Synthesis,Structure And Physicochemical Properties Of Energetic Complexes Based On Tris(5-Aminotetrazole) Triazine

Energetic complexes based on nitrogen-rich ligands are very popular in energy-containing materials due to their high density,low sensitivity,good thermal stability and controllable structure.In this paper,seven high-energy and insensitive complexes were designed and synthesized.The results show that these seven complexes not only have excellent detonation performance,but also have a good promoting effect on the combustion decomposition of AP,the common oxidant of solid propellant.According to the principle of coordination chemistry,the nitrogen-rich heterocyclic ligand 3?5-amino tetrazolium?-triazine?H₃TATT?was self-assembled with Cu???,Mn???,Co???,Ni???,Zn???and Pb???ions,and 7 cases of complexes were synthesized by hydrothermal method in this paper:Cu?HTATT??H₂O?₂?1?,[Cu₃?TATT?₂?H₂O?₂]_n?2?,{[Zn₂?HTATT?₂?H₂O?₂]·3H₂O}_n?3?,{[Pb Zn?TATT??OH??H₂O?]_n?4?,[Co?HTATT?]_n?5?,[Ni?HTATT?]_n?6?,{[Mn₄?TATT?₂?OH?₂?H₂O?₂]·H₂O}_n?7?.?1?Seven complexes were characterized by X-ray single crystal diffraction,infrared analysis and elemental analysis,and their crystal structure and experimental conditions were compared and analyzed.The results show that the single crystal samples of the target complexes are easy to be obtained at neutral,weak acidity and high temperature,and the three tetrazole branches of the"Y"ligand H₃TATT are prone to a certain degree of torsion in the coordination process,showing a variety of coordination patterns,and combining with metal ions to form a multi-dimensional structure.The presence of solvent molecules leads to the formation of a large number of hydrogen bonds in the structure,which contributes to the enhancement of structural stability.?2?The TG-DSC test of 7 complexes showed that complex 1-7 had good thermal stability,and complex 5 and 6 had better thermal stability due to complex coordination mode and structural reinforcement.The specific heat capacity of 7 complexes was measured by C80microcalorimeter.The kinetic calculation of the thermal decomposition process of complex1-7 was carried out based on the Kissinger method and Ozawa-Doyle method,and the apparent activation energy and pre-exponential factor of the complexes were obtained.?3?The density functional theory and Kamlet-Jacobs equation were used to estimate the detonation heat?Q?,detonation speed?D?and detonation pressure?P?of complexes 1-7.The results of impact sensitivity and friction sensitivity tests show that complexes 1-7 are not sensitive to external stimuli.Corresponding magnetic tests were performed on complexes 5and 7.?4?The effects of complexes 1-7 on the thermal decomposition properties of ammonium perchlorate?AP?and hexogen?RDX?were studied by DSC method.The results showed that all the seven complexes had obvious promoting effect on the combustion decomposition of AP,which not only advanced the exothermic peak temperature of AP to a certain extent,but also increased the heat release,of which complex 5 had the best catalytic effect.The effect of 7complexes on the exothermic peak temperature of RDX was not obvious,and the change of decomposition peak temperature was not significant.The complexes 1-2,4-6 all increased the heat release of RDX to different degrees.