CHINESE JOURNAL OF ENERGETIC MATERIALS
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氘化对TATP结构和热行为的影响
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1.北京理工大学机电学院, 北京 100081;2.北京理工大学材料学院, 北京 100081

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Effect of Deuteration on the Structure and Thermal Behavior of TATP
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1.School of Mechatronical Engineering, Beijing Institute of Technology, Beijing 100081, China;2.School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China

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    摘要:

    为了研究氘化对三过氧化三丙酮(TATP)化学键振动性质以及热分解行为的影响,分别以丙酮和丙酮-d6为原料,过氧化氢为氧化剂,硫酸为催化剂,制备了TATP和氘代三过氧化三丙酮(TATP-d18)。采用核磁共振波谱、傅里叶变换红外光谱和差示扫描量热法对TATP和TATP-d18进行表征,使用Kissinger法、Ozawa法和Friedman法计算得到了TATP和TATP-d18的非等温反应动力学参数。结果表明,TATP-d18分子中各化学键的振动频率相比于TATP表现出不同程度的红移现象,C—H(D)键伸缩振动频率之比(νC—H/νC—D)约为1.36;由Kissinger法、Ozawa法和Friedman法所得TATP-d18的表观活化能(EK=80.54 kJ·mol-1EO=83.56 kJ·mol-1EF=72.27 kJ·mol-1)均高于这3种方法计算得到的TATP的表观活化能(EK=67.91 kJ·mol-1EO=71.01 kJ·mol-1EF=63.79 kJ·mol-1),这表明TATP-d18具有更高的热稳定性;计算所得的TATP与TATP-d18的热爆炸临界温度分别为402.37 K和423.46 K,这也证实了TATP-d18具有更高的热稳定性;计算得到了TATP和TATP-d18的非等温分解过程热力学参数,证明了TATP和TATP-d18不会自发发生热爆炸。

    Abstract:

    To investigate the effect of deuteration on the vibrational properties of chemical bonds of triacetone triperoxide (TATP) and its thermal decomposition behavior, TATP and deuterated triacetone triperoxide (TATP-d18) were prepared by using acetone and acetone-d6 as raw materials, respectively, with hydrogen peroxide acting as the oxidant source and sulfuric acid as the catalyst. TATP and TATP-d18 were characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The non-isothermal reaction kinetic parameters of TATP and TATP-d18 were calculated with Kissinger, Ozawa, and Friedman methods. The results show that the deuteration of TATP results in an evident red-shift phenomenon, and the ratio of the stretching frequencies of C—H(D) bonds (νC—HC—D) is about 1.36. The apparent activation energy of TATP-d18EK=80.54 kJ·mol-1EO=83.56 kJ·mol-1EF=72.27 kJ mol-1) is higher than that of TATP (EK=67.91 kJ·mol-1EO=71.01 kJ·mol-1EF=63.79 kJ·mol-1), indicating that TATP-d18 has higher thermal stability. The calculated thermal explosion critical temperatures for TATP (Tb=402.37 K) and TATP-d18Tb=423.46 K) also confirm that deuteration improves the thermal stability of TATP-d18. Finally, the calculated thermodynamic parameters for the non-isothermal decomposition processes of TATP and TATP-d18 indicate that TATP and TATP-d18 would not spontaneously undergo thermal explosions.

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引用本文

方祝青,李树奎,刘吉平,等.氘化对TATP结构和热行为的影响[J].含能材料, 2022, 30(7):687-693. DOI:10.11943/CJEM2022047.
FANG Zhu-qing, LI Shu-kui, LIU Ji-ping, et al. Effect of Deuteration on the Structure and Thermal Behavior of TATP[J]. Chinese Journal of Energetic Materials, 2022, 30(7):687-693. DOI:10.11943/CJEM2022047.

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  • 收稿日期: 2022-03-08
  • 最后修改日期: 2022-05-05
  • 录用日期: 2022-04-11
  • 在线发布日期: 2022-05-05
  • 出版日期: 2022-07-25