季戊四醇四硝酸酯及其结构相似物的爆轰性能和热解机理的理论研究-Theoretical Study on Detonation Performances and Pyrolysis Mechanism of Pentaerythritol Tetranitrate and its Analogue Compounds

季戊四醇四硝酸酯及其结构相似物的爆轰性能和热解机理的理论研究

2013,21(5):570-577

杨俊清¹, 王桂香¹, 高贫², 贡雪东¹

(1.南京理工大学化学系, 江苏南京 210094; 2. 国家民用爆破器材质量监督检测中心, 江苏南京 210094)

摘要：采用密度泛函理论B3LYP/6-31G^*方法研究了季戊四醇的五个结构相似的硝酸酯基(—ONO₂)和叠氮基(—N₃)衍生物, 包括四叠氮基季戊烷(TAPE)、三叠氮基季戊醇硝酸酯(PTAN)、二叠氮基季戊二醇二硝酸酯(PDADN)、叠氮基季戊三醇三硝酸酯(PATN)和季戊四醇四硝酸酯(PETN)。优化了分子几何构型。进行了振动分析。估算了密度、生成热、热力学函数、爆轰性能和比冲。计算了可能的热解引发键的键离解能(E_BD)和氢转移反应的活化能(E_a)。结果表明, 与PTAN、PDADN、PATN和PETN比较, TAPE的生成热最大, 比冲与PETN相当。PATN的爆轰性能和稳定性与PETN接近, 优于其它衍生物, 包括PDADN。含—N₃的TAPE的热解由氢转移导致—N₃热裂解放出N₂引发, 其E_a为130.57 kJ·mol^-1。含—ONO₂的其它衍生物的热裂解均由O—NO₂键断裂开始, E_BD为130.91~137.45 kJ·mol^-1。这些能量值满足高能化合物的稳定性指标要求。

关键词：物理化学; 季戊四醇; 叠氮基; 硝酸酯基; 爆轰性能; 热分解机理

Theoretical Study on Detonation Performances and Pyrolysis Mechanism of Pentaerythritol Tetranitrate and its Analogue Compounds

YANG Jun-qing¹, WANG Gui-xiang¹, GAO Pin², GONG Xue-dong¹

(1. Nanjing University of Science and Technology, Department of Chemistry, Nanjing 210094, China; 2. National Civil Blasting Equipment Quality Supervision and Testing Center, Nanjing 210094, China)

Abstract： Five structurally similar —ONO₂ and —N₃ derivatives of pentaerythritol, including tetraazido pentaerythritol (TAPE), pentaerythritol triazido nitrate (PTAN), pentaerythritol diazido dinitrate (PDADN), pentaerythritol azido trinitrate (PATN), and pentaerythritol tetranitrate (PETN) were studied by the B3LYP/6-31G ^* method. The molecular geometric configurations were optimized and vibration analyses were performed. Their densities, heats of formation, thermodynamic functions, detonation performances and specific impulses were estimated. The bond dissociation energy (E_BD) of the possible trigger bond and the activation energy (E_a) of the hydrogen transfer reaction were computed. The results show that in comparison with PTAN, PDADN, PATN and PETN, TAPE has the maximum heat of formation among five derivatives and specific impulse level approaching that of PETN. The detonation performance and stability of PATN are close to those of PETN, and better than that of other derivatives, including PDADN. The pyrolysis of TAPE with —N₃ is initiated from the transfer of H to —N₃ which leads to the elimination of N₂ and has an E_a of 130.57 kJ·mol^-1. The pyrolysis of other derivatives containing —ONO₂ is started from the rupture of the O—NO₂ bond with an E_BD of 130.91~137.45 kJ·mol^-1. These energy values satisfy the stability requirements for the energetic compounds.

Key words：physical chemistry; pentaerythritol; azido group; nitrate; detonation performance; pyrolysis mechanism

收稿日期：2013-05-21

基金项目：高等学校博士点新教师基金项目(No.20103219120014)、中国博士后特别资助基金项目(No.201003588)和南京理工大学“卓越计划、紫金之星”基金项目。

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