杯［4］芳烃的热分解动力学研究

通过热失重分析法（TG）研究了杯［4］芳烃与对叔丁基杯［4］芳烃在氮气氛围下的热稳定性，利用Kissinger方法和Flynn?Wall?Ozawa方法分析计算二者的热解表观活化能，通过Coats?Redfern方法确定了热分解动力学机理与模型，并分别求出了材料主降解阶段的非等温动力学方程。结果表明，Kissinger和Flynn?Wall?Ozawa方法求得的杯［4］芳烃的表观活化能分别为166.64 kJ/mol和175.79 kJ/mol，求得的对叔丁基杯［4］芳烃脱叔丁基过程的表观活化能分别为153.97 kJ/mol和166.81 kJ/mol，其自身苯环热分解过程的表观活化能分别为248.38 kJ/mol和252.92 kJ/mol，两物质的热性能在氮气氛围下都表现得较为稳定，且分解温度对于高分子材料的适应性较强；杯［4］芳烃热分解机理函数为g（α）=［-ln（1-α）］^3/2，反应级数n=3/2，其非等温热分解机理属于随机成核和随后生长反应，对叔丁基杯［4］芳烃脱叔丁基过程的热分解机理函数为g（α）=［-ln（1-α）］^2/3，反应级数n=2/3，其非等温热分解机理属于随机成核和随后增长反应，自身苯环热分解过程的热分解机理函数为g（α）=α²，反应级数n=2，其非等温热分解机理属于一维扩散反应。

Study on Thermal Decomposition Kinetics of Calixarene

The thermal stability of calixarene and p?tert?butylcalixarene was studied by thermogravimetric analysis （TG） under a nitrogen atmosphere， and their apparent activation energy were calculated using the Kissinger’s and Flynn?wall?Ozawa’s methods. The thermal decomposition kinetic mechanisms and models were determined from the Coats?Redfern method. The apparent activation energy of calixarene was determined to be 166.64 kJ/mol and 175.79 kJ/mol through the Kissinger’s and Flynn?wall?Ozawa’s methods， respectively. The apparent activation energy of 4?tert?butylcalixarene were calculated to be 153.97 kJ/mol and 166.81 kJ/mol through the Kissinger’s and Flynn?wall?Ozawa’s methods， respectively. The results indicated that the thermal properties of two compounds were relatively stable in nitrogen， and their decomposition temperatures had a strong adaptability to polymer materials. The thermal decomposition mechanism function and reaction order of calixarene were determined to be g（α）=［-ln（1-α）］^3/2 and n =3/2， respectively. Its non?isothermal thermal decomposition mechanism belongs to the random nucleation and subsequent growth reaction. The thermal decomposition mechanism function and reaction order of 4?tert?butylcalixarene were determined to be g（α）=［-ln（1-α）］^2/3 and n=2/3， respectively. Its non?isothermal thermal decomposition mechanism belongs to the random nucleation and subsequent growth reaction. The thermal decomposition mechanism function and reaction order of 4?tert?butylcalixarene for the thermal decomposition process of benzene ring were determined to be g（α）=α² and n=2， respectively. Its non?isothermal thermal decomposition mechanism belongs to the one?dimensional diffusion reaction.