6-氨基胍基-1,2,4,5-四嗪-3-酮的合成、晶体结构和热分解行为

Synthesis,Crystal Structure and Thermal Decomposition Behavior of 6-Aminoguanidine-1,2,4,5-tetrazine-3-one

以3,6-双(3,5-二甲基吡唑基)-1,2,4,5-四嗪(BT)和硝基胍为原料,经亲核取代、还原反应,合成了6-氨基胍基-1,2,4,5-四嗪-3-酮(AGTzO),采用X-射线单晶衍射对AGTzO的结构进行表征;利用差示扫描量热法(DSC)和热重法(TG-DTG)研究了AGTzO的热分解行为;用Kissinger法和Ozawa法对不同升温速率下AGTzO的DSC曲线进行分析,获得热分解动力学参数,并分析了其热安全性。结果表明,AGTzO·H2O的晶体属于正交晶系,Pbca空间群,每个晶胞包含8个AGTzO·H2O分子,晶体密度为1.639g/cm3;AGTzO·H2O的活化能(E)和指前因子(A)分别为173.03kJ/mol、1015.96s-1;自加速分解温度(TSADT)、热点火温度(Tbe)和热爆炸临界温度(Tbp)分别为232.05、234.93和236.91℃;用氮当量公式计算AGTzO·H2O的爆速(D)为8421m/s,爆压(p)为30.4GPa,其爆轰性能与TATB(D=8114m/s,p=31.2GPa)相当。

Using 3,6-bis(3,5-dimethyllpyrazolyl)-1,2,4,5-tetrazine(BT)and nitroguanidine as raw materials,6-aminoguanidine-1,2,4,5-tetrazine-3-one(AGTzO)was synthesized by the reactions of nucleophilic substitution and reduction.The structure of AGTzO was characterized by single crystal X-ray diffraction.The thermal decomposition behavior of AGTzO was analyzed by differential scanning calorimetry(DSC)and thermogravimetry(TG-DTG).The kinetic parameters were obtained by Kissinger and Ozawa methods using DSC curves at different heating rates,and the thermal safety was analyzed.The results show that the crystal of AGTzO·H2O belongs to the orthorhombic system,Pbca space group.Each unit cell contains eight AGTzO·H2O molecules,and the crystal density is 1.639g/cm3.The apparent activation energy(E)and pre-exponential constant(A)are 173.03 kJ/mol and 1015.96s-1,respectively.The self-accelerating decomposition temperature(TSADT),the thermal ignition temperature(Tbe)and the critical temperature of thermal explosion(Tbp)are 232.05,234.93,and 236.91℃,respectively.The nitrogen equivalent formula was used to calculate the detonation velocity D(8421m/s)and the detonation pressure p(30.4GPa)of AGTzO·H2O.Its detonation performance is close to that of TATB(D=8114m/s,p=31.2GPa).