Study On The Design And Synthesis Of Several New Tetrazole Energetic Compounds

Pursuing the advantages of high detonation performance,low cost and good chemical stability are the important principles of developing new energetic materials.The decomposition products of tetrazole compounds are low pollution and theirs high energy density,which has become a research hotspot in the field of energetic materials in recent years.In this paper,some new energetic materials containing tetrazole ring were designed and synthesized.Subsequently,the properties of these compounds were tested.The main contents are as follows:Starting with the construction of molecular modules?structural units,connecting units and functional groups?,six energetic molecular structures were designed with tetrazole ring,triazole ring and fuzzan ring as the main structural units and–NH₂,-NO₂ as the main functional group.The molecular models were modeled and optimized by GaussView,and then the density,enthalpy of formation and sensitivity of the molecule were calculated which studied at the level of 6-31G⁺⁺based on B3LYP method of density functional theory.The detonation performance parameters were predicted by K-J formula.Combined with the results of performance and the analysis of the feasibility of the synthesis of six compounds,two kinds of compounds were selected for synthesis studied,which were 5-?3-nitro-1,2,5-oxadiazol-4-yl?-hydroxy-tetrazol-1-ol and 4,5-Bis?1-hydroxytetrazol-5-yl?-1,2,3-triazole.5-?3-nitro-1,2,5-oxadiazol-4-yl?-hydroxy-tetrazol-1-ol was synthetized from malononi-rile through five-step reaction such as nitrification,cyclization,diazotization,substitu-tion and oxidation.The corresponding synthesis mechanisms were explored.And all of the compounds were characterized by infrared spectrum?IR?,melting point test,element analysis and nuclear magnetic resonance?NMR?.The synthetic route of the intermediate 3-amino-4-aminoximofuroxan was optimized,and the yield reached 93.0%.Two oxidants?“Hydrogen peroxide+Methane sulfonic acid+Sodium tungstate”and“Hydrogen peroxide+Methane sulfonic acid”?were used to study the oxidation reaction.The thermodynamic properties of the product were studied by DSC.The thermal decomposition temperature of the compound was162?.The sensitivity of compound is 22cm.4,5-Bis?1-hydroxytetrazol-5-yl?-1,2,3-triazole and its nitrogen-rich salts were synthetized from Diaminomalenitrile through five-step reaction such as diazotization coupling,diazo,substitution,cyclization and double decomposition.The corresponding synthesis mechanisms were explored.And all of the compounds were characterized by infrared spectrum?IR?,melting point test,element analysis and nuclear magnetic resonance?NMR?.The use of hydroxylamine solution in the synthesis of 4,5-diamidoxime-1,2,3-triazole was discussed in this paper.It was decided to replace the highly toxic hydroxylamine solution with hydroxylamine hydrochloride,and to optimize the process after substitution.The yield was 76.8%.The thermodynamic properties of several energetic compounds have been studied by DSC.The thermal decomposition temperature of the compounds are between 216 and 288?,and the decomposition of compound“e”?4,5-Bis?1-hydroxytetrazol-5-yl?-1,2,3-triazole 5-AT acid?is relatively fast,which has the potential as a gas generator for airbag.