(1.中北大学 环境与安全工程学院,山西 太原 030051; 2.山西省超细粉体工程技术研究中心,山西 太原 030051)

有机化学; 共晶; 3-氨基-4-(四唑-5-基)呋咱; HAFT; EDN; 晶体结构; 热分析

Synthesis, Crystal Structure and Thermal Decomposition Performance of HAFT·EDN Cocrystal
WU Bi-dong1,2, WANG Miao1,2, LIU Shu-jie1,2, WANG Jing-yu1,2

(1.School of Environment and Safety Engineering, North University of China, Taiyuan 030051,China; 2.Shanxi Engineering Technology Research Center for Ultrafine Powder, Taiyuan 030051,China)

organic chemistry; cocrystal; 3-amino-4-(tetrazol-5-yl)-furazan; HAFT; EDN; crystal structure; thermal analysis

DOI: 10.14077/j.issn.1007-7812.202004015


以3-氨基-4-(四唑-5-基)呋咱(HAFT)和硝酸乙二胺(EDN)为原料,制备得到二元共晶HAFT·EDN,采用X射线衍射仪(XRD)、红外光谱、元素分析和X-射线单晶衍射仪表征了目标物结构; 采用差示扫描量热(DSC)对HAFT·EDN共晶进行了热性能测试,并测试了其撞击感度和摩擦感度; 通过Kissinger法、Ozawa法和Starink法计算分析了非等温动力学、热爆炸临界温度等性能参数。 结果 表明,该晶体属于单斜晶系,空间群为P21/c,晶体学参数为:a=7.515(4)Å,b=9.823(5)Å,c=14.828(8)Å,β=86.152(9)Å,V=1092.1(10)Å3,Dc=1.680g/cm3,其活化能为127.58kJ/mol,热爆炸临界温度为283.7℃,分解反应过程活化熵(ΔS≠)为-44.08kJ/mol,活化焓(ΔH≠)为119.68kJ/mol,吉布斯自由能(ΔG≠)为143.33kJ/mol,具有较好的稳定性,对撞击和摩擦刺激均钝感。

By using 3-amino-4-(tetrazol-5-yl)furazan(HAFT)and ethylenediaminenitrate(EDN)as raw materials, a binary cocrystal HAFT·EDN was prepared. X-ray diffractometry(XRD), infrared spectroscopy, elemental analysis and single crystal X-ray diffractometry were used to characterize the structure. The thermal properties of HAFT·EDN cocrystal were tested by differential scanning calorimetry(DSC). The impact and friction sensitivities were also tested.The Kissinger method, Ozawa method and Starink method were used to calculate and analyze the non-isothermal kinetic parameters and thermal explosion critical temperature.The results show that HAFT·EDN cocrystal belongs to monoclinic system with P21/c space group, crystallographic parameters: a=7.515(4)Å, b=9.823(5)Å, c=14.828(8)Å, β=86.152(9)Å, V=1092.1(10)Å3 and Dc=1.680g/cm3, where HAFT is presented as electrically neutral state. The activation energy is 127.58kJ/mol, and the thermal explosion critical temperature is 283.7℃. The activation entropy(ΔS≠)of the decomposition reaction process is -44.08kJ/mol, the activation enthalpy(ΔH≠)is119.68kJ/mol, and the Gibbs free energy(ΔG≠)is 143.33kJ/mol, showing good thermal stability and low sensitivity towards impact and friction stimuli.