1,3,4-噁二唑联呋咱含能化合物的设计及构效关系理论研究  

A Series of Energetic Compounds Based on 1,3,4-Oxadiazole-furazan:Molecular Design and Theory Study of Structure-energetic Properties Relationship

作　　者：薛琪[1,2] 毕福强 王子俊[1,2] 廉鹏 张家荣[1,2] 吴敏杰 王伯周[1,2] XUE Qi;BI Fu-qiang;WANG Zi-jun;LIAN Peng;ZHANG Jia-rong;WU Min-jie;WANG Bo-zhou(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《火炸药学报》2021年第4期461-467,共7页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21805223)。

摘　　要：在4种1,3,4-噁二唑联呋咱分子骨架上引入三硝基甲基、氟代偕二硝基、硝基及硝氨基等含能基团,设计了5类共10种含能化合物;采用密度泛函方法B3LPY/6-31G(d,p)基组,研究了化合物的物化性能、爆轰性能(密度、生成焓、氧平衡、爆速、爆压)与安全性能(静电势分布和键解离能)间的构效关系。结果表明,三硝基甲基及氟代偕二硝基可大大改善呋咱衍生物的爆轰性能,而联四芳环的1,3,4-噁二唑联呋咱的共轭母体骨架可有效提高致爆基团中C—NO2的键离解能,是设计高能不敏感含能化合物的有效方法;其中,3,3′-二(5-三硝基甲基-1,3,4-噁二唑)-4,4′-偶氮呋咱(E-1)密度为1.969g/cm^(3),爆速达9130m/s,爆压为38.82GPa,最弱键(C—NO2)键离解能为131.57kJ/mol,表现出优异的综合性能。Based on four kinds of furazan-1,3,4-oxadiazole skeletons,ten novel energetic compounds in five classes were designed by introducing trinitromethyl,fluorodinitromethyl,nitro,nitroamino and other energetic groups.The structure-performance relationship,including physicochemistry-detonation performances(density,enthalpy of formation,oxygen balance,detonation velocity,detonation pressure)and safety performances electrostatic potential distribution and bond dissociation energy,was studied by density functional theory at B3LPY/6-31G(d,p).The results show that the trinitromethyl and fluorodinitromethyl groups can greatly improve the detonation performances of furazan derivatives,and the furazan-1,3,4-oxadiazole-based conjugate skeleton construction containing four aromatic rings can effectively increase the BDE of C—NO2 bond,which provides an effective approach for designing high energy low sensitivity energetic compounds.Among them,3,3′-bis(5-trinitromethyl-1,3,4-oxadiazole)-4,4′-azofurazan(E-1)shows an excellent overall performance with the density of 1.969g/cm^(3),detonation velocity of 9130m/s,detonation pressure of 38.82GPa and the weakest bond dissociation energy of 131.57kJ/mol.

关 键 词：量子化学 含能材料 1 3 4-噁二唑联呋咱 分子设计 密度泛函理论 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O641[理学—物理化学]