5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐的合成、晶体结构及性能

以3,4-二氨基呋咱为原料,经重氮化-叠氮化、氧化-环化等反应合成了一种新型无氢富氮含能材料5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐(AFTF);采用红外光谱、核磁共振、元素分析等方法表征了目标物的结构;获得了AFTF的单晶并进行了晶体结构解析;采用DSC方法研究了AFTF的热稳定性,初步探讨了氧化-环化反应机理;采用Gaussian 09程序CBS-QB3方法计算了AFTF的固相生成热,基于晶体密度和固相生成热,利用EXPLO5爆轰软件预估了AFTF的爆轰性能。结果表明,化合物AFTF晶体为正交晶系,空间群为P 2(1)2(1)2(1),晶胞参数为:a=8.1782(17),b=8.6446(18),c=11.521(2),V=814.5(3)3,Z=4,μ=0.151 mm^-1,F(000)=440;AFTF的熔点为101.02℃,热分解温度为186.39℃;AFTF晶体密度为1.795 g/cm 3(296 K),氮含量为63.6%,理论爆速为8.982 km/s,爆压为33.5 GPa,生成热为1178.9 kJ/mol,爆热为6450.8 kJ/kg,表明AFTF是一种爆轰性能优良的无氢富氮高能量密度化合物,有望应用于高能推进剂或气体发生剂领域;低熔点特性有望使其作为熔铸炸药载体使用。

Synthesis,Crystal Structure and Properties of 5-(4-Azidofurazan-3-yl)-[1,2,3] triazolo[4,5-c]furazan Inner Salt

A new hydrogen-free and nitrogen-rich energetic material,5-(4-azidofurazan-3-yl)-[1,2,3]triazolo[4,5-c]furazan inner salt,was synthesized via diazotization-azidation and oxidative-cyclization reactions using 3,4-diaminofurazan as starting material.The structure of target compound was characterized by means of IR spectra,1H NMR,13 C NMR,14 N NMR,15 N NMR and elemental analysis.The single crystal of AFTF was obtained and analyzed.The thermal stability of AFTF was studied by DSC method.The reaction mechanism of oxidative-cyclization was investigated.Based on the heats of formation calculated from CBS-QB3 method by Gaussian 09 program and the crystal density,the detonation parameters of AFTF were computed using EXPLO5 program.The results show that the crystal of AFTF belongs to a orthorhombic system and space group P 2(1)2(1)2(1)with cell parameters:a=8.1782(17),b=8.6446(18),c=11.521(2),V=814.5(3)3,Z=4,μ=0.151 mm^-1,F(000)=440.DSC analysis showes the melting point and thermal decomposition peak temperature of AFTF are 101.02℃and 186.39℃,respectively.The crystal density of AFTF is 1.795 g/cm 3(296 K),the content of nitrogen is 63.6%,the detonation velocity is 8.982 km/s,the detonation pressure is 33.5 GPa,the heat of formation is 1178.9 kJ/mol and the detonation energy is 6450.8 kJ/kg.As a hydrogen-free and nitrogen-rich high energy density compound with preferable detonation properties,AFTF can be applied to high energy propellants and gas generators,as well as the carrier of melt-cast explosives because of its low melting point.