一种碳前驱物热解反应的热力学和动力学研究

根据量子化学理论研究了碳前驱物CH3－Ar-CH2-NH2的热裂解机理，利用Gaussian98程序包听AM1法，用UHF计算对化合物五种可能的热裂解路径进行了热力学和动力计算，结果表明，碳前驱物CH3－Ar-CH2-NH2将首先发生生成自由基CH3－Ar-CH2和NH2．的热裂解主反应，活化能Ea=230.78kg/mol，而碳前驱物CH3－Ar-CH2-NH2的实验表观活化能Ea=206.78kg/mol.键能的计算值与实验值符合得比较好，通过分析优化的反应物及产物自由基的部分结构参数，了解了理论支持主反应原因，计算的产物自由基的空间构型表明主反应路径生成的产物自由基相互间若进行筒环缩合反应，获得得分子平面取向性很好的稠环芳烃产物。

THERMODYNAMICS AND KINETICS ABOUT PYROLYSIS OF A CARBON MATRIX COMPOUND

The pyrolysis mechanism of carbon matrix compound CH3-Ar-CH2-NH2 was studied. Using the AM1 method and UHF calculation in Gaussian 98 program package, thermodynamic and kinetic data for 5 types of designed pyrolysis path of the compound were calculated. The calculation result showed that the reaction producing CH3-Ar-CH2 and NH2 is the main pyrolysis reaction path. The calculated activation energy is Ea=230.78kJ/mol, while the experimental apparent activation energy of the compound is Ea=206.78kJ/mol. Comparing with experiment data demonstrated that the calculated bond energy parameters are reliable. Parts of the optimized geometry parameters of the reactant and production free radicals were analyzed. After the compound CH3-Ar-CH2-NH2 as carbon matrix compound are Pyrolyzed, the equilibrium geometries of produced free radicals show that plane orientation of the polymeric ring aromatic moleculars will be good when free radicals polymerized are fused aromatic ring structure.