Synthesis,Structure And Combustion Catalytic Activity Of Triazoly Energetic Complex

The researchers have been devoted to improve the combustion performance and the energy level of solid propellants.In recent years,energetic complexes as a combustion catalyst have attracted the interest of researchers,in which energy ligands would ensure them with high energy and the metal center would provide good catalytic activity.Nitrogen-rich heterocycles contain a lot of energy,the introduction of nitro into nitrogen-rich heterocycles can further accelerate the release of energy.Based on the above considerations,six energetic complexes:{[Zn（Hddt）（H₂O）2]·H₂O}n（1）、[Cu₃（ddt）₂（H₂O）2]n（2）、[Co（dnbt）（H₂O）4]ClO₄（3）、[Cu₂（dnbt）₂（H₂O）₃（CH₃OH）]·342O（4）、[Pb（dnbt）（H₂O）₃]n（5）、[Ags（dnbt）4]n（6）were synthesized with 4,5-di（1H-tetrazol-5-yl）-2H^-1,2,3-triazole（H3ddt）and 3,3’-dinitro-5,5’-bis(1H^-1,2,4-triazole)（H2dnbt）as energy ligands by hydro/solvothermal method.The structures and physicochemical properties of the 1-6 were characterized.The effect of 1-6 on the combustion of the solid propellant were studied.The main research contents are as follows:1.The structure analysis shows that H3ddt can exhibit different coordination modes under different conditions.Zn（Ⅱ）and Hddt^2-forms a one-dimensional chain structure in 1;while ddt3-and Cu（Ⅱ）to form a three dimensional framework structure in 2.H2dnbt has the some form(dnbt^2-)in 3-6,the oxygen atoms of the nitro groups also participated in the coordination in 5 and 6,due to Ag（Ⅰ）/Pb（Ⅱ）and oxygen atoms have strong affinity.With the coordination of more coordination sites,the dimensions of 3-6 are gradually increased(3/4-0D,5^-1D,6-3D).2.The thermal decomposition behavior of 1-6 were studied by TG-DSC.The results show that the six complexes have high thermal stability,and the thermal decomposition temperature of 5 and 6 exceeds 300℃.Combined with Kissinger’s and Ozawa-Doyle’s methods,the non-isothermal kinetics of 1-6 were studied,and the apparent activation energies and pre-exponential factors were calculated.3.The constant volume energy of combustion of 1-6 were measured by a rotating-oxygen bomb calorimeter,which were used to calculate the standard molar enthalpy of formation.According to the K-J equation,the detonation performances of 1-6 were estimated.The heats of detonation,detonation pressure and detonation velocity ranges from 0.78 to 1.76 kcal·g^-1,31-39 GPa,8000-8400 m·s^-1,respectively.At the same time,the sensitivity test found that the impact of 1-6 were greater than 40 J,the friction sensitivity is greater than 360 N.4.The effects of complexes on the thermal decomposition of ammonium perchlorate（AP）and ammonium dinitramide（ADN）were studied by DSC.The results showed that 2 and 4 have obvious catalytic effect on thermal decomposition of AP,which can convert the slow decomposition process of pure AP to a rapid decomposition process.When the mass ratio is 1:3（2/4:AP）,the decomposition peak temperature can drop to 325℃ and 319℃,respectively.4 has high catalytic activity for ADN,when the addition of catalyst is only 2%,the decomposition peak temperature can reduce 19.2℃.