摘要
以3-氨基-4-偕氯肟呋咱为原料,通过五步反应制备得到3-硝氨基-4-偕二硝基甲基呋咱二肼盐(化合物6)。采用核磁(氢谱、碳谱),红外,元素分析和X射线单晶衍射表征确定了其结构。结果表明,其晶体属于单斜晶系,P21/n空间群,晶胞参数为a=3.7236(4)?;b=14.3867(18)?;c=20.386(2)?;β=92.432(5)°;V=1091.1(2)?3;Z=4;Dc=1.815 g·cm^(-3)。晶体中,阳离子与阴离子之间存在的大量氢键作用,这有利于分子稳定性的提高。水合肼的加入导致了N,N'-亚甲基联3-硝氨基-4-偕二硝基甲基呋咱(化合物5)中C—N键的断裂和化合物6的生成。依据Gaussian 09计算得到化合物6的生成焓为291.7 kJ·mol^(-1),采用经验公式计算得其室温下(298 K)晶体密度为1.782 g·cm^(-3)。使用EXPLO 5计算得到化合物6的爆速(D)与爆压(p)分别为9032 m·s^(-1),35.9 GPa,优于黑索今(D=8848 m·s^(-1),p=34.8 GPa)。通过BAM标准方法测得化合物6的撞击感度为4 J,摩擦感度为76 N。
Dihydrazinium 3-dinitromethyl-4-nitraminofurazan(compound 6)was prepared via five steps of reaction using 3-ami-no-4-chloroximinofurazan as raw material.Its structure was characterized and determined by nuclear magnetic resonance(1H spectrum and 13C spectrum),infrared spectroscopy,element analysis,and X-ray single crystal diffraction.Results show that the crystal belongs to monoclinic system with space group P21/n and unit cell parameters of a=3.7236(4)A,b=14.3867(18)A,c=20.386(2)A,β=92.432(5)°,V=1091.1(2)A3,Z=4,Dc=1.815 g cm^-3.A large number of hydrogen bonds exist between cat-ions and anions in the crystal,which is conducive to the improvement of molecular stability.The addition of hydrazine results in the cleavage of the C-N bond in N,N'-methylene-3-nitroamino-4-dinitromethylfurazan(compound 5)and the formation of compound 6.The enthalpy of formation of compound 6 calculated by Gaussian 09 is 291.7 kJ·mol-1 and the crystal density at 298 K calculated by empirical formula is 1.782 g·cm^-3,the detonation velocity(D)and detonation pressure(p)of compound 6 calculated by EXPLO 5 are 9032 m·s-1 and 35.9 GPa,respectively,which are superior than those(D=8848 m·s-1,p=34.8 GPa)of RDX.The impact sensitivity of compound 6 determined by standard BAM method is 4 J and the friction sensitivity is 76 N.
作者
林智辉
孙琦
陆明
LIN Zhi.-hui;SUN Qi;LU Ming(China North Chemical Industries Group Corporation Limited,Beijing 100089,China;School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2018年第10期864-868,共5页
Chinese Journal of Energetic Materials
基金
国家自然科学基金-联合基金资助(U1530101)
作者简介
林智辉(1976-),男,研究员,主要从事火炸药技术研究与科研管理工作。e-mail:zhlin513@163.com.;通信联系人:陆明(1963-),男,教授,主要从事新型含能材料设计与合成研究。e-mail:luming302@126.com.
