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 在线发表日期: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 Published:2017-06-05 Online: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.

参考文献

[1] HUDDLESTON J G, WILLAUER H D, SWATLOSKI R P, et al. Room temperature ionic liquids as novel media for ‘clean’ liquid-liquid extraction[J]. Chem Comm, 1998, 16:1765-1766.
[2] SEDDON K R. Ionic liquids for clean technology[J]. J Chem Tech Biotech, 1997, 68(4):351-356.
[3] CHAUVIN Y, OLIVIER H. Nonaqueous ionic liquids as reaction solvents[J]. Chemtech, 1995, 25(1):26-30.
[4] SEDDON K R. Room-temperature ionic liquids:neoteric solvents for clean catalysis[J]. Kinet Catal, 1996, 37(5):693-697.
[5] HALLETT J P, WELTON T. Room-temperature ionic liquids:solvents for synthesis and catalysis[J]. Chem Rev, 2011, 111(5):3508-3576.
[6] HOLBREY J D, SEDDON K R. The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals[J]. J Chem Soc Dalton Trans, 1999, 13:2133-2140.
[7] WELTON T. Room-temperature ionic liquids. solvents for synthesis and catalysis[J]. Chem Rev, 1999, 99(11):2071-2083.
[8] KEIM W, WASSERSCHEID P. Ionic liquids-new solutions for transition metal catalysis[J]. Angew Chem Int Ed, 2000, 39(21):3772-3789.
[9] SALZER A. Ionic liquids:not so green[J]. Chem & Eng News, 2002, 80(17):4.
[10] ROGERS R D. Reply to Ionic liquids:Not so green[J]. Chem & Eng News, 2002, 80(17):4-5.
[11] HASSOUN E A, ABRAHAN M, AL-GHAFRI V K, et al. Cytotoxicity of the ionic liquid, 1-N-butyl-3-methyl imidazolium chloride[J]. Res Commun Pharmacol Toxicol, 2002, 7(1):23-31.
[12] SWATLOSKI R P, HOLBREY J D, ROGERS R D. Ionic liquids are not always green:hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate[J]. Green Chem, 2003, 5:361-363.
[13] WAZER J R. Phosphorous and its Compounds[M]. Wiley, New York, 1958.
[14] VISSER A E, SWATLOSKI R P, REICHERT W M, et al. Traditional extractants in nontraditional solvents:groups 1 and 2 extraction by crown ethers in room-temperature ionic liquids[J]. Ind Eng Chem Res, 2000, 39(10):3596-3604.
[15] LALL S I, MANCHENO D, CASTRO S, et al. Polycations. Part X. LIPs, a new category of room temperature ionic liquid based on polyammonium salts[J]. Chem Commun, 2000, 24:2413-2414.
[16] GUBICZA L, NEMESTOTHY N, FRATER T, et al. Enzymatic esterification in ionic liquids integrated with pervaporation for water removal[J]. Green Chem, 2003, 5:236-239.
[17] KROON M C, BUIJS W, PETERS J, et al. Quantum chemical aided prediction of the thermal decomposition mechanisms and temperatures of ionic liquids[J]. Thermochim Acta, 2007, 465(1):40-47.
[18] YOGESH R J, DAE Y C. Synthesis of symmetrical organic carbonates via significantly enhanced alkylation of metal carbonates with alkyl halides/sulfonates in ionic liquid[J]. J Org Chem, 2005, 70(26):10774-10777.
[19] LI Y Z, QIU L, YIN Q Y, et al. Spectroscopy study on synthesis of diisopropyl coumarin-3-phosphate by ³¹P NMR[J]. Chinese J Magn Reson, 2016, 33(1):133-141. 李远哲, 邱莉, 尹秋月, 等. ³¹P NMR在二异丙基香豆素-3-膦酸酯合成中的应用研究[J]. 波谱学杂志, 2016, 33(1):133-141.
[20] LI Y, LI L S, LAN Y J. Calculation of ¹⁹F NMR chemical shifts of fluoroaromatics[J]. Chinese J Magn Reson, 2012, 29(2):258-277. 李燕, 李临生, 兰云军. 氟苯类化合物¹⁹F NMR化学位移的计算[J]. 波谱学杂志, 2012, 29(2):258-277.
[21] JAMESON C J, JAMESON A K, WILLE S. Effects of intermolecular interactions and intramolecular dynamics on nuclear resonance in nitrogen trifluoride, phosphorus trifluoride, phosphoryl fluoride, and phosphorus pentafluoride[J]. J Phys Chem, 1979, 83:3372-3378.
[22] MICHAL J. Ab initio study of the shielding and spin-spin coupling constants in ClF₃, PF₃ and PF₅[J]. Chem Phys Lett, 2004, 385(1,2):122-126.
[23] CHRISTOPHE R, LAURENT M, JEANPIERRE D, et al. Berry pseudorotation mechanism for the interpretation of the ¹⁹F NMR spectrum in PF₅ by Ab initio molecular dynamics simulations[J]. Chem Phys Chem, 2006, 7(2):407-413.
[24] CAMMARATA L. KAZARIAN S G, SALTER P A, et al. Molecular states of water in room temperature ionic liquids[J]. Phys Chem Chem Phys, 2001, 3(23):5192-5200.

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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