5-酮-3-(5’-氨基-3’-偶氮异呋咱)-异呋咱和5,5’-二酮-3,3’-偶氮异呋咱的晶体结构和热稳定性  

Crystal Structure and Thermal Stability of 3-(5’-Amino-3’-diazenyl-1’,2’,4’-oxadiazol)-5-one-1,2,4-oxadiazol(BAKIF)and 3,3’-Azo-1,2,4-oxadiazol-5,5’-dione(BDKIF)

作　　者：吴克林 杨红伟[1] 程广斌[1] WU Ke-lin;YANG Hong-wei;CHENG Guang-bin(School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]南京理工大学化工学院

出　　处：《含能材料》2019年第7期609-615,I0006,共8页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21676147,21875110)

摘　　要：以二氰胺钠为原料,经环化、偶联、硝化三步反应分别合成了5-酮-3-(5′-氨基-3′-偶氮异呋咱)-异呋咱(BAKIF)和5,5′-二酮-3,3′-偶氮异呋咱(BDKIF)。采用溶剂挥发法从甲醇中得到了BAKIF·2H2O和BDKIF的单晶。利用X-射线单晶衍射技术对它们的单晶结构进行了表征。用DSC-TG研究了它们的热稳定性。采用EXPLO5预测了它们的的爆轰性能。结果表明,BAKIF·2H2O分子在173K下晶体密度为1.645g·cm-3,该晶体属于正交晶系,P212121空间群,晶胞参数为a=4.6661(4)A,b=13.5836(10)A,c=14.8537(10)A,V=941.46(12)A^3,Z=4,μ=0.149mm^-1,F(000)=480。BDKIF分子在173K下晶体密度为1.708g·cm-3,该晶体属于三方晶系,R-3空间群,晶胞参数为a=20.4183(12)A,b=20.4183(12)A,c=4.8017(7)A,V=1733.7(3)A3,Z=9,μ=0.153mm^-1,F(000)=900。5℃·min^-1时,BAKIF和BDKIF的放热峰温度分别为290.01℃和149.75℃。BAKIF的理论爆速和理论爆压分别为7292m·s^-1和21.5GPa,BDKIF的理论爆速和理论爆压分别为7363m·s^-1和20.7GPa,均优于TNT,认为它们是潜在的钝感含能材料。3-(5′-Amino-3′-diazenyl^-1′,2′,4′-oxadiazol)-5-one^-1,2,4-oxadiazol(BAKIF)and 3,3′-azo^-1,2,4-oxadiazol-5,5′-di- one(BDKIF)were synthesized respectively via three step reactions of cyclization,coupling and nitrification using sodium dicy- anamide as raw material. The single crystals of BAKIF and BDKIF were obtained by solvent evaporation method from methanol. Their crystal structures were characterized by X-ray single-crystal diffraction technique. Their thermal stabilities were studied by DSC-TG. Their detonation performances were predicted by EXPLO5. The results show that the crystal density of BAKIF·2H2O molecule is 1.645 g·cm^-3 at 173 K. The crystal belongs to orthorhombic system,space group P212121 with cell parameters of a= 4.6661(4)A,b=13.5836(10)A,c=14.8537(10)A,V=941.46(12)A3,Z=4,μ=0.149 mm^-1,F(000)=480. The crystal densi- ty of BDKIF molecule is 1.708 g·cm-3 at 173 K. The crystal belongs to trigonal system,space group R-3 with cell parameters of a =20.4183(12)A,b=20.4183(12)A,c=4.8017(7)A,V=1733.7(3)A^3,Z=9,μ=0.153 mm^-1,F(000)=900. The exothermic peak temperature of BAKIF and BDKIF at 5 ℃·min^-1 is 290.01 ℃ and 149.75 ℃,respectively. Theoretical detonation velocity and theoretical detonation pressure are 7292 m·s^-1 and 21.5 GPa for BAKIF,and 7363 m·s^-1 and 20.7 GPa for BDKIF,which are superior to those of TNT. Considering that they are potential insensitive energetic materials.

关 键 词：含能材料 5-酮-3-(5′-氨基-3′-偶氮异呋咱)-异呋咱(BAKIF) 5 5′-二酮-3 3′-偶氮异呋咱(BDKIF) 晶体结构 热性能 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]