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ANPyOPb(Ⅱ)含能配合物安全性能和非等温热分解反应动力学
作者:
作者单位:

(1. 浙江工业大学安全科学与工程系, 浙江 杭州 310014; 2. 南京理工大学化工学院, 江苏 南京 210094; 3. 江苏大学环境与安全工程学院, 江苏 镇江 212013; 4. 江苏大学能动学院, 江苏 镇江 212013; 5. 西安近代化学研究所, 陕西 西安 710065; 6. 甘肃银光化学工业集团有限公司, 甘肃 白银 730900)

作者简介:

成健(1982-),男,讲师,主要从事高能钝感炸药及其金属配合物的研究与应用。e-mail: chengjian09@foxmail.com 通信联系人: 李振明(1964-),男,副教授,主要从事材料安全性评估与管理研究。e-mail: lizmzf@163.com

通讯作者:

李振明(1964-),男,副教授,主要从事材料安全性评估与管理研究。e-mail: lizmzf@163.com

基金项目:

火炸药十二五预研项目(62201070102)和江苏省高校自然科学研究面上项目(16KJB150010).


Safety Properties and Non-isothermal Kinetics of Energetic Pb(Ⅱ) Complex of ANPyO
Author:
Affiliation:

(1. Department of Safety Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China; 2. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China; 3. School of Environment and Safety Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China; 4. School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, China; 5. Xi′an Modern Chemistry Research Institute, Xi′an, 710065, China; 6. Research institute of Gansu Yinguang Chemical Industry Group, Baiyin, 730900, China)

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    摘要:

    为提高2, 6-二氨基-3, 5-二硝基吡啶-1-氧化物(ANPyO)Pb(Ⅱ)(Pb-ANPyO)含能配合物能量水平, 获得安全性能和热分解特性参数。以ANPyO和醋酸铅为原料, N, N-二甲基甲酰胺(DMF)为溶剂, 合成了ANPyOPb(Ⅱ)含能配合物。采用红外光谱(FTIR), 元素分析和X射线光电子能谱分析(XPS)表征其结构, 测试了其撞击感度和摩擦感度, 采用差热分析-热重法(DSC-TG)研究其在不同升温速率下的热分解行为, 利用Kissinger公式, Ozawa公式, 热力学关系式和Zhang-Hu-Xie-Li公式分别计算了配合物热分解反应的表观活化能和热力学参数, 以及配合物的热安全性参数。结果表明, 配合物分子式为Pb(C5H3N5O5), 特性落高和摩擦感度分别为238 cm和0。配合物在25~500 ℃范围内的热分解过程由一个吸热熔融峰和一个分解放热峰组成, 相应峰温分别为265.0 ℃和332.6 ℃。用Kissinger法和Ozawa法所得配合物放热分解反应的活化能分别为202.42 kJ·mol-1和197.40 kJ·mol-1, 放热分解反应的活化熵, 活化焓和活化自由能分别为149.5 J·mol-1·K-1, 197.7 kJ·mol-1, 112.1 kJ·mol-1, 热爆炸临界温度和自加速分解温度分别为586.6 K和572.4 K。

    Abstract:

    To improve the energy levels of of energetic Pb(Ⅱ) complex of 2, 6-diamino-3, 5-dinitropyridine-1-oxide [ANPyO Pb(Ⅱ)] and obtain the safety and thermal decomposition characteristic parameters of ANPyO Pb(Ⅱ), energetic complex ANPyO Pb(Ⅱ) was synthesized using ANPyO and lead acetate as raw materials, N, N-dimethylformamide(DMF) as solvent. Its structure was characterized by infrared(IR) spectroscopy, elemental analysis and X-ray photoelectron spectroscopy(XPS). Its impact sensitivity and friction sensitivity were tested. The thermal decomposition behavior of the complex was studied by differential scanning calorimetry-thermogravimetry(DSC-TG) at the different heating rate, the apparent activation energy and thermodynamic parameters for thermal decomposition reaction of the complex, and thermal safety parameters of the complex were calculated by Kissinger′s formula, Ozawa′s formula, thermodynamic reaction formula and Zhang-Hu-Xie-Li formula, respectively. The results show that the molecular formula of the complex is Pb(C5H3N5O5). Impact and friction sensitivity of the complex are 238 cm and 0, respectively. The thermal decomposition process of ANPyO Pb(Ⅱ) in the temperature range of 25-500 ℃ consists of one endothermic melting peak and one exothermic decomposition peak, corresponding peak temperatures are 265.0 ℃ and 332.6 ℃. The apparent activation energy for the thermal decomposition reaction of Pb-ANPyO obtained by Kissinger method and Ozawa method is 202.42 kJ·mol-1 and 197.40 kJ·mol-1, respectively. The entropy of activation, enthalpy of activation, free energy of activation of the exothermic decomposition reaction are 149.5, 197.7 kJ·mol-1 and 112.1 kJ·mol-1, the critical temperature of thermal explosion and self-accelerating decomposition temperature of the complex are 586.6 K and 572.4 K, respectively.

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成健,刘祖亮,李振明,等. ANPyOPb(Ⅱ)含能配合物安全性能和非等温热分解反应动力学[J].含能材料, 2016, 24(12):1161-1167. DOI:10.11943/j. issn.1006-9941.2016.12.005.
CHENG Jian, LIU Zu-liang, LI Zhen-ming, et al. Safety Properties and Non-isothermal Kinetics of Energetic Pb(Ⅱ) Complex of ANPyO[J]. Chinese Journal of Energetic Materials, 2016, 24(12):1161-1167. DOI:10.11943/j. issn.1006-9941.2016.12.005.

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  • 收稿日期: 2016-04-12
  • 最后修改日期: 2016-08-10
  • 录用日期: 2016-09-12
  • 在线发布日期: 2016-12-26
  • 出版日期: 2016-12-23