2,4,6-三氨基-1,3,5-三嗪-1,3-二氧化物(TATDO)的热分解特性

Thermal Decomposition Characteristics of 2,4,6-Triamino-1,3,5-triazine-1,3-dioxide (TATDO)

为了促进新型N-氧化含能化合物2,4,6-三氨基-1,3,5-三嗪-1,3-二氧化物(TATDO)的应用,采用差示扫描量热仪(DSC)、热重分析仪(TG/DTG)和热重-质谱-红外(TG-MS-FTIR)三联用技术等对其热分解特性进行了研究。结果表明,TATDO只有一个放热分解过程,10.0℃/min下外推起始温度为295.2℃,峰温为315.8℃,放热量约为1532J/g,质量损失约为41%,表明TATDO的热稳定性良好。用Kissinger方法获得TATDO的表观活化能和指前因子,分别为377.10kJ/mol和10^(31.80)s^(-1)。TATDO热分解产生的主要气体产物为H_(2)O、NH_(3)和CO,并且从分子及自由基结构模型和解离能的角度推测其热分解机理可能为:首先分子内氢转移(从TATDO到TATDO′的互变异构),然后氮氧键断裂氧化生成NH_3和碳氮聚合物。

For promoting the application of novel N-oxide energy-containing compounds 2,4,6-trimino-1,3,5-triazine-1,3-dioxide(TATDO),the thermal decomposition characteristics of the compound were studied by using differential scanning calorimeter(DSC),thermogravimetric analyzer(TG-DTG)and thermogravimetric-mass-infrared spectrometry(TG-MS-FTIR)techniques.The results show that there is only one exothermal decomposition process of TATDO with an extrapolated starting point temperature of 295.2℃,a decomposition peak temperature of 315.8℃,a heat release of 1532 J/g and a mass loss of about 41%at a heating rate of 10.0℃/min,indicating the good thermal stability of TATDO.The apparent activation energy and pre-exponential factor of the decomposition process were calculated by Kissinger method to be 377.10 kJ/mol and 1031.80 s^(-1),respectively.Moreover,the main thermal decomposition gas products of TATDO are H_(2)O,NH_(3) and CO,and the possible thermal decomposition mechanism through the molecular and free radical structure model and dissociation energy was inferred that firstly intramolecular hydrogen transfer(tautomerism from TATDO to TATDO′),followed by nitrogen-oxygen bond cleavage and being oxidized to generate NH 3 and carbon-nitrogen polymers.