Synthesis And Characterization Of N-Fluorodinitromethyl-Func-Tionalized Polynitro-Triazole/Pyrazole And Optimization Of Synthe-Sis Process Of 1,1′-Dihydroxy-5,5′-Azotetrazole

Most traditional energetic materials are composed of C,H,O,N organic skeletons and explosophore groups,which could release a lot of chemical energy under certain conditions such as heat,friction,impact and electrostatic discharge.Energetic materials play an important role in the development of the national economy and the defense industry.Compared with C,H,O,N atoms,fluorine atom has the largest electronegativity,the smallest atomic radius apart from hydrogen atom.Thus,the introduction of fluorine atom into energetic compounds would improve the oxygen balance and also form intramolecular/intermolecular hydrogen bonds,giv-ing rise to the enhanced density and stability.The fluorine-containing explosives become one of the research hotspots in the field of energetic materials due to these unique advantages.N-fluorodinitromethyl-functionalized polynitro-triazole/pyrazole were synthesized and characterized by IR spectrum,elemental analysis,multinuclear NMR spectroscopy as well as differential scanning calorimetry（DSC）.The crystal packing characteristic of honeycomb co-nstruction for 1-fluorodinitromethyl-3-nitro-1,2,4-triazole and intermolecular/intramolecular interactions were thoroughly explored.The compound 1-fluorodinitromethyl-3-nitro-1,2,4-tri-azole melts at 74℃and decomposes at 167℃,while 1-fluorodinitromethyl-3,4-dinitropyraz-ole melts at 47℃and decomposes at 207℃.Both two compounds show zero oxygen balan-ce,high density(1.88 g·cm^-3),and high detonation performances(v_D=8591-8607 m·s^-1,P=32.7-32.9 GPa).The compound 1-fluorodinitromethyl-3-nitro-1,2,4-triazole（IS=14 J,FS=204 N）has an impact sensitivity comparable to the TNT（IS=15 J,）and significantly better than the 1-fluorodinitromethyl-3,4-dinitropyrazole（IS=10 J,FS=168 N）.The suitable mel-ting point（74℃）and acceptable impact sensitivity（IS=14 J）suggest that 1-fluorodinitrom-ethyl-3-nitro-1,2,4-triazole as a melt-cast explosive carrier and a replacer for TNT.In addition,the high energy explosive 1,1′-dihydroxy-5,5′-azotetrazole has been reported in 2013 which exhibits excellent detonation performance and the potential value of application.Its single crystal density is as high as 1.92 g·cm^-3,and its theoretical detonation velocity and detonation pressure are 9584 m·s^-1 and 39.9 GPa,respectively.In this thesis,the optimum re-action conditions of each step were deeply explored.The optimized operation process of 1,1′-dihydroxy-5,5′-azotetrazole would offer key theoretical and technical support for scale-up pro-duction.