3,3′-双(2-硝胺基-1,3,4-噁二唑-4-基)-5,5′-联-1,2,4-噁二唑及其含能离子盐的合成及性能  

Synthesis and Properties of 3,3′-Bis(2-nitroamino-1,3,4-oxadiazol-4-yl)-5,5′-linked-1,2,4-oxadiazole and Its Energetic Salts

作　　者：廖思丞 邓沐聪 宋思维 靳云鹤 刘天林 张庆华[1] LIAO Si-cheng;DENG Mu-cong;SONG Si-wei;JIN Yun-he;LIU Tian-lin;ZHANG Qing-hua(Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621999,China)

机构地区：[1]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》2020年第7期632-637,I0006,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金面上基金(21875228);国家自然科学基金青年基金(21702196)。

摘　　要：以乙二肟为原料,经取代、环化、硝化等五步反应合成了四联环含能化合物3,3'-双(2-硝胺基-1,3,4-噁二唑-4-基)-5,5'-联-1,2,4-噁二唑(BNOBO)。利用BNOBO的酸性,设计、合成了BNOBO的铵盐、肼盐和羟胺盐等三种含能离子盐(5-7)。并采用红外光谱、核磁等进行了结构表征。采用溶剂挥发法培养了BNOBO铵盐的晶体,该晶体属于单斜晶系,C2/c空间群,晶胞参数为a=1 2.7490(8) nm,b=9.5957(7) nm,c=18.5965(12) nm,V=2272.1 (3) nm^3,Z=4。利用差示扫描量热(DSC)和热重(TG)等热分析方法研究了BNOBO及其三种离子盐的热性能,基于密度仪获得的实测密度,运用EXPLO5 v6.02软件计算了目标化合物的爆轰性能,并利用BAM感度仪测试了撞击和摩擦感度。研究结果表明,所得化合物中BNOBO的热分解温度最高为21℃,其密度最高为1.90 g·cm^-3、BNOBO的计算爆速和爆压分别达到8789 m·s^-1和32.7 GPa,离子盐5的撞击感度大于20J,摩擦感度为220 N。A new energetic compound 3,3’-bis(2-nitroamino-1,3,4-oxadiazol-4-yl)-5,5’-linked-1,2,4-oxadiazole(BNOBO)was synthesized starting from glyoxime through a five-step reaction.Based on the acidity of BNOBO,three energetic salts(5-7)were obtained through the reactions between BNOBO and aqueous ammonia,hydrazine and hydroxylamine,respectively.The structures of as-synthesized compounds were characterized by single-crystal X-ray diffraction,IR,NMR and element analysis.The crystal of BNOBO ammonium salt was obtained through solvent evaporation method,the obtained results show that it belongs to a monoclinic system and C2/c space group with a=12.7490(8)nm,b=9.5957(7)nm,c=18.5965(12)nm,V=2272.1(3)nm3 and Z=4.Their thermal stability,density,detonation properties and sensitivity were evaluated by TG/DSC analysis,densitometer,EXPLO5 v6.02 software and BAM sensitivity tester,respectively.Among these new energetic compounds,BNOBO possesses the highest measured density of 1.90 g·cm^-3 and the highest onset decomposition temperature of 215℃.The calculated detonation velocity and pressure of BNOBO are as high as 8789 m·s^-1 and 32.7 GPa,respectively.These new energetic compounds also exhibit relatively low mechanical sensitivities,in which energetic salt 5 display the low impact sensitivity of more than 20 J and friction sensitivity of 220 N.

关 键 词：含能材料 3 3'-双(2-硝胺基-1 3 4-噁二唑-4-基)-5 5'-联-1 2 4-噁二唑 含能离子盐 合成 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]