醚基高铼酸盐离子液体的催化性能研究

doi:10.11949/0438-1157.20191367

摘要/Abstract

摘要：

自合成两种新型醚基高铼酸盐离子液体：1-(2-甲氧基乙基)-3-乙基咪唑高铼酸盐（[C₂2O1Im][ReO₄]）和1-(2-乙氧基乙基)-3-乙基咪唑高铼酸盐（[C₂2O2Im][ReO₄]），并利用核磁共振氢谱/碳谱、拉曼光谱、质谱和差示扫描量热等方法表征，确定是目标产物。环氧化合物是一种化学性质活泼且易转化为其他物质的有机合成中间体，烯烃的环氧化反应是合成环氧化合物的一种重要途径，因此建立以新型醚基高铼酸盐离子液体为溶剂兼催化剂的环辛烯环氧化均相反应体系，系统研究反应温度、时间、氧化剂用量、催化剂用量及循环使用等因素的影响。结果表明，产率大于90%，反应选择性大于99%，催化剂循环5次，产率无明显下降。

关键词: 醚基, 铼离子液体, 均相催化, 环氧化, 选择性

Abstract:

Two novel ether-based perrhenate ionic liquids 1-(2-methoxyethyl)-3-ethylimidazolium perrhenate ([C₂2O1Im][ReO₄]) and1-(2-ethoxyethyl)-3-ethylimidazolium perrhenate ([C₂2O2Im][ReO₄]) were synthesized and characterized by nuclear magnetic resonance spectroscopy (¹H NMR,¹³C NMR), Raman spectroscopy (Raman), electrospray ionization mass spectrometry (ESI-MS), differential scanning calorimetry (DSC). As a sort of organic synthesis intermediates which is chemically active and easily converted into other substances, epoxy compounds occupy an extremely important position in various industries of national production. The epoxidation of olefins is an important way to synthesize epoxy compounds. Therefore, two novel ether-based perrhenate ionic liquids were used as catalyst and solvent in the reaction system of cyclooctene epoxidation to epoxycyclooctane, respectively. The effects of reaction temperature, time, oxidant amount, catalyst amount and its recycle were investigated systematically. The results showed that the yield was more than 90%, the reaction selectivity was more than 99%, the catalyst was cycled 5 times, and the yield did not decrease significantly.

Key words: ether group, perrhenate ionic liquids, homogeneous catalysis, epoxidation, selectivity

中图分类号:

TQ 028.8

马晓雪, 梁坤豪, 魏杰, 宋宗仁, 肖传佑, 巩璐, 房大维. 醚基高铼酸盐离子液体的催化性能研究[J]. 化工学报, 2020, 71(1): 314-319.

Xiaoxue MA, Kunhao LIANG, Jie WEI, Zongren SONG, Chuanyou XIAO, Lu GONG, Dawei FANG. Study on catalytic properties of novel ether-based perrhenate ionic liquids[J]. CIESC Journal, 2020, 71(1): 314-319.

图/表 7

图1 离子液体[C22O1Im][ReO4]和[C22O2Im][ReO4]的合成路线

Fig.1 Synthetic route of ionic liquids [C22O1Im][ReO4] and [C22O2Im][ReO4]

图2 离子液体[C22O1Im][ReO4]和[C22O2Im][ReO4]催化环辛烯环氧化

Fig.2 Epoxidation of cyclooctene catalyzed by ionic liquids [C22O1Im][ReO4] and [C22O2Im][ReO4]

图3 催化剂用量对催化产率的影响

Fig.3 Effect of amount of catalyst on catalytic yield

图4 反应时间对催化产率的影响

Fig.4 Effect of reaction time on catalytic yield

图5 反应温度对催化产率的影响

Fig.5 Effect of reaction temperature on catalytic yield

图6 氧化剂过氧化脲用量对催化产率的影响

Fig.6 Effect of amount of oxidant urea peroxide on catalytic yield

图7 离子液体循环次数对催化产率的影响

Fig.7 Effect of cycle times of ionic liquid on catalytic yield

参考文献 33

1	Rogers R D , Seddon K R . Ionic liquids — solvents of the future?[J]. Science, 2003, 302: 792-793.
2	Zhang J L , Han B X , Li J S , et al . Carbon dioxide in ionic liquid microemulsions[J]. Angew. Chem. Int. Ed., 2011, 50: 9911-9915.
3	Zhang Q H , Zhang S G , Deng Y Q . Recent advances in ionic liquid catalysis[J]. Green Chem., 2011, 13: 2619-2637.
4	Maton C , De Vos N , Stevens C V . Ionic liquid thermal stabilities: decomposition mechanisms and analysis tools[J]. Chem. Soc. Rev., 2013, 42: 5963-5977.
5	Chatel G , Pereira J F B , Debbeti V , et al . Mixing ionic liquids — “simple mixtures” or “double salts”? [J]. Green Chem., 2014, 16: 2051-2083.
6	Lei Z G , Dai C N , Chen B H . Gas solubility in ionic liquids[J]. Chem. Rev., 2014, 114: 1289-1326.
7	Zhang Q H , Shreeve J M . Energetic ionic liquids as explosives and propellant fuels: a new journey of ionic liquid chemistry[J]. Chem. Rev., 2014, 114: 10527-10574.
8	Hu J Y , Ma J , Zhu Q G , et al . Transformation of atmospheric CO₂ catalyzed by protic ionic liquids: efficient synthesis of 2-oxazolidinones[J]. Angew. Chem. Int. Ed., 2015, 54: 5399-5403.
9	Webb P B , Sellin M F , Kunene T E , et al . Continuous flow hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic systems[J]. J. Am. Chem. Soc., 2003, 125: 15577-15588.
10	Zhao Y F , Yu B , Yang Z Z , et al . A protic ionic liquid catalyzes CO₂ conversion at atmospheric pressure and room temperature: synthesis of quinazoline-2, 4-(1H, 3H)-diones[J]. Angew. Chem. Int. Ed., 2014, 53: 5922-5925.
11	Passos H , Freire M G , Coutinho J A P . Ionic liquid solutions as extractive solvents for value-added compounds from biomass[J]. Green Chem., 2014, 16: 4786-4815.
12	Visser A E , Swatloski R P , Reichert W M , et al . Task-specific ionic liquids for the extraction of metal ions from aqueous solutions[J]. Chem. Commun., 2001, 135-136.
13	Jiang X C , Nie Y , Li C X , et al . Imidazolium-based alkylphosphate ionic liquids — a potential solvent for extractive desulfurization of fuel[J]. Fuel, 2008, 87: 79-84.
14	Sun X Q , Luo H M , Dai S . Ionic liquids-based extraction: a promising strategy for the advanced nuclear fuel cycle[J]. Chem. Rev., 2012, 112: 2100-2128.
15	Wang C M , Zheng J J , Cui G K , et al . Highly efficient SO₂ capture through tuning the interaction between anion-functionalized ionic liquids and SO₂ [J]. Chem. Commun., 2013, 49: 1166-1168.
16	Yang D Z , Hou M Q , Ning H , et al . Reversible capture of SO₂ through functionalized ionic liquids[J]. ChemSusChem, 2013, 6: 1191-1195.
17	Bates E D , Mayton R D , Ntai I , et al . CO₂ capture by a task-specific ionic liquid[J]. J. Am. Chem. Soc., 2002, 124: 926-927.
18	Doroodian A , Dengler J E , Genest A , et al . Methylguanidinium borohydride: an ionic-liquid-based hydrogen-storage material[J]. Angew. Chem. Int. Ed., 2010, 49: 1871-1873.
19	Kang X C , Sun X F , Han B X . Synthesis of functional nanomaterials in ionic liquids[J]. Adv. Mater., 2016, 28: 1011-1030.
20	Kang X C , Zhang J L , Shang W T , et al . One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel[J]. J. Am. Chem. Soc., 2014, 136: 3768-3771.
21	Kang X C , Zhu Q G , Sun X F , et al . Highly efficient electrochemical reduction of CO₂ to CH₄ in an ionic liquid using a metal-organic framework cathode[J]. Chem. Sci., 2016, 7: 266-273.
22	An K , Alayoglu S , Musselwhite N , et al . Designed catalysts from Pt nanoparticles supported on macroporous oxides for selective isomerization of n-hexane[J]. J. Am. Chem. Soc., 2014, 136: 6830-6833.
23	Tsunashima K , Sugiya M . Physical and electrochemical properties of low-viscosity phosphonium ionic liquids as potential electrolytes[J]. Electrochemistry Communications, 2007, 9: 2353-2358.
24	Kuhlmann E , Himmler S , Giebelhaus H , et al . Imidazolium dialkylphosphates—a class of versatile, halogen-free and hydrolytically stable ionic liquids[J]. Green Chem., 2007, 9: 233-242.
25	Zhang J H , Fang S H , Qu L , et al . Synthesis, characterization, and properties of ether-functionalized 1, 3-dialkylimidazolium ionic liquids[J]. Ind. Eng. Chem. Res., 2014, 53: 16633-16643.
26	Ganapatibhotla L V N R , Zheng J , Roy D , et al . PEGylated imidazolium ionic liquid electrolytes: thermophysical and electrochemical properties[J]. Chem. Mater., 2010, 22: 6347-6360.
27	Dzyuba S V , Bartsch R A . Expanding the polarity range of ionic liquids[J]. Tetrahedron Lett., 2002, 43: 4657-4659.
28	Kuznetsova N I , Kuznetsova L I , Likholobov V A . Catalytic properties of Cr-containing heteropolytungstates in H₂O₂ participated reactions: H₂O₂ decomposition and oxidation of unsaturated hydrocarbons with H₂O₂ [J]. J. Mol. Catal. A Chem., 1996, 108: 135-143.
29	Wolf P F , Barnes R K . Borate ester-induced decomposition of alkyl hydroperoxides. The epoxidation of olefins by electrophilic oxygen[J]. J. Org. Chem., 1969, 34: 3441-3445.
30	Crivello J V , Bo Y . Studies of synthesis and cationic photopolymerization of three isomeric monoterpene diepoxides[J]. J. Polym. Sci., Part A: Polym. Chem., 1995, 33: 1881-1890.
31	巩璐 . 醚基功能化铼离子液体性质及其在环辛烯环氧化中的应用[D]. 沈阳: 辽宁大学, 2019.
	Gong L . Properties of ether-functionalized rhenium ionic liquid and their applications in cyclooctene epoxidation[D]. Shenyang: Liaoning University, 2019.
32	Wilkes J S , Zaworotko M J . Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J]. J. Chem. Soc., Chem. Commun., 1992, 13: 965-967.
33	Rost A M J , Schneider H , Zoller J P , et al . Methyltrioxorhenium heterogenized on commercially available supporting materials as cyclooctene metathesis catalyst[J]. Journal of Organometallic Chemistry, 2005, 690: 4712-4718.

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