Thermal Decomposition Study Of Azo-triazole And Synthesis And Theoretical Studies Of Energetic Salts Based On 3,3’-difluoro-azetidine

Nitrogen-rich compounds have many advantages,such as high nitrogen content,high enthalpy of formation,easy to achieving oxygen balance,and environmentally friendly.They have broad application prospects such as the new insensitive explosive,low siganature propellant,low smoke and gunpowder residue and other areas.The thermal analysis of energetic materials has a great significance of the establishment of the qualitative description and mathematical model of the law of the reaction in the combustion process,the kinetic parameters and the calculation of the thermodynamic parameters.Energetic ion sals is an important research direction of energetic materials.It is consisted of cation and anion.And it has a low vapor pressure,good thermal stability and eco-friendly decomposition products.This paper reviews the thermal analysis in the field of energetic materials applications and progress of heterocyclic compounds.Five different heating rates of TG-DSC tests of 1,1’-azobis-1,2,3-trizole and 4,4’-azobis-1,2,4-trizole were carried out and we got the decomposition characteristics of them and a pyrolysis gas chromatograghy-mass spectrometry was conducted at 400 ℃ and 500 ℃ and we got the decomposition product and the proportion of the two temperature.Depending on the heating rate and peak temperature respectively,we calculated activation energy of thermal decomposition of the two compound in Kissinger method and Ozawa method, and results of 1,1’-azobis-1,2,3-trizole were 297.11 kJ?mol-1 and 284.42 kJ?mol-1, results of 4,4’-azobis-1,2,4-trizole were 398.55 kJ?mol-1,384.70 kJ?mol-1. Test and analysis results show that Kissinger method and Ozawa method is suitable for studying the thermal decomposition characteristics of such multi-nitrogen compounds, but the error is slightly larger; high-temperature thermal mass spectrometry confirmed, both pyrolysis product is more complex, the proportion of small gas components, we need to be possible to use it as an energetic material for further modification.Through the introduction of C—F bond and azetidine,we designed and synthesized a series of high tension heterocyclic energetic salt 3,3’-difluoro-azetidine energetic salt In the paper, we selected 3,3’-difluoro-azetidine as reaction subustrates, and designed,synthesized 3,3-difluoro-azetidine hydrochloride, 3,3’-difluoro-azetidine nitrates, 3,3’-difluoro-azetidine perchlorate, 3,3’-difluoro-azetidine nitroformate salt. 3,3’-difluoro-azetidine nitro-tetrazolium salt, 3,3’-difluoro-azetidine dinitro-triazole salt All the products were fully characterized by IR、1H-NMR、13C-NMR and elemental analysis and the structures of the compounds were confirmed by X-ray crystallography.In this thesis, the structures of compounds were optitimizated and by splitting the substituents, we got the key equation.A series of tests were carried out of them, such as friction sensitivity,electrostatic sensitivity and impact sensitivity, and they were compared by 2,4,6-trinitrotoluene( TNT).Such a family of energetic salts have low sensitivities.The detonation velocity( except 3,3’-difluoro-azetidine hydrochloride) are greater than 7700 m?s-1. And the burst pressure(except 3,3’-difluoro-azetidine hydrochloride)are greater than 26 GPa.And the specific impulse(except 3,3’-difluoro-azetidine hydrochloride) are more than 200 s.They can meet the requiements of high energy density of the materials. And they have a good respect. Meanwhile, the sensitivity of 3,3’-difluoro-azetidine nitroformate salt, 3,3’-difluoro-azetidine dinitramide salt, 3,3-difluoro-azetidine nitro-tetrazolium salt, 3,3-difluoro-azetidin dinitro-triazole salt has significantly improved as compared with the molecular.