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程序包中的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学计算.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=230.78kJ/mol,而碳前驱物CH3 Ar-CH2 NH2的实验表观活化能Ea=206.78kJ/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的原因;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稠环缩合反应,将获得分子平面取向性很好的稠环芳烃产物.
参考文献
| [1] | Carroll, Thomas J. (Salem, NH), Connors. Jr, Donald F. (Tewksbury, MA), Suplinskas, Raymond J. (Haverhill, MA), Thurston, Garrett S. (Lowell, MA); United States Patent, No. 5397595(1995) |
| [2] | E.Bruneton, B.Nancy, A.Oberlin, 35(10～11), 1593～1598(1997) |
| [3] | Thurston, Garrett S. (Lowell, MA), Suplinskas, Raymond J. (Haverhill, MA), Carroll, Thomas J. (Salem,NH), Connors. Jr, Donald F. (Tewksbury, MA), Scaringella, David T. (Franklin, MA), Krutenat, Richard C.(Belmont, MA),United States Patent No. 5,733, 611(1998) |
| [4] | 翟高红,碳/碳复合材料碳源化合物热解机理研究,硕士论文,西北大学(2000)(ZHAI Gao-Hong, Studied on Pyrolysis Mechanism of the Carbon Source Compound used for Carbon/Carbon Composite Material Master＇s thesis of Northwest university, (2000)) |
| [5] | Gaussian 98, Revision A.6, M.J.Frisch, G.W.Trucks, H.B.Schlegel, G.E.Scuseria, M.A.Robb, J.R.Cheeseman,V.G.Zakrzewski, J.A.Montgomery, Jr., R.E.Stratmann, J.C.Burant, S.Dapprich, J.M.Millam, A.D.Daniels,K.N.Kudin, M.C.Strain, O.Farkas, J.Tomasi, V.Barone, M.Cossi, R.Cammi, B.Mennucci, C.Pomelli,C.Adamo, S.Clifford, J.Ochterski, G.A.Petersson, P.Y.Ayala, Q.Cui, K.Morokuma, D:K.Malick,A.D.Rabuck, K.Raghavachari, J.B.Foresman, J.Cioslowski, J.V.Ortiz, B.B.Stefanov, G.Liu, A.Liashenko,P. Piskorz, I.Komaromi, R.Gomperts, R.L.Martin, D.J.Fox, T.Keith, M.A.A1-Laham, C.Y.Peng,A.Nanayakkara, C.Gonzalez, M.Challacombe, P.M.W.Gill, B.Johnson, W.Chen, M.W.Wong, J.L.Andres,C.Gonzalez, M.Head-Gordon, E.S.Replogle, J.A.Pople, Gaussian, Inc., Pittsburgh PA, 1998 |
| [6] | 南京大学化学系有机教研室编,有机化学(北京,人民教育出版社,1978)p.16(Organic Chemistry, edited by Teaching and Research Section of Chemistry Department in Nanjing University (Beijing, People Education Press, 1978) p.16) |
| [7] | 付献彩,沈文霞,姚天杨编,物理化学,第四版(北京,高等教育出版社,1997)p.756(FU Xiancai, SHEN Wenxia, YAOTianyang, Physical Chemistry I, 4th edition (Beijing, Higher Education Press, 1997) p.756) |
| [8] | 大谷杉郎,真田雄三著,张名大,杨俊英译,碳化工学(兰州,甘肃文化出版社,1985)p.25(Ooya Sugirou, Zhen Tian Xiong-San, Translated by Lanzhou Charcoal Research Institute, et al, Introduction to Carbonization Engineering (Lanzlou, Ganshu Culture Press, 1985)p.25) |
| [9] | 付献彩,陈瑞华编,物理化学,(北京,人民教育出版社,1982)p.235～236(FU Xiancai, CHEN Ruihua, Physical Chemistry 2, (Beijing, People Education Press, 1982) p.235) |
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