3,4-双(3′-硝基苯-1′-基)氧化呋咱的热分解机理及量子化学研究  

Thermal Decomposition Mechanism and Quantum Chemistry Study on 3,4-Bis(3′-nitrophenyl-1′-yl) furoxan

作　　者：薛云娜[1] 杨建明[1] 王晓红[1] 余秦伟[1] 廉鹏[1] 李亚妮[1] 来蔚鹏[1] 吕剑[1] 薛永强[2] 

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]太原理工大学化工学院,山西太原030024

出　　处：《含能材料》2011年第1期13-18,共6页Chinese Journal of Energetic Materials

基　　金：国防973项目资助(批准号:613740203)

摘　　要：采用Gaussian 98中的DFT-B3LYP方法在6-31G(d,p)基组水平下对3,4-双(3′-硝基苯-1′-基)氧化呋咱进行结构全优化及Wiberg键级计算,并采用TG-DSC-FITR-MS分析方法对其热分解机理进行研究。在优化的几何构型中,氧化呋咱环的六个原子为共平面结构,其中O—N配位键与双键相似。呋咱环内靠近配位氧的O—N键级最弱,为0.8769。结合热解气相产物分析与键级计算推测3,4-双(3′-硝基苯-1′-基)氧化呋咱的热解初始步骤为氧化呋咱环内N—O键的断裂;推测其热分解反应历程为氧化呋咱环首先开环分解为气体小分子及硝基苯,硝基苯再经自由基分解或异构化为亚硝基氧苯分解。The structure of3,4-bis （3＇-nitrophenyl-l＇-yl） furoxan was estimated by a B3LYP method based on 6-31G（d,p） basis set and the stable geometric configuration and Wiberg bond order were obtained. Thermal decomposition mechanism of 3,4-bis （3＇-nitrophenyl-l＇-yl） furoxan was studied by means of simultaneous TG-DSC-FITR-MS. In the geometric configuration afteroptimization,the atoms of furoxan are in one plane and N--O coordination bond is similar to double bond because of conjugate. The bond order of the N--O single bond near N--O coordination bond is0.8769. The initiation step of thermal decomposition is the cleavage of incited N--O single bond. Thermal decomposition mechanism of the title compound was supposed,namely at first,furoxan ring fission occured and produced some small molecular routes that either free radical cleavage or isomerization to nitrosophenol gas and nitrobenzol ,then nitrobenzol decomposed by two

关 键 词：物理化学 氧化呋咱 硝基苯 量子化学 热分解机理 

分 类 号：TQ560.1[化学工程—炸药化工]