔融过程,而是直接分解.采用B3 PW91/6-31G(d,p)方法对DNDTz进行结构优化,获得稳定构型、键级和热力学性质以及温度与内能、热容和熵的关系式;用Monte-Carlo方法结合Politzer校正公式,得到DNDTz的理论密度为1.812 g/cm3,用VLW公式预测其爆速为8.604 km/s.