Synthesis Of Dinitroacetyleneguanidine And Its Derivatives

Multi-nitroacetyleneguanidine is a class of nitroguanidine derivatives that exhibit excellent detonation performances and good thermal stability, so it became one of the focuses in new energetic materials. Multi-nitroacetyleneguanidine contains imide groups in the molecule, therefore the amino, nitro, azido, nitroformate groups of energetic groups are introduced in multi-nitroacetyleneguanidine which can increase the nitrogen content and impove the density、detonation performances. In this paper, some relatively good performance of energetic compounds were synthesized using the 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0] octane as mother skeleton. The main contents was summarized as follows:The process study of 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0] octane was magnified based on the synthesis of 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0] octane.2,6-diamino-3,7-dis(nitroimino)-2,4,6,8-tetrazabicyclo[3.3.0] octane was prepared of 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0] octane and O-(diphenyl-phosphinyl)-hydroxylamine as amination reagent by NaH and 1,4-dioxane. Its structure was characterized; the affecting factors were discussed.2,6-dinitro-3,7-dis(nitroimino)-2,4,6,8-tetrazabicyclo[3.3.0] octane (TNGG) was synthesized using 3,7-bis(nitroimino)-2,4,6,8-tetraazabicyclo[3.3.0] octane as raw material and acetic anhydride as acylation reagent by acylation reaction and nitration reaction. Its structure was characterized. The factors affecting the yield of TNGG was investigated. Its thermal decomposition behavior was studied by thermogravimetric-differential scanning calorimetry(TG-DSC) analysis; Based on the density, the detonation performance of TNGG were obtained by isodesmic reaction and Kamlet-Jacobs formula; its impact sensitivity and friction sensitivity were tested; the distribution of carbon atoms charges of TNGU and tetranitroglycoluril (TNGU) was calculated at the B3LYP/6-31 G(d,p) theoretical level of density functional theory, the hydrolysis stability of TNGG and TNGU is discussed. Results indicate that the yield of TNGG is up to 31.3% under the optimum synthetic conditions of reaction time 15 min, reaction temperature 25℃ and 98% fuming nitric acid/phosphorus pentoxide as nitrating system. The TG-DSC curves show that the thermal decomposition of the compound is completed within 700℃, with the mass loss about 100%. The thermal decomposition peak temperature of TNGG is 182.6℃, indicating that it has a good thermal stability. Theoretical calculations show that the theoretical detonation velocity and detonation pressure of TNGG are 9.76 km·s-1 and 44.0 GPa, respectively, better than those of HMX and RDX.