Studies on High-Nitrogen Contented Energetic Salts from Amino-triazoles

Author:Wu Jin Zuo

Supervisor:zhang jian guo


Degree Year:2017





The high-nitrogen contented energetic salts from amino-triazoles are not only possess special properties(low vapor pressures,high densities and adjustable sentivities),but also show large ring tension,easily meet the oxygen balance and their combustion products are the eco-friendly dinitrogen gas.Therefore,much attention has been focused on amino-triazoles in the flied of energetic materials.Three series of 29 high-nitrogen contented energetic salts based on 1-amino-1,2,3-triazole,3,4-diamino-triazole or 3-hydraziono-4-amino-1,2,4-triazole were designed and synthesized.The structures were characterized through single crystal X-ray diffraction,EA,MS and IR spectroscopy.Furthermore,the thermal stabilities,sensitivities and detonation performance were investigated.The main contents are summarized as follows:The crystal structure of DATr was determinded for the first time,it belongs to monoclinicsystem,P2(1)/c group.Using the Gaussian process,the positions of three kinds of amino triazole are most likely to accept the proton were theoretically studied.A series of high-nitrogen contented energetic salts based on 1-ATZ were prepared.With DSC analysis,all salts showed their decomposition temperature ranging from 160 oC to 182oC.The heats of formation of these energetic salts were calculated based on the designed isodesmic reactions to be in the range of-75.8 to 1500.1 kJ·mol-1,most salts of heats of formation were far higher than that of RDX.Detonation detonation velocitiy was predicted from 6699 to 8231 m·s-1.Their impact sensitivities were determined to be 1.5->40 J.A series of nitrogen-rich energetic salts of DATr were designed and synthesized.The thermal behaviors were measured by DSC,most of the salts show good themal stability(decomposition temperature>200 oC).Positive heats of formation(except 2.13)were calcutated from 33.7 kJ·mol-11 to 1332.5 kJ·mol-1.The calculated detonation velocitiy by Kamlet-Jacobs equations are as ranging form 7014 m·s-11 to 8752 m·s-1.Additionally,the sensitivities results show that most of these salts were less sensitive than RDX.The direct acid-base reactions of HATr with free heterocyclic acids give rise to the mono-protonated HATr salts,while the double protonated HATr salts were prepared by the treatment of HATr·2HCl underwent the metathesis reactions with corresponding silvers.The heats of formation of these energetic salts were calculated based on the designed isodesmic reactions to be in the range of-491.4-1108.2 kJ·mol-1.The calculated detonation velocitiy D=7380-8455 m·s-1.Their impact and friction sensitivities were determined to be IS=4->40 J,FS=42–288 N.The thermal stabilities of the DATr-based energetic salts were better than those of the 1-ATZ-based energetic salts and the HATr-based energetic salts when paired a common anion.Regarding to sensitivity properties of 1-ATZ、DATr、HATr based energetic salts paired a common anion,the 1-ATZ-based energetic salts were the most sensitive,while HATr-based energetic salts were least sensitive.This indicates the HATr-based energetic salts possess the highest possibility of the formation of hydrogen bonds.