Studies On Synthesis And Properties Of Trinitroethyl Energetic Materials Derived From High Nitrogen Compounds

The trinitroethyl group is a kind of classis energetic group which is rich in oxygen and nitrogen elements.Introducing it as a modification group into the nitrogen-oxygen heterocyclic compounds can greatly improve its density and detonation performance.Therefore,the characteristics of such energetic compounds are very important for the research of new energetic materials such as propellants and explosives.In this paper,some new trinitroethyl energetic materials derived from high nitrogen compounds are synthesized,the main research contents are as follows:1.Studies on the synthesis and properties of energetic compounds based on 3,3’-diamino-4,4’-bifuranA simple method for the synthesis of 3,3’-diamino-4,4’-bifuran（37）is presented,which is synthesized by dichloroglyoxime through cyanation,addition and cyclization reaction.The intermediate addition product 4,4-diamino-1,2,3,4-tetraoximyl butane can be oxidized to obtain furoxan product（38）,rearrange furazan（39）was obtained by rearrangement reaction of compound 37.According to the Mannich reaction principle,compounds 37,38,and 39 which were used as substrates reacted with 2,2,2-trinitroethanol to obtain energetic compounds 40～42,Compound 40 was treated with100%nitric acid to obtain nitration product 43.The structure and properties of the above compounds were characterized by IR,NMR,DSC,X-ray single crystal diffraction and so on.The single crystal density of compound 40 is 1.83 g.cm^-3,and the thermal decomposition temperature is 194.5℃.EXPL05 estimates the detonation performance of compound 40(D=9045 m s^-1,P=37.1 GPa)is better than RDX(D=8795 m s^-1;P=34.9 GPa),and the impact sensitivity（IS=40J）is much higher than RDX（IS=7J）,which indicated that this material is a potential substitute for the traditional energetic materials.2.Studies on the synthesis of energetic compounds based on N,N-bis（1H-tetrazol-5-yl）amineN,N-bis（1H-tetrazol-5-yl）amine was synthesis via a novel route by intramolecular cyclization conditioning the reaction system,in which sodium dicyandiamide and sodium azide was used as the main raw materials,ammonium saltation under the condition of ammonia gives compound 44.Amination reaction of compound 44 with amination reagents（HOSA,MSH and PHA）can obtain N,N-bis（amino-tetrazol-5-yl）amine（45）.Compound 45 reacted with 2,2,2-trinitroethanol to obtain N,N-bis（trinitroethylamino-tetrazol-5-yl）amine（46）.The reaction mechanism from the starting material to the synthesis of the target product was analyzed.The reaction conditions were optimized and the structure of the synthesized compounds were characterized by IR,¹H NMR,and ¹³C NMR.3.Studies on the synthesis of energetic compounds based on 2,4-diamino-3,5-dinitropyrazole4-chloropyrazole is nitrated with nitric-sulfur mixed acid to obtain 4-chloro-3,5-dinitropyrazole,and ammoniated with ammonia to obtain 4-amino-3,5-dinitropyrazole（47:LLM-116）,Ammonium salts can be obtained after high-temperature amination.2,4-diamino-3,5-dinitropyrazole（48:DADNP）can be obtained from the ammonium salt by using the amination reagents.The reactions of 2,2,2-trinitroethanol with compounds 47 and 48 obtained the corresponding trinitroethyl energetic compounds.The reaction conditions were optimized and the structures of the synthesized compounds were characterized by ¹H NMR and ¹³C NMR.