离子液体热分解机理的原位变温多核核磁共振研究

doi:10.11938/cjmr20170204

波谱学杂志 ›› 2017, Vol. 34 ›› Issue (2): 156-163.doi: 10.11938/cjmr20170204

离子液体热分解机理的原位变温多核核磁共振研究

李森, 郑俊鹏, 郭鸣明

中国石油化工股份有限公司北京化工研究院, 北京 100013

收稿日期:2016-05-03 修回日期:2017-04-17 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 李森,Tel:010-59202620,E-mail:lisen01.bjhy@sinopec.com;郭鸣明,Tel:010-59202187,E-mail:guomm.bjhy@sinopec.com. E-mail:lisen01.bjhy@sinopec.com;guomm.bjhy@sinopec.com
基金资助:
中国石化基础性前瞻性研究资助项目（14-16ZS0402）.

In Situ Variable-Temperature Multi-Nuclear NMR Studies of the Thermal Decomposition Mechanism of Ionic Liquid

LI Sen, ZHENG Jun-peng, GUO Ming-ming

SINOPEC Beijing Research Institute of Chemical Industry, Beijing 100013, China

Received:2016-05-03 Revised:2017-04-17 Online:2017-06-05 Published:2017-06-05

摘要/Abstract

摘要： 利用原位变温核磁共振氢谱（¹H NMR）、核磁共振氟谱（¹⁹F NMR）和核磁共振磷谱（³¹P NMR）等NMR技术研究特定温度下离子液体的热分解机理．在温度低至80℃时，1-丁基-3-甲基咪唑阳离子（C₄mim⁺）和六氟磷酸根阴离子（PF₅—）组成的离子液体[C₄mim][PF₅]呈现1个缓慢但明显的分解过程．无水[C₄mim][PF₅]在温度高于80℃时开始分解，生成少量的五氟化磷（PF₅）和氟化氢（HF），氟化氢中的氢原子来自于1-丁基-3-甲基咪唑环2位上的氢原子．在丢掉这个氢原子后，阳离子成环形成一个卡宾，并与PF₅形成卡宾/PF₅复合物．定量NMR分析显示在分解反应达到平衡状态时，自由态PF₅和卡宾/PF₅复合物的比例为7∶3．

关键词: 离子液体, 原位变温多核核磁共振, 热分解机理

Abstract: In situ variable-temperature ¹H, ¹⁹F and ³¹P NMR spectroscopy was employed to study the thermal decomposition mechanisms of ionic liquid. At a temperature as low as 80℃, ionic liquid[C₄mim] [PF₅], composed of 1-butyl-3-methylimidazolium cation (C₄mim⁺) and hexafluorophosphate anion (PF₅^-), had a slow, but detectable decomposition. For dehydrated[C₄mim] [PF₅], the ionic liquid started to decompose at temperature higher than 80℃. Small amount of PF₅ and HF formed first. The proton in HF came from the proton at 2-position of 1-butyl-3-methylimidazolium cation ring. After losing the proton, a carbene structure was formed, which then formed complex with PF₅. Free PF₅ and PF₅/carbene complex reached equilibrium at a ratio of 7:3.

Key words: in situ variable-temperature multi-nuclear NMR, ionic liquid, thermal decomposition mechanism

中图分类号:

O482.53

李森, 郑俊鹏, 郭鸣明. 离子液体热分解机理的原位变温多核核磁共振研究[J]. 波谱学杂志, 2017, 34(2): 156-163.

LI Sen, ZHENG Jun-peng, GUO Ming-ming. In Situ Variable-Temperature Multi-Nuclear NMR Studies of the Thermal Decomposition Mechanism of Ionic Liquid[J]. Chinese Journal of Magnetic Resonance, 2017, 34(2): 156-163.

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离子液体热分解机理的原位变温多核核磁共振研究

In Situ Variable-Temperature Multi-Nuclear NMR Studies of the Thermal Decomposition Mechanism of Ionic Liquid

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离子液体热分解机理的原位变温多核核磁共振研究

In Situ Variable-Temperature Multi-Nuclear NMR Studies of the Thermal Decomposition Mechanism of Ionic Liquid

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