The Study Of Energetic Compounds Based On 1H,1'H-5,5'-bitetrazole-1,1'-diol

1H,1'H-5,5'-bitetrazole-1,1'-diol is a promising energetic compound with the advantages like stable,safe,insensitive and environmental-friendly.It also has a high nitrogen and oxygen-containing.In order to explore the practical application as the energetic materials,we systematically study on the structures and properties of 30 species of energetic compounds based on 1H,1'H-5,5'-bitetrazole-1,1'-diol.The main contents and conclusions in this paper are summarized as follows:The 1H,1'H-5,5'-bitetrazole-1,1'-diol is synthesized by using hydroxylamine hydrochloride and ethanedial as the starting reagents,and fully characterized by modern analytical technologies including elemental analysis,Fourier Transform infrared spectroscopy?FT-IR?spectroscopy,NMR spectrum and mass spectrum.The monocrystal of the compound is obtained,and the structure is determined by single crystal X-ray diffraction.The thermal decomposition behavior is studied based on technologies of DSC and TG-DTG.The optimized geometry of 1H,1'H-5,5'-bitetrazole-1,1'-diol is optimized by using Gaussian 09 program.The results show that the structure optimized at B3LYP/6-311++g**level is most consistent with experimental structure.The theoretical calculations of the electronic structure,natural bond orbital charge and frontier orbital energy of the compound are also studied.5 kinds of alkali metal salts,4 kinds of alkaline earth salt,8 kinds of transition metal salts,16 kinds of nitrogen-rich organic salts,1 kind of coordination polymer and 1 kind of cocrystal based on 1H,1'H-5,5'-bitetrazole-1,1'-diol are designed,synthesized,and fully characterized by modern spectroscopic techniques.Single crystals are obtained by solvent evaporation method,and the crystal structures are analyzed.The thermal decomposition behavior of the compounds are analyzed by DSC and TG-DTG,the non-isothermal kinetic parameters are calculated,as well as the critical temperature of thermal explosion.The enthalpy of formation are determined from the combustion heat data measured by using the oxygen bomb calorimetry.The sensitivities towards impact and friction are also tested.Among the metal salts,the dipotassium 5,5'-bis?tetrazole-1-oxide?has a stable crystal structure without toxic heavy metals in it.It has a good thermal stability with a decomposition temperature beginning at 307?,and the critical temperature of thermal explosion is 342.9?.It is sensitive to mechanical stimulation.All the results provideing a promising future for the salt using as a kind of green heat-resisting initiating explosive.Among the organic salts,the hydrazine 5,5'-bitetrazole-1,1'-dio has the highest density of 1.912 g cm^-3 under 298K.It has a good thermal stability with the decomposition temperature above 200°C.Theoretical detonation performances of the salt are higher than those of RDX,and in the same level of TKX-50.While the sensitivities towards impact and friction are better than that of TKX-50.The salt has provided a promising future by using as a kind of insensitive explosive alternative.A novel energetic coordination polymer,or a new anionic metal-organic framework?MOFs?,of{TAG[Li?BTO??H₂O?]}_n,and a novel cocrystal energetic material BTO/ATZ based on 1H,1'H-5,5'-bitetrazole-1,1'-diol are developed and characterized.The crystal structures and properties are discussed in detail.The discovery contributes significantly to the expansion and application of 1H,1'H-5,5'-bitetrazole-1,1'-diol in the field of novel nitrogen-rich insensitive anionic metal-organic frameworks and cocrystal explosives.