两种偶氮类化合物热稳定性的实验与理论研究
摘要本文应用差示扫描量热仪（DSC）和绝热加速量热仪（ARC）对偶氮二异丁腈(AIBN)和偶氮二环己基甲腈（ACCN）的热分解过程进行了系统的实验研究，并通过动力学计算软件（AKTS）计算了其动力学参数。利用量子化学计算软件Gaussian 03计算得出了两种物质的稳定构型及其主要参数。DSC曲线表明AIBN和ACCN的放热分解伴随着熔化吸热，相互竞争使得净放热量减少；动力学计算结果表明两者的活化能E和ln(A()f())在整个反应进程中不是固定不变的，说明两种物质的分解反应不遵循单一的反应机理；ARC研究表明，0.178g的 AIBN即显示出热爆炸特性，由T-TMR曲线外推得到50kg包装的AIBN和ACCN的TSADT分别为79.97℃和96.93℃。Gaussian计算结果表明，键级的数值随计算方法与基组的不同而不同；ACCN与AIBN相比，能量更低，更稳定；两种物质分子中的—C-N—单键键解离能均在30kJ/mol左右。63764
毕业论文关键字 AIBN ACCN 热稳定性 热动力学参数 稳定构型 键解离能
毕业设计说明书（论文）外文摘要
Title Experiment and theoretical study on the thermal stability of two kinds of azo compounds
Abstract
The thermal decomposition processes of azoisobutyronitrile and azo dicyclohexyl carbonitrile have been investigated experimentally and theoretically through differential scanning calorimeter (DSC)and accelerating rate calorimeter (ARC). The thermal kinetic parameters were calculated by the Advanced Kinetics and Technology Solutions (AKTS), a dynamic and thermal stability analysis software. The stable configuration and main parameters of the two kinds of materials were got by using quantum chemical calculation software Gaussian 03. DSC curves show that the exothermic decomposition reaction takes place with the endothermic melting process, competing with each other, leading the net heat to drop down. With Friedman differential method and Ozawa integral method, the activation energy and ln(A()f()) were calculated, showing that they are not fixed in the process of reaction, so we can draw a conclusion that the decomposition process does not follow the single reaction mechanism. ARC research shows that 0.178g AIBN displays the thermal explosion properties. And the TSADT values for 50kg package are 79.97℃ and 96.93℃ respectively. Gaussian calculation results reveal that the values of the bond order vary with the calculation method and basis set. Compared with AIBN, the total energy of ACCN is lower and the - C - N - bond energy is higher, making it more stable.
Keywords AIBN ACCN thermal stability thermal kinetic parameters stable configuration bond break energy
1 引言 1
1.1 研究背景及意义 1
1.3 本论文的研究内容 3
2 AIBN和ACCN热稳定性的实验研究 4
2.1 差示扫描量热测试 4
2.2 绝热加速量热测试 13
3 AIBN和ACCN热稳定性的理论研究 21
3.1 Gaussian理论介绍 21
3.2 计算方法介绍 23
3.3 结果与讨论 23
结论 28
致谢 30
参考文献