Carboxylic Acid Regulation Iii / Tetrazole Transition Metal-containing With The Synthesis, Structure And Catalytic Combustion

Triazole, tetrazole and their derivatives have attracted a wide spread attention of researchers because their good coordination ability and various coordination modes. Meanwhile, the energy complexes with triazole and tetrazole can be used as combustion catalyst in solid propellant owing to the high energy, high densities and low sensitivity. In pursuit of the novel structure and the coordination of high energy, stability and oxygen balance of propellant components, co-ligangs carboxylic acid (malonic acid, succinic acid, fumaric aicd, 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid and 2,6-pyridine-dicarboxylic acid) are introduced to the triazole/tetrazole systems (1,2,4-triazole, 3,5-diamine-1,2,4-triazole, 3-diamine-5-carboxylic acid-1,2,4-triazole, 5-aminotetrazole) complexes of transition metals. Using solution method and hydrothermal/solvothermal method, thirty new Cu, Co, Ni complexes are prepared and characterized by chemical analyses, elemental analyses, IR spectra, TG-DTG techniques. The structures of twenty complexes among them are determained by X-ray single crystal diffraction. The main research contents and conclusions in this dissertation are summarized as follow:1. The structure analysis results of complexes reveal that the triazole ligand may coexist in two states of neutral and anion; tetrazole acting as a neutral unidentate ligand coordinate with metal. Metal and triazole/tetrazole can be built mononuclear, binuclear and trinuclear complexes. Carboxylic acid ligands are introduced the M- triazole/tetrazole system, leading to coordination polymers and supermolecular structures by different coordination modes and intermolecular interaction.2. The thermokinetic research of liquid-phase reactions of complexes reveal that all the liquid phase formation reaction of the complexes are exothermic and benefit the proceeding of reactions. The thermal stability of the complexes reveals that the dehydration products of complexes possess high thermal stability (most main framework still keep stabilization above 300℃). Compared with the complexes contained aliphatic acids, the complexes contained aromatic acids exhibit higher stability because of the steady cluster structures and chelate ring.3. The effects on the thermal decomposition behavior of complexes for the main component of propellant (AP,HMX,RDX,NC/NG) are investigated by DSC technique. The results indicate that all the binary mixture system composed of complexes and main component of propellant shows ahead of decomposed peak temperature, increase of heat and decrease of active energy during thermal decomposition. The complexes can be used as energetic combustion catalyst in propellants. The increasing of oxygen content in complexes have a significant influence on the thermal decomposition of mixture system, which approves that the idea adding carboxylic acid to the M/triazole/tetrazole system is reasonable for the combustion catalysis in double-base solid propellant.