Synthesis, Characterize And Properties Of Insensitive Explosive About Pyridine Derivatives

In this paper, the synthesis, structure characterization and comprehensive performance of the multi-amino and multi-nitropyridines and their oxides were studied systematically, especially 2,6-diamino-3,5-dinitropyridine-l-oxide (ANPyO), 2,4,6-triamino-3,5-dinitropyridine-l-oxide (TANPyO) and metal complex of ANPyO.ANPyO was synthesized by using 2,6-diaminopyridine as primary material, followed by salifying reaction, nitration and N-oxidation. The overall yield and product purity were improved to 75% and 99% compared with 45% and 95% of primitive methods, respectively. This method has more mild condition, more security and is conducive to enlarge; Another new synthetic method of ANPyO was explored by using 2,6-diaminopyridine as the starting material, followed by acetylation, N-oxidation and nitration. The overall yield was improved to 81%. ANPyO was also synthesized by nitration of 2,6-diacetamidopyridine-l-oxide using N2O5/solvents as the nitration reagent, and the yield was improved to 92.5%. This innovative method has advantages of fast reaction, short reaction time, low reaction temperature and greatly improved yield. Refining ANPyO by acylation,recrystallization and deoxidation, we found that this process overcomes defects of the presence of trifluoroacetic acid as solvent, which has the high cost,toxicity and unstable performance, by contrast sample size distribution thermal decomposition properties,SEM test and sensitivity test. The result shows that the better size, micro structure and security of sample is obtained under 50℃using DMF and Ammonia as the solvent and animation reagent, respectively. The crystal of ANPyO is belong to monoclinic system, space group is C2/c. Cell parameters are:a=1.4838(3) nm, b=0.73280 (15) nm, c=0.74930(15)nm,α=90.00°,β=111.59(3)°,γ= 90.00°, V=0.7576(3)nm3, Z=4, Dc=1.886 g·cm-3, F (000)= 440. The structure of ANPyO was identified by 1HNMR, IR and MS.TANPyO was synthesized by vicarious nucleophilic substitution reaction and oxidative amination of ANPyO. For the VNS amination to synthesis TANPyO, the effect of the reaction solvents, the molar ratio of the catalyst and the stereo-electronic of reactants on the yields of target compounds were investigated. For the oxidative amination to synthesis TANPyO, the amination system and the resistance effects on the yields of target compounds were investigated. The yields of TANPyO were 83.6% and 85.4% respectively. TANPyO was synthesized by vicarious nucleophilic substitution reaction and oxidative amination of 2-amino-3,5-dinitropyridine-1-oxide. For the VNS amination to synthesis TANPyO, the stereo-electronic effects and activity of amination agent, the electronic structure of substrate on yields of target compounds were investigated. For the oxidative amination to synthesis TANPyO, the effect of different solvents and amination system on yields of TANPyO were investigated. The yield of TANPyO were 76% and 80%, respectively, and the structure of TANPyO was characterized by 1H NMR, IR and MS.In this paper, the synthesis of 3,5-diamino-2,4,6-triinitropyridine and its oxide were explored by using 3-fluoropyridine as the starting material followed by oxidation, nitration, methoxylation (amination) and nitration. Combined with the existing research results and reaction mechanism, we discussed the possible reasons that the target compound could not be obtained in various ways. This can provid experience and foundation for the synthesis of 3,5-diamino-2,4,6-triinitropyridine and its oxide.In this paper, a new concept-coordinated high-energy insensitive explosives was proposed by the study on the molecular structure of ANPyO. The ANPyO transition metal complexes M(ANPyO)n were synthesized in an innovative way. The synthesis, structure characterization and overall performance of copper complex of ANPyO and nickel complex of ANPyO were discussed. Element analysis showed that the atomic composition of M(ANPyO)n was M(C5H4N5O5)n. Infrared spectrum analysis showed that the amidogen of M(ANPyO)n coordinated with metal ions, forming the coordination compounds. The crystal diffraction results of Ni(ANPyO)2Py2 indirectly proved that Ni(C5H4N5O5) is a coordination compound, in which an amino of each ANPyO molecular lost an atom of hydrogen and coordinated with Ni2+, an oxygen of the N+-O- structure units coordinated with Ni2+. Crystal diffraction results of Co(ANPyO)3 directly demonstrated that:Co(ANPyO)3 was coordination compounds, in which one amino of ANPyO lost a hydrogen atom to form coordination bonds with Co3+, the oxygen atomic of N+-O- structural units to form coordination bonds with Co3+, three ANPyO removed the proton formed six-coordinated octahedral structure of the deformity with Co3+.In the final part, overall performances of ANPyO, TANPyO and ANPyO transition metal complexes M(ANPyO)n were studied preliminarily. The basic data such as thermal sensitivity, impact sensitivity, friction sensitivity, detonation performance, and compatibility with other materials were obtained. The elementary properties of the ANPyO and TANPyO such as detonation velocity (>7800ms-1), detonation pressure (>28.0Gpa) and impact sensitivity (>250cm) were investigated. The results show that ANPyO, TANPyO and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are about equal in the detonation and safety properties. The elementary properties of the M(ANPyO)n such as detonation velocity(>8200ms-1), detonation pressure (>32.0Gpa) and impact sensitivity (>300cm) were investigated. The results show that M(ANPyO)n can provide the energy close to RDX and the sensitivity close to TATB.In this paper, penetration power of ANPyO was explored preliminarily. The result indicates that under charging quality of 230g, propellant density of 1.70 g·cm-3, penetration depth of ANPyO power can attain about 92.6 percent of 8701, penetration volume of ANPyO power can reach 66.4 percent of 8701.