合成黑索今中副产物3,5-二硝基-1-氧-3,5-二氮杂环己烷的晶体结构及热分解动力学

引用本文: 李静, 陈丽珍, 王建龙, 兰贯超, 侯欢, 李满. 合成黑索今中副产物3,5-二硝基-1-氧-3,5-二氮杂环己烷的晶体结构及热分解动力学[J]. 物理化学学报, 2015, 31(11): 2049-2056. doi: 10.3866/PKU.WHXB201510092 shu

Citation: LI Jing, CHEN Li-Zhen, WANG Jian-Long, LAN Guan-Chao, HOU Huan, LI Man. Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane[J]. Acta Physico-Chimica Sinica, 2015, 31(11): 2049-2056. doi: 10.3866/PKU.WHXB201510092 shu

合成黑索今中副产物3,5-二硝基-1-氧-3,5-二氮杂环己烷的晶体结构及热分解动力学

1.
中北大学化工与环境学院, 太原 030051

通讯作者: 王建龙

基金项目:
国家自然科学基金(11447219) (11447219)

国防产品创新项目资助

摘要: 直接法硝解乌洛托品制备黑索今的过程中合成了一种新型的环形副产物, 采用硅胶柱层析法分离得到3,5-二硝基-1-氧-3,5-二氮杂环己烷, 洗脱剂为: 丙酮/二氯甲烷, 梯度洗脱. 以丙酮为溶剂培养得到了3,5-二硝基-1-氧-3,5-二氮杂环己烷单晶, 用元素分析、傅里叶变换红外(FTIR)光谱、核磁共振氢谱(NMR)以及质谱(MS)对其结构进行了表征, 用X射线单晶衍射仪测定了其晶体结构. 结果表明, 晶体C₃H₆N₄O₅分子量为178.12,属于单斜晶系, 空间群P121/n1, 晶胞参数: a = 0.58128(13) nm, b = 1.72389(14) nm, c = 0.71072(6) nm, β =112.056°, V = 0.66006(16) nm³, Z = 4, D_C= 1.792 g·cm^-3, μ = 0.17 mm^-1, F(000) = 368.0, 最终偏差因子R =0.0397. 用同步热分析仪技术研究了3,5-二硝基-1-氧-3,5-二氮杂环己烷的热行为, DSC曲线上在383.15和519.05 K分别有一个尖锐的熔化吸热峰和分解放热峰. 另外, 根据Kissinger方程及Flynn-Wall-Ozawa方程和不同升温速率下的TG曲线计算得到了该化合物的热分解动力学参数(活化能和指前因子), 利用Coats-Redfern法研究了该物质的热分解机理. 结果表明: 3,5-二硝基-1-氧-3,5-二氮杂环己烷是一种低熔点、热稳定性好的化合物. Kissinger方程计算其活化能为212.32 kJ·mol^-1, 指前因子为6.20×10²⁰ s^-1, Flynn-Wall-Ozawa方程计算其活化能为210.39 kJ·mol^-1, 该物质的热分解动力学方程为G(α) = (1-α)^-1-1, 反应级数为2.

关键词:

English

Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane

1.
School of Chemical Engineering and Environment, North University of China, Taiyuan 030051, P. R. China

Corresponding author: 王建龙

Received Date: 16 July 2015
Fund Project:
国家自然科学基金(11447219)

国防产品创新项目资助

Abstract: A new cyclic byproduct was formed during hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) preparation by direct nitration. Silicone column chromatography with acetone and dichloromethane in various ratios as the eluent was used to separate 3,5-dinitro-1-oxygen-3,5-diazacyclohexane from the product mixture. A single crystal of 3,5-dinitro-1-oxygen-3,5-diazacyclohexane was grown from acetone, and characterized using elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry (MS). Its structure was determined using an X-ray single-crystal diffractometer. The results indicate that the crystal molecular weight is 178.12. It belongs to the monoclinic system with the space group P121/n1, a = 0.58128(13) nm, b = 1.72389(14) nm, c = 0.71072(6) nm, β = 112.056°, V = 0.66006(16) nm³, Z = 4, D_C= 1.792 g·cm^-3, μ = 0.17 mm^-1, and F(000) = 368.0; the final deviation factor R is 0.0397. Differential scanning calorimetrythermogravimetry (DSC-TG) was used to investigate the thermal behavior of the title compound. Sharp peaks were observed at 383.15 K (melting) and 519.05 K (decomposition). The kinetic parameters were obtained using the Kissinger and Flynn-Wall-Ozawa methods and the TG data at different heating rates. The Coats-Redfern method was used to study the thermal decomposition mechanism of 3,5-dinitro-1-oxygen-3,5-diazacyclohexane. The results show that the title compound is a low-melting-point compound with good stability; its apparent activation energy and pre-exponential factor, calculated using the Kissinger equation, are 212.32 kJ·mol^-1 and 6.20×10²⁰ s^-1, respectively. The apparent activation energy, calculated using the Flynn-Wall-Ozawa equation, is 210.39 kJ·mol^-1. G(α) = (1-α)^-1-1 (n = 2) obtained using Coats-Redfern method is regarded as the most appropriate thermal decomposition kinetic equation.

Key words:

RDX
/ 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane
/ Crystal structure
/ Thermal decomposition kinetics
/ Apparent activation energy
/ Mechanism

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沈阳化工大学材料科学与工程学院沈阳 110142

合成黑索今中副产物3,5-二硝基-1-氧-3,5-二氮杂环己烷的晶体结构及热分解动力学

通讯作者: 王建龙

English

Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane

Corresponding author: 王建龙

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

合成黑索今中副产物3,5-二硝基-1-氧-3,5-二氮杂环己烷的晶体结构及热分解动力学

通讯作者: 王建龙

English

Crystal Structure and Thermal Decomposition Kinetics of Byproduct of Synthesis of RDX: 3,5-Dinitro-1-oxygen-3,5-diazacyclohexane

Corresponding author: 王建龙

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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