Synthesis Of Several Kinds Of Heat-resistant Energetic Compounds Derived From Pyrazine

2,6-diamino-3,5-dinitropyrazine(ANPZ)is not only a kind of single heat-resistant explosives derives from pyrazine,but also the synthetic intermediate of 2,6-diamino-3,5-dinotropyrazine-l-oxide(LLM-105)which is a new insensitive thermal energetic material.According to the primary synthesis process of ANPZ,the acetonitrile used in the amination has toxicity and corrosivity,therefore it is very significant to improve the synthetic process of ammonofication.2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)is one of the most thermal explosives in the world.However,its detonation properties are not perfect.So it is the hot topic that the synthesis of a new energetic material which has better thermal stablity and denotation properities as PYX by replacing the pyridine to pyrazine in the molecule structure.ANPZ was synthesized by 2,6-dichloropyrazine via substitution,nitration,amination.The nitric acid and sulfuric acid was used as nitrion system in the nitrification.In the ammonofication mixed solvent of ethanol and acetonitrile was used as the reaction solvent.The optimum condictions were obtained through single factor experiments and orthogonal experiments.The optimum condiction of the nitrion are that the volume ratio between H2SO4 and HNO3 was 3:1,reaction temperature was 20 ?,reaction time was 3 h with the yield of 63.8%;the optimum condictions of ammonofication were that the optimal solvent was the mixed solvent of ethanol and acetonitrile,the volume ratio of ethanol,acetonitrile and ammonia was 1.5:1.5:1,reaction temperature was 70 ?,reaction time was 3h,with the yield of 96%.2,6-bis(picrylamino)pyrazine was synthesized by 2,6-diaminopyrazine and 2,4,6-trinitrochlorobenzene via condensation.2,4,6-trinitrochlorobenzene was prepared by 2,4-dinitrochlorobenzene via nitrion and 2,6-diaminopyrazine was prepared by iminodicaetonitrile via nitrosation cyclization.The conditions of nitrion and condensation were optimized.The optimum condiction of the nitrion were that the ratio of H2SO4 and KNO3 was 0.098 mol:22 mL,reaction temperature was 140 ?,reaction time was 5 h with the yield of 57.4%;the optimum condiction of ammonofication were that the optimal solvent was isopropanol,reaction temperature was 85 ?,the catalyst was pyridine,reaction time was 5 h with the total yield of 72%.Its thermal stability was analyzed by DSC and the decomposition temperature was 314 ?.2,6-bis(picrylamino)-3,5-dinitropyrazine(BPNP)was synthesized by 2,6-bis(picrylamino)prazine via nitrion.The nitrion conditions were optimized by single factor experiments.The effect of the nitrition was the best,while the volume ratio between H2SO4 and HNO3,reaction temperature and reaction time were V(H2SO4):V(HNO3)=4:1,50 ? and 3 h,respectively.The decomposition temperature of BPNP is 374.3 ?,which was investigated by TG and DSC.The density and detonation velocity of BPNP are 1.81 g/cm3 and 8.13 km/s,which is higher than PYX and HNS.The detonation pressure and hso are 26.25 GPa and 83 cm.2,6-bis(picrylamino)-3,5-dinitropyrazine-l-oxide(BPNPO)is designed based on the structure of BPNP and its correlation properties are calculated.The density,detonation heat,detonation velocity,detonation pressure and hso are 1.86 g/cm3,1453.61 cal/g,8.69 km/s,30.38 GPa and 122 cm.The value of h50 is lower than PYX and HNS,and other properties are higher than PYX and HNS.