Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction f...Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction from the readily available reactant.Their energetic salts with high nitrogen content were proved to be rare examples of divalent monocyclic/fused cyclic cationic salts according to the single crystal analyses.The structure of intermediate B was also identified and verified by its trivalent cation crystal 17.5H_2O indirectly.Energetic compounds 2-8 and 10-17 were fully characterized by NMR spectroscopy,infrared spectroscopy,differential scanning calorimetry,elemental analysis.These energetic salts exhibit good thermal stability with decomposition temperatures ranged from 182℃to 245℃.The sensitivity of compounds 2,6,10 and 14 is similar or superior to that of RDX while the others were much more insensitive to mechanical stimulate.Furthermore,detonation velocity of 10(8843 m/s)surpass that of RDX(D=8795 m/s).Considering the high gas production volume(≥808 L/kg)of 2,4,10and 12,constant-volume combustion experiments were conduct to evaluate their gas production capacities specifically.These compounds possess much higher maximum gas-production pressures(P_(max):7.88-10.08 MPa)than the commonly used reagent guanidine nitrate(GN:P_(max)=4.20 MPa),which indicate their strong gas production capacity.展开更多
In this study,a new energetic hybrid skeleton was constructed through the integration of nitropyrazole and 1,3,4-oxadiazole skeletons in a molecule.Furthermore,the energetic precursor(2),the azo-bridged compound(3),th...In this study,a new energetic hybrid skeleton was constructed through the integration of nitropyrazole and 1,3,4-oxadiazole skeletons in a molecule.Furthermore,the energetic precursor(2),the azo-bridged compound(3),the neutral nitramine(4)and the corresponding energetic salts(5-7)were synthesized.Their physicochemical and energetic properties we re experimentally and theo retically evaluated.Among the developed compounds,the azo-bridged compound(3)and dihydroxylammoinium(6)display high detonation performances(3,D_(v)=8904 m/s,P=34.47 GPa;6,D_(v)=9025 m/s,P=34.66 GPa),moderate sensitivities(3,IS=16 J,FS=120 N;6,IS=20 J,FS=312 N)and good densities(3,1.87 g/cm^(3);6,1.81 g/cm^(3)),which indicates that they have the potential to replace the traditional high-energy explosive RDX.The results show that the integration of different energetic skeletons can achieve a good balance between energy and sensitivity.展开更多
In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged ring...In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged rings by introducing multiple nitrogen heterocycles at different sites of fused rings is still difficult to progress,which seriously limits the emergence of advanced energetic compounds.In this study,a series of energetic materials choosing different nitrogen rich heterocycles at the vacancies of the fused ring,i.e.,neutral compound 5,6 and their ionic derivatives(compounds 7-12)were designed and synthesized.Compounds 5 and 6 were further confirmed by single crystal X-ray diffraction,while the crystal analysis and theoretical calculations were carried out to explore the relationship between crystal structure and physicochemical properties.All of the newly synthesized compounds(5-12)are insensitive to mechanical stimulation(IS>40 J;FS≥342 N)and they own the high detonation velocity(D:8322-9075 m/s).Notably,hydrazine salt 11 own the higher detonation velocity(9075 m/s)and powder density(1.83 g/cm^(3)),but exhibits lower sensitivity(IS>40 J)than the classical energetic compound RDX(8795 m/s,1.80 g/cm^(3),7.5 J).It is obvious that the combination of 5,6-fused triazolo-triazine and nitropyrazole-tetrazole may be a new energetic skeleton for synthesising the heterocyclic compounds with balanced energy-stability.展开更多
Cocrystallization is a promising technique for the design and preparation of new explosives,and the stability of cocrystal is highly concerned by the researchers.In order to make a better understanding of the behavior...Cocrystallization is a promising technique for the design and preparation of new explosives,and the stability of cocrystal is highly concerned by the researchers.In order to make a better understanding of the behavior of cocrystal under the extreme conditions,DFT(density functional theory) calculation is performed to investigate the effect of hydrostatic pressure on geometrical and electronic structures of the cocrystal BTF(benzotrifuroxan)/TNA(2,4,6-trinitroaniline).When the hydrostatic pressure is applied,the lattice constants,volume,density and total energy change gradually except at the pressures of 40 GPa and 79e83 GPa.It is noteworthy that new chemical bonds form when the pressure is up to83 GPa.The band gap of the cocrystal becomes smaller when the pressure is applied,and finally the cocrystal shows a characteristic of metal.The mechanical property of cocrystal is calculated by MD(molecular dynamics) simulation.The results show that the cocrystal has a better ductibility at low temperature,and has the best tenacity at 295 K.展开更多
基金supported by the National Natural Science Foundation of China(No.21875110,22075143)the Science Challenge Project(No.TZ2018004)the Qing Lan Project for the grant。
文摘Monocyclic nitrogen-rich 3-(aminomethyl)-4,5-diamine-1,2,4-triazole(1)and fused cyclic 3,7-diamine-6-(aminomethyl)-[1,2,4]triazolo[4,3-b][1,2,4]triazole(9)were synthesized through the convenient cyclization reaction from the readily available reactant.Their energetic salts with high nitrogen content were proved to be rare examples of divalent monocyclic/fused cyclic cationic salts according to the single crystal analyses.The structure of intermediate B was also identified and verified by its trivalent cation crystal 17.5H_2O indirectly.Energetic compounds 2-8 and 10-17 were fully characterized by NMR spectroscopy,infrared spectroscopy,differential scanning calorimetry,elemental analysis.These energetic salts exhibit good thermal stability with decomposition temperatures ranged from 182℃to 245℃.The sensitivity of compounds 2,6,10 and 14 is similar or superior to that of RDX while the others were much more insensitive to mechanical stimulate.Furthermore,detonation velocity of 10(8843 m/s)surpass that of RDX(D=8795 m/s).Considering the high gas production volume(≥808 L/kg)of 2,4,10and 12,constant-volume combustion experiments were conduct to evaluate their gas production capacities specifically.These compounds possess much higher maximum gas-production pressures(P_(max):7.88-10.08 MPa)than the commonly used reagent guanidine nitrate(GN:P_(max)=4.20 MPa),which indicate their strong gas production capacity.
基金support from the National Natural Science Foundation of China[No.22075143,21875110]the Science Challenge Project[TZ2018004]the Qing Lan Project for the grant。
文摘In this study,a new energetic hybrid skeleton was constructed through the integration of nitropyrazole and 1,3,4-oxadiazole skeletons in a molecule.Furthermore,the energetic precursor(2),the azo-bridged compound(3),the neutral nitramine(4)and the corresponding energetic salts(5-7)were synthesized.Their physicochemical and energetic properties we re experimentally and theo retically evaluated.Among the developed compounds,the azo-bridged compound(3)and dihydroxylammoinium(6)display high detonation performances(3,D_(v)=8904 m/s,P=34.47 GPa;6,D_(v)=9025 m/s,P=34.66 GPa),moderate sensitivities(3,IS=16 J,FS=120 N;6,IS=20 J,FS=312 N)and good densities(3,1.87 g/cm^(3);6,1.81 g/cm^(3)),which indicates that they have the potential to replace the traditional high-energy explosive RDX.The results show that the integration of different energetic skeletons can achieve a good balance between energy and sensitivity.
基金supported by the National Natural Science Foundation of China(Grant No.21875110,22075143)the Science Challenge Projectthe Qing Lan Project for the grant。
文摘In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged rings by introducing multiple nitrogen heterocycles at different sites of fused rings is still difficult to progress,which seriously limits the emergence of advanced energetic compounds.In this study,a series of energetic materials choosing different nitrogen rich heterocycles at the vacancies of the fused ring,i.e.,neutral compound 5,6 and their ionic derivatives(compounds 7-12)were designed and synthesized.Compounds 5 and 6 were further confirmed by single crystal X-ray diffraction,while the crystal analysis and theoretical calculations were carried out to explore the relationship between crystal structure and physicochemical properties.All of the newly synthesized compounds(5-12)are insensitive to mechanical stimulation(IS>40 J;FS≥342 N)and they own the high detonation velocity(D:8322-9075 m/s).Notably,hydrazine salt 11 own the higher detonation velocity(9075 m/s)and powder density(1.83 g/cm^(3)),but exhibits lower sensitivity(IS>40 J)than the classical energetic compound RDX(8795 m/s,1.80 g/cm^(3),7.5 J).It is obvious that the combination of 5,6-fused triazolo-triazine and nitropyrazole-tetrazole may be a new energetic skeleton for synthesising the heterocyclic compounds with balanced energy-stability.
基金the support of the National Natural Science Foundation of China (Grant No. 61106078)
文摘Cocrystallization is a promising technique for the design and preparation of new explosives,and the stability of cocrystal is highly concerned by the researchers.In order to make a better understanding of the behavior of cocrystal under the extreme conditions,DFT(density functional theory) calculation is performed to investigate the effect of hydrostatic pressure on geometrical and electronic structures of the cocrystal BTF(benzotrifuroxan)/TNA(2,4,6-trinitroaniline).When the hydrostatic pressure is applied,the lattice constants,volume,density and total energy change gradually except at the pressures of 40 GPa and 79e83 GPa.It is noteworthy that new chemical bonds form when the pressure is up to83 GPa.The band gap of the cocrystal becomes smaller when the pressure is applied,and finally the cocrystal shows a characteristic of metal.The mechanical property of cocrystal is calculated by MD(molecular dynamics) simulation.The results show that the cocrystal has a better ductibility at low temperature,and has the best tenacity at 295 K.
