4,4'-二(氯偕二硝基甲基)-3,3'-偶氮呋咱的晶体结构和热稳定性  

Crystal Structure and Thermal Stability of 4,4'-Bis(chlorodinitromethyl)-3,3'-azofurazan

作　　者：顾昊[1] 马卿[2] 杨红伟[1] 程广斌[1] 范桂娟[2] 

机构地区：[1]南京理工大学化工学院,江苏南京210094 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2017年第7期585-590,共6页Chinese Journal of Energetic Materials

基　　金：中国工程物理研究院科学技术发展基金项目(2015B0302055);国家自然科学基金青年基金项目(11402237);国家自然科学基金-中国工程物理研究院联合基金重点项目(U1530262)

摘　　要：为了获得4,4'-二(氯偕二硝基甲基)-3,3'-偶氮呋咱(BCNAF)的晶体结构,以4,4'-二氰基-3,3'-偶氮呋咱为原料,经三步合成了BCNAF。以无水甲醇为溶剂,采用溶剂挥发法获得了目标化合物的黄色块状单晶。利用X-射线单晶衍射技术对单晶结构进行了表征。结果表明,该分子在293(2)K下晶体密度为1.869 g·cm^(-3),单晶结构为单斜晶系,空间群为P2_1/n,晶胞参数为a=7.5846(14),b=8.4227(15),c=12.324(2),β=90.880(4)°,V=787.2(2)~3,Z=2,μ=0.494 mm^(-1),F(000)=440。分子结构高度对称,分子间存在的π-π堆积作用以及卤键作用,可以提高BCNAF的稳定性。用差热扫描量热对晶体进行热分析,结果表明其分解温度为142℃。基于Guassian 09和等键反应计算得到其固相生成热为816.5 k J·mol^(-1),优于RDX。采用EXPLO5预测其理论爆速为8400 m·s^(-1),爆压为30.8 GPa,与RDX相当。4,4＇-Bis（chlorodinitromethyl） -3,3 ＇-azofurazan （BCNAF） was synthesized by using 4,4＇-dicyano-3,3 ＇-azofurazan as the starting material. The single crystal of target compound was cultivated by slow evaporation from methanol and its crystal structure was determined by X-ray single-crystal diffraction. Results show that it belongs to monoclinic system, space group P21/n, with cell parameters ofa=7.5846（14） A,b=8.4227（15） A,c=12.324（2）A,β=90.880（4）°,V=787.2（2） A3,Z=2,μ=0.494 mm-1, F（000） = 440. Crystal packing suggests that BCNAF is stabilized by highly symmetric structure, intermolecular π-π interaction as well as intramolecular halogen bonds. The thermal behavior of 4,4＇-bis （ chlorodinitromethyl ） -3,3＇-azofurazan was studied by using DSC-TG instrument, which showed that its decomposition peak was 142 ℃. Its calculated heats of formation is 816.5 kJ · mol-1 by using Guassian09 and isodesmic reactions, which is higher than that of RDX. Its calculated detonation velocity （D） and detona- tion pressure （p） by EXPLO5 code are 8400 m ·s-1 and 30.8 GPa ,respectively, which are close to those of RDX.

关 键 词：含能材料 4 4'-二(氯偕二硝基甲基)-3 3'-偶氮呋咱(BCNAF) 晶体结构 热性能 

分 类 号：TQ560.1[化学工程—炸药化工]