The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,...The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,3-triazolium nitrate(1b),3,4,5triamino-1,2,4-triazolium nitrate(2a),3,4,5-triamino-1,2,4-triazolium dinitramide(2b)were precisely measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution(△difH m ),standard molar enthalpies of dissolution(△difH m ),apparent activation energy(E),pre-exponential constant(A),kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 to 353 K,standard molar heat capacity(C p,m)and enthalpy,entropy and Gibbs free energy at 283–353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion(Tb),self-accelerating decomposition temperature(TSADT)and adiabatic time-to-explosion(t)of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.展开更多
A series of 3-nitro-5-nitroimino-1,2,4-oxadiazole-based energetic salts were synthesized from 3-nitro-5-nitroimino-1,2,4-oxadiazole anion and nitrogen-rich cations. They were fully characterized by IR,elemental analys...A series of 3-nitro-5-nitroimino-1,2,4-oxadiazole-based energetic salts were synthesized from 3-nitro-5-nitroimino-1,2,4-oxadiazole anion and nitrogen-rich cations. They were fully characterized by IR,elemental analysis and NMR spectroscopy. The structure of triaminoguanidinium salt（1-e） was confirmed by single crystal X-ray diffraction. All salts showed good thermal stability with decomposed temperature ranging from 155 8C to 258 8C, and positive heats of formation from 226.0 k J/mol to554.1 k J/mol. Thus, the theoretic detonation pressure was predicted from 28.70 GPa to 37.60 GPa and velocities from 8526 m/s to 9354 m/s. Among them, guanidinium salt（1-c） exhibited both high decomposition temperature（258 8C） and detonation velocity（9319 m/s）.展开更多
以1H,4H-6-硝基吡唑[4,3-c]并吡唑-3-羧酸为起始原料,经过一步脱羧硝化反应得到1H,4H-3,6-二硝基吡唑[4,3-c]并吡唑(DNPP),收率76.7%,然后与硝酸铅、3,6-二肼基-1,2,4,5-四嗪反应合成了DNPP碱式铅盐(PbDNPP)与DNPP的3,6-二肼基-1,2,4,5...以1H,4H-6-硝基吡唑[4,3-c]并吡唑-3-羧酸为起始原料,经过一步脱羧硝化反应得到1H,4H-3,6-二硝基吡唑[4,3-c]并吡唑(DNPP),收率76.7%,然后与硝酸铅、3,6-二肼基-1,2,4,5-四嗪反应合成了DNPP碱式铅盐(PbDNPP)与DNPP的3,6-二肼基-1,2,4,5-四嗪含能离子盐(DHT-DNPP)。采用红外光谱、1 H NMR、13 C NMR、质谱及元素分析等对其结构进行了表征,利用DNPP质谱裂解碎片信息,探讨了热解反应机理,揭示了其裂解微观反应过程。采用DSC和TG-DTG法研究了DNPP及其两种盐的热行为。结果表明,DNPP、Pb-DNPP和DHT-DNPP的放热分解峰分别为256.4、319.1和174.3℃,显示Pb-DNPP比DNPP和DHT-DNPP有更好的热稳定性。展开更多
以1,3,5-三硝基-2-氯苯和水合肼为起始原料,经过取代、环化反应得到4,6-二硝基苯并连三唑-1-氧化物(DNBTO),收率55.3%,并采用酸碱中和、离子交换等反应设计并合成了DNBTO的羟胺盐(HA-DNBTO)、三氨基胍盐(TAG-DNBTO)、脒基脲盐(M-DNBTO)...以1,3,5-三硝基-2-氯苯和水合肼为起始原料,经过取代、环化反应得到4,6-二硝基苯并连三唑-1-氧化物(DNBTO),收率55.3%,并采用酸碱中和、离子交换等反应设计并合成了DNBTO的羟胺盐(HA-DNBTO)、三氨基胍盐(TAG-DNBTO)、脒基脲盐(M-DNBTO)、3,6-二肼基-1,2,4,5-四嗪盐(DHT-DNBTO)以及乙二酰肼盐(OH-DNBTO)5种含能离子盐。用红外光谱、1 H NMR、13 C NMR及元素分析等进行了结构表征;采用DSC和TG-DTG法研究了DNBTO及其5种含能离子盐的热行为。用Gaussian 09程序和VLW爆轰方程,计算了DNBTO及5种含能离子盐的物化及爆轰性能。结果表明,升温速率10℃/min时,DNBTO、HA-DNBTO、TAG-DNBTO、M-DNBTO、DHT-DNBTO和OH-DNBTO的放热分解峰温度分别为201.3、213.0、209.9、240.5、133.7、197.7℃,M-DNBTO表现出更好的热稳定性;DNBTO及其5种含能离子盐的密度在1.59~1.69g/cm3之间,爆速在6 783.6~7 681.3m/s之间;DHT-DNBTO的生成焓最高,为1 081.4kJ/mol;HA-DNBTO的爆轰性能最佳,爆速为7 681.3m/s,爆压为25.5GPa。展开更多
基金supported by the National Natural Science Foundation of China (20573098)the Science and Technology Foundation of National Key Lab of Science and Technology on Combustion and Explosion in China (9140C3503030805)
文摘The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,3-triazolium nitrate(1b),3,4,5triamino-1,2,4-triazolium nitrate(2a),3,4,5-triamino-1,2,4-triazolium dinitramide(2b)were precisely measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution(△difH m ),standard molar enthalpies of dissolution(△difH m ),apparent activation energy(E),pre-exponential constant(A),kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 to 353 K,standard molar heat capacity(C p,m)and enthalpy,entropy and Gibbs free energy at 283–353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion(Tb),self-accelerating decomposition temperature(TSADT)and adiabatic time-to-explosion(t)of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.
基金financial support from the National Natural Science Foundation of China(Nos.21372027 and 21172203)
文摘A series of 3-nitro-5-nitroimino-1,2,4-oxadiazole-based energetic salts were synthesized from 3-nitro-5-nitroimino-1,2,4-oxadiazole anion and nitrogen-rich cations. They were fully characterized by IR,elemental analysis and NMR spectroscopy. The structure of triaminoguanidinium salt（1-e） was confirmed by single crystal X-ray diffraction. All salts showed good thermal stability with decomposed temperature ranging from 155 8C to 258 8C, and positive heats of formation from 226.0 k J/mol to554.1 k J/mol. Thus, the theoretic detonation pressure was predicted from 28.70 GPa to 37.60 GPa and velocities from 8526 m/s to 9354 m/s. Among them, guanidinium salt（1-c） exhibited both high decomposition temperature（258 8C） and detonation velocity（9319 m/s）.
文摘以1H,4H-6-硝基吡唑[4,3-c]并吡唑-3-羧酸为起始原料,经过一步脱羧硝化反应得到1H,4H-3,6-二硝基吡唑[4,3-c]并吡唑(DNPP),收率76.7%,然后与硝酸铅、3,6-二肼基-1,2,4,5-四嗪反应合成了DNPP碱式铅盐(PbDNPP)与DNPP的3,6-二肼基-1,2,4,5-四嗪含能离子盐(DHT-DNPP)。采用红外光谱、1 H NMR、13 C NMR、质谱及元素分析等对其结构进行了表征,利用DNPP质谱裂解碎片信息,探讨了热解反应机理,揭示了其裂解微观反应过程。采用DSC和TG-DTG法研究了DNPP及其两种盐的热行为。结果表明,DNPP、Pb-DNPP和DHT-DNPP的放热分解峰分别为256.4、319.1和174.3℃,显示Pb-DNPP比DNPP和DHT-DNPP有更好的热稳定性。
文摘以1,3,5-三硝基-2-氯苯和水合肼为起始原料,经过取代、环化反应得到4,6-二硝基苯并连三唑-1-氧化物(DNBTO),收率55.3%,并采用酸碱中和、离子交换等反应设计并合成了DNBTO的羟胺盐(HA-DNBTO)、三氨基胍盐(TAG-DNBTO)、脒基脲盐(M-DNBTO)、3,6-二肼基-1,2,4,5-四嗪盐(DHT-DNBTO)以及乙二酰肼盐(OH-DNBTO)5种含能离子盐。用红外光谱、1 H NMR、13 C NMR及元素分析等进行了结构表征;采用DSC和TG-DTG法研究了DNBTO及其5种含能离子盐的热行为。用Gaussian 09程序和VLW爆轰方程,计算了DNBTO及5种含能离子盐的物化及爆轰性能。结果表明,升温速率10℃/min时,DNBTO、HA-DNBTO、TAG-DNBTO、M-DNBTO、DHT-DNBTO和OH-DNBTO的放热分解峰温度分别为201.3、213.0、209.9、240.5、133.7、197.7℃,M-DNBTO表现出更好的热稳定性;DNBTO及其5种含能离子盐的密度在1.59~1.69g/cm3之间,爆速在6 783.6~7 681.3m/s之间;DHT-DNBTO的生成焓最高,为1 081.4kJ/mol;HA-DNBTO的爆轰性能最佳,爆速为7 681.3m/s,爆压为25.5GPa。
