4,4′-偶氮-1H-1,2, 4-三唑-5-酮铵盐AZTO.H2O的制备及热化学性质
2015,23(8):741-745
摘要：以4-氨基-1, 2, 4-三唑-5-酮(ATO)为原料，通过高锰酸钾氧化制备了一种新型高能有机铵盐4, 4′-偶氮-1H-1, 2, 4-三唑-5-酮铵盐(AZTO·H2O)。用差示扫描量热法研究了其的热行为。用Kissinger法和Ozawa法计算了其非等温热分解反应的动力学参数。结果表明，其分解热、表观活化能和指前因子分别为247.46 kJ·mol-1、177.80 kJ·mol-1和1015.74 s-1。其热爆炸临界温度和298.15 K下的摩尔热容分别为233.1 ℃和271.45 J·mol-1·K-1。它的绝热至爆炸时间为72.8~74.7 s。描述AZTO·H2O放热分解反应的动力学方程为：$\frac{{{\rm{d}}\alpha }}{{{\rm{d}}\mathit{T}}}{\rm{ = }}\frac{{{{10}^{15.74}}}}{\beta } \times 4(1 - \alpha ){[{\rm{ln}}(1 - \alpha )]^{\frac{3}{4}}}\exp ( - 1.774 \times {10^5}/\mathit{RT})$ 。
关键词：含能材料; 4,4′-偶氮-1H-1,2,4-三唑-5-酮铵盐; 热性能; 绝热至爆炸时间; 制备
4,4′-偶氮-1H-1,2, 4-三唑-5-酮铵盐AZTO·H2O的制备及热化学性质研究
Abstract：A new high-energy organic ammonium salt 4, 4′-azo-1H-1, 2, 4-triazol-5-one ammonium salt (AZTO·H2O) was synthesized via potassium permanganate oxidation using 4-amino-1, 2, 4-triazol -5-one (ATO) as starting material. The thermal behaviors of AZTO·H2O was studied by differential scanning calorimetry. The kinetic parameters of non-isothermal exothermic decomposition reaction were calculated by Kissinger method and Ozawa method. Results show that the decomposition heat, apparent activation energy and pre-exponential factor of AZTO·H2O are 247.46 kJ·mol-1, 177.80 kJ·mol-1 and 1015.74 s-1 respectively. The critical temperature of thermal explosion and molar heat capacity at 298.15 K for AZTO·H2O is 233.10 ℃ and 271.45 J·mol-1·K-1, respectively. The adiabatic time-to-explosion is between 72.8 s and 74.7 s. The kinetic equation describing the exothermic decomposition reaction of AZTO·H2O is $\frac{{{\rm{d}}\alpha }}{{{\rm{d}}\mathit{T}}}{\rm{ = }}\frac{{{{10}^{15.74}}}}{\beta } \times 4(1 - \alpha ){[{\rm{-ln}}(1 - \alpha )]^{\frac{3}{4}}}\exp ( - 1.774 \times {10^5}/\mathit{RT})$ .
Key words：energetic materials; 4,4′-azo-1H-1,2, 4-triazol-5-one ammonium salt (AZTO·H2O); thermal property; adiabatic time-to-explosion; preparation
收稿日期：2014-06-26
基金项目：陕西省科学技术研究发展计划项目(2013K02-25)； 第47批留学回国人员科研启动基金教外司留(1792)； 陕西省教育厅科研计划项目(14JF025)
