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合成了2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)Bi(Ⅲ)含能配合物,采用FTIR、元素分析和XPS光电子能谱表征了含能配合物的结构。根据结构表征结果推测,ANPyOBi(Ⅲ)含能配合物的分子式为Bi(C5H4N5O5)3,金属离子与配体的配比为1∶3。其中,可能的配位方式为:每个配体ANPyO 2-位的氨基脱去一个氢原子,分别以NH和N→O结构单元中N原子和O原子与Bi(Ⅲ)形成配位键。ANPyOBi(Ⅲ)含能配合物的撞击感度、摩擦感度和冲击波感分别为220cm、36 kg和5.8 mm。采用TG-DTG和DSC测试考察了ANPyOBi(Ⅲ)含能配合物的热分解行为,配合物在50~450℃范围内热分解过程由一个吸热熔融峰和分解放热峰组成,相应的峰温分别为320.6℃和346.5℃,配合物热分解剩余残渣量为31.2%。同时,考察了配合物对高氯酸铵热分解的催化作用,并采用Kissinger法对纯AP和AP混合物热分解过程低温分解阶段和高温分解阶段的表观活化能和指前因子进行了计算。结果表明,ANPyOBi(Ⅲ)含能配合物可使高氯酸铵高温分解阶段和低温分解阶段的峰温提前63.6℃和63.1℃,表观活化能降低23.1 kJ/mol和61.5 kJ/mol,表观分解热增加339.3 J/g。可发现,ANPyOBi(Ⅲ)含能配合物对AP的热分解具有显著的催化作用。
The energetic complexes of 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO) Bi (Ⅲ) were synthesized and characterized by FTIR, elemental analysis and XPS photoelectron spectroscopy Structure. According to the results of structure characterization, the formula of ANPyOBi (Ⅲ) containing complex is Bi (C5H4N5O5) 3, and the ratio of metal ions to ligand is 1: 3. Among them, the possible coordination mode is as follows: the amino group at the 2-position of ANPyO of each ligand takes off a hydrogen atom and forms a coordinate bond with Bi (III) through the N atom and the O atom in NH and N → O structural units respectively. The impact sensitivities, friction sensitivities and shock wave sensitivities of energetic complexes of ANPyOBi (Ⅲ) were 220 cm, 36 kg and 5.8 mm, respectively. The thermal decomposition behavior of ANPyOBi (Ⅲ) -containing complexes was investigated by TG-DTG and DSC. The thermal decomposition of ANPyOBi (Ⅲ) complexes was composed of an endothermic melting peak and an exothermic decomposition peak at 50-450 ℃. The corresponding peak temperatures 320.6 ℃ and 346.5 ℃, respectively. The residual amount of thermal decomposition residue was 31.2%. At the same time, the catalytic effect of the complex on the thermal decomposition of ammonium perchlorate was investigated. The apparent activation energy and the pre-exponential factor in the pyrolysis and pyrolysis phases of pure AP and AP mixtures were calculated by Kissinger method. The results showed that the peak energies of ammonium perchlorate at 63.6 ℃ and 63.1 ℃ in the pyrolysis and pyrolysis stages of ammonium perchlorate and the apparent activation energy decreased by 23.1 kJ / mol and 61.5 kJ / mol, respectively, with the energetic complex of ANPyOBi (Ⅲ) The observed heat of decomposition increased by 339.3 J / g. It can be found that ANPyOBi (Ⅲ) containing complexes have a significant catalytic effect on the thermal decomposition of AP.