三聚氰酸为基的2,4,6-三氧-1,3,5三嗪烷-1-三氨基胍盐的合成、晶体结构和热性能

摘要

以三聚氰酸钠(CANa)和三氨基胍盐酸盐(TAG-HCl)为原料,通过一步复分解反应制备了一种富氮含能化合物——2,4,6-三氧-[1,3,5]三嗪烷-1-三氨基胍盐(1),收率91%.采用X-射线单晶衍射、UV-Vis、FTIR、1H NMR以及元素分析等对产物进行了结构表征.计算了产物的生成焓和爆轰参数.通过差示扫描量热法(DSC,10 K·min-1)和热重-傅里叶变换红外光谱联用分析了其热稳定性、非等温热分解动力学和热分解过程.通过落锤法测试了产物的撞击感度.结果表明,化合物1的晶体为单斜晶系,P21/n空间群,计算密度为1.676 g·cm-3,生成焓为327.9 kJ·mol-1,爆速为7900 m·s-1,爆压为26.5 GPa.化合物具1有良好的热稳定性,分解峰值温度为538.9 K,提出了N2气氛下可能的热分解机理.且化合物1对撞击非常钝感,撞击感度大于60 J,优于TATB(50 J).%A nitrogen-rich energetic compound—triaminoguanidinium 2,4,6-trioxo-1,3,5-triazinan-1-ide (1) was prepared with a yield of 91% via one-step metathesis reaction using triaminoguanidinium hydrochloride ( TAG-HCl) and sodium cyanurate ( CANa) as raw materials. The structure of the product was characterized by X-ray single-crystal diffraction, UV-Vis, FT-IR, 1 H NMR, mass spectrometry and elemental analysis. The enthalpy of formation and detonation parameters of the product were calculated. Its thermal stability, non-isothermal reaction kinetics and decomposition process were studied by differential scanning calorimetry( DSC) at a heating rate of 10 K·min-1 and thermogravimetric ( TG) analysis coupled with Fourier transform infrared spectroscopy ( FTIR) . The impact sensitivity of the product was determined by the drop hammer test. Results show that the crystal of compound 1 is monoclinic, space group P21/n with a calculated density of 1. 676 g·cm-3 . Its enthalpy of formation is 327. 9 kJ mol-1 , the detonation velocity 7900 m·s-1 , and the detonation pressure 26. 5 GPa. Probable thermal decomposition mechanism of 1 under N2 atmosphere as shown in the text is proposed. Compound 1 is very insensitive to impact, and the impact sensitivity is greater than 60 J, which is better than that of TATB (50 J).