推进剂中GAP单体氮消除的反应机理  

Theoretical calculation on the N_2 elimination of GAP monomer

作　　者：李江[1] 李疏芬[1] 王天放[1] 李全新[1] 俞书勤[1] 

机构地区：[1]中国科学技术大学化学物理系

出　　处：《推进技术》2005年第4期371-375,384,共6页Journal of Propulsion Technology

基　　金：国家自然科学基金资助项目(50176047)。

摘　　要：利用B3LYP方法和TST-RRKM理论研究了GAP的一种单体CH3CHOHCH2N3的N2消除反应。计算发现该单体存在三种异构体,得到的反应势垒显示在常温下这些异构体就可以自由转换。计算结果显示有两条反应路径可以解离生成亚胺和N2,反应势垒分别为160.2kJ/mol和164.7kJ/mol,反应放热为213.7kJ/mol,与前人的实验结果相当吻合。计算得到的反应速率常数有着明显的负温度效应,并且随着反应压强的增加而增大。压强为0.1MPa时,反应速率在900K时达到极大值,为1.53×10-12cm3.mol-1.s-1。The N2elimination reactions for one of GAP （ glycidyl azide polymer） monomer, CH3CHOHCH2N3 , were explored with B3LYP method and TST-RRKM theory. Three isomers of CH3 CHOHCH2 N3 were considered and the calculated transition barriers indicate that these isomers can transform to others freely at room temperature. Two reaction pathways were found to yield imine and N2 with reaction barrier of 160.2 kJ/mol and 164.7 kJ/mol, respectively. The whole process is exothermic with a released energy of 213.7 kJ/mol. These data agree well with the experimental measurements. The reaction rate constants show strong negative temperature-dependence and pressure-dependence. The rate constant reaches the maximum value of 1.53×10^-12cm^3·mol^-1·s^-1 with the pressure of 0.1 MPa and the temperature of 900K.

关 键 词：固体推进剂 GAP单体 分解 反应动力学 

分 类 号：O633.1[理学—高分子化学]