端叠氮聚叠氮缩水甘油醚的热分解动力学

Thermal Decomposition Kinetic Study of Azido-terminated Glycidiyl Azide-polymer

为了解端叠氮聚叠氮缩水甘油醚(GAPA)的热分解动力学和热安全性,采用差示扫描量热法(DSC)、热重法(TG)对GAPA进行了热分解特性研究。根据GAPA在升温速率为2,5,10,20℃·min^(-1)时放热峰温和分解深度,考察了GAPA热分解反应的表观活化能、指前因子和热分解动力学方程,计算出热力学参数和热安全性参数。结果表明,GAPA的热分解反应过程分为两个阶段,表观活化能EK为218.47 kJ·mol^(-1),指前因子A_K为1.06×10^(22)s^(-1),自发火温度T_(bpo)为506.55 K,自加速分解温度T_(SADT)为496.78 K,以及活化自由能(ΔG~≠)、活化焓(ΔH~≠)和活化熵(ΔS~≠)分别为132.76 kJ·mol^(-1)、214.34 kJ·mol^(-1)和164.21 J·mol^(-1)·K^(-1)。

To understand the thermal decomposition kinetics and thermal safety property of azido-terminated glycidyl azide polymer （GAPA）, its thermal decomposition characteristics was investigated through differential scanning calorimetry（DSC） and thermal gravimetry（TG）. The apparent activation energy, pre-exponential factor and thermal decomposition kinetic equation were studied based on the DSC curve peak temperatures and the TG curve decomposition degrees at heating rates of 2 ℃·min^-1, 5 ℃·min^-1 , 10 ℃·min^-1 and 20 ℃·min^-1. Its kinetic parameters thermodynamic and thermal safety parameters were calculated. The study indicates that there are two stages in the GAPA thermal decomposition reaction with the apparent activation energy EK =218.47 kJ · mol^-1, pre-exponential factor AK = 1.06 × 10^22 s^-1 , self-ignition temperature Tbpo = 506.55 K, self-accelerated decomposition temperature Ts^oT =496.78 K, free energy of activation △G^gb =132.76 kJ · mol^-1 , enthalpy of activation AH^≠ =214.34 kJ · mol^-1 and entropy of activation DS^≠=164.21 J · mol^-1·K^-1.