Synthesis, Thermodynamic Properties And Combustion Thermal Properties Of Triadimekon Derivatives And Their Salts

The new energetic compounds usually contains a large number of high-energy chemical bonds, such as C-N, C=N, N-N and N=N bonds. The existence of high-energy chemical bonds results in the high chemical reactivity of the new energetic compounds. Besides, the special structures of new energetic compounds leads to the unique properties in physics and chemistry. Compared to traditional energetic materials, the new energetic compounds has better physical and chemical properties and thermodynamic properties and is more promising to promote the development of military weapons. Based on these advantages, the investigation on the preparation and properties of new energetic compounds has attracted much attention.We have synthesized six kinds of energetic materialsin the paper, namely, ZTO, K(ZTO)·H2O, Ni(ZTO)·H2O, Ni(ZTO)·(phen)3·H2O, Cr(ZTO)3·H2O and Nd(ZTO)3·H2O. And the main results are as follows.By means of DSC and TG/DTG methods, the thermal behaviors of four compounds selected randomly were studied under non-isothermal conditions. We take the Ozawa method, Kissinger method, Integral method and Differential method to calculate the kinetic parameters and thermal decomposition mechanism of Ni(ZTO)·H2O、Ni(ZTO)·(phen)3·H2O、 Cr(ZTO)3·H2O and Nd(ZTO)3·H2O compounds in the thermal decomposition process, including the enthalpy of activation (△H≠), entropy of activation (△S≠), Gibbs free energy of activation (△G≠) and critical temperature of thermal explosion (Tb).The heat values of combustion of ZTO, K(ZTO)·H2O, Ni(ZTO)·H2O, Ni(ZTO)·(phen)3·H2O, Cr(ZTO)3·H2O and Nd(ZTO)3·H2O were characterized. The corresponding Standard enthalpies of combustion of the six energetic compounds (△cHmθ) are respectively (2251.35±11.18) kJ·mol-1, (1804.66±4.29) kJ·mol-1, (1500.23±5.31) kJ·mol-1, (11022.27±49.20) kJ-mol-1, (4529.29±41.43) kJ-mol-1, (3966.54±9.48) kJ·mol-1, and the corresponding standard enthalpies of formation(△fHmθ) are separately (-107.15±11.19) kJ·mol-1, (666.51 ±4.30) kJ·mol-1, (418.04±5.34) kJ·mol-1, (8492.32±49.48) kJ·mol-1, (1613.92±41.43) kJ·mol-1, (2399.93±9.61) kJ·mol-1.The continuous specific heat capacity of ZTO、K(ZTO)·H2O、Ni(ZTO)·H2O、 Ni(ZTO)·(phen)3·H2O、Cr(ZTO)3·H2O and Nd(ZTO)3·H2O were determined. Based on the standard of 298.15 K, the thermodynamic values (enthalpy, entropy and Gibbs free energy) of the six compounds were analyzed through thermodynamic equations when the temperature changed from 283K to 353 K. The adiabatic time-to-explosion of ZTO、K(ZTO)·H2O、 Ni(ZTO)·H2O、Ni(ZTO)·(phen)3·H2O、Cr(ZTO)3·H2O and Nd(ZTO)3·H2O were calculated by using thermal decomposition parameters and Cp functions, which cold be directly used to estimate the thermal stability and the safety of energetic material.