ANPyO Bi(Ⅲ)含能配合物的合成、表征、热分解行为及其对高氯酸铵热分解的催化作用（英文）

Synthesis,characterization and catalytic effect on thermal decomposition of AP:an eco-friendly energetic Bi(Ⅲ) complex of ANPyO

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。

In this research, an eco-friendly, energetic Bi （Ⅲ） complex of 2,6-diamino-3,5-dinitropyridine- 1-oxide （ANPyO） was synthesized and its structure was characterized by FTIR, elemental analyses and XPS measurements. Based on the results of structure analyses, we speculate that chemical constitution of the complex can be deduced as Bi（ C5H4N5O5 ）3, and the ratio of Bi （Ⅲ） and ANPyO is 1 ： 3. The central Bi（Ⅲ） ion contributes its six empty orbitals to accommodate the long pair electrons from the imine N atoms and N→O O atoms from three different deprotonated ANPyO molecules. Impact sensitivity, friction sensitivity and shock wave sensitivity of Bi（Ⅲ） complex of ANPyO are 220 cm, 36 kg and 5.8 ram, respectively. The thermal decomposition behavior of Bi （Ⅲ） complex of ANPyO was studied by TG-DTG and DSC measurements. The thermal decomposition of the complex consists of one endothermic （320.6 ℃ ） and one exothermic （346.5 ℃ ） peaks in the temperature range of 50-450 ℃ with 31.2% residue. Meanwhile, the catalytic performance of the complex on the thermal decomposition of ammonium perchlorate （ AP ） was analyzed by TG-DTG and DSC analyses, the apparent activation energy and pre-exponential factor of pure AP and AP mixture in the low temperature decomposition stage and high temperature decomposition stage were calculated by Kissinger＇s formula as well. The results show that Bi（Ⅲ） complex of ANPyO makes the exothermic peak temperatures and activation energy values of high temperature decomposition stage and low temperature decomposition stage for AP decrease by 63.6 ℃, 63.1 ℃, 23.1 kJ/mol and 61.5 kJ/mol, respectively, the apparent exothermic quantity for AP increase by 339.3 J/g, revealing that the complex has good cat- alytic effects on the thermal decomposition of AP.