CN103193710B - A kind of Three-ingredient eutectic ionic liquid and preparation method thereof - Google Patents
A kind of Three-ingredient eutectic ionic liquid and preparation method thereof Download PDFInfo
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- CN103193710B CN103193710B CN201310119547.9A CN201310119547A CN103193710B CN 103193710 B CN103193710 B CN 103193710B CN 201310119547 A CN201310119547 A CN 201310119547A CN 103193710 B CN103193710 B CN 103193710B
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Abstract
The present invention relates to a kind of Three-ingredient eutectic ionic liquid and preparation method thereof, it consists of ILC, REC and HBD, and wherein ILC is take chlorion as anion ion liquid, and REC is rare earth chloride metal-salt, and HBD is many hydrogen bonding compounds.Preparation method is: by ILC, REC and HBD 1:1:n in molar ratio, wherein n=0.5 ~ 4, mix, and after being heated to 100 ~ 140 DEG C, keeping 2 ~ 4h to melt completely to mixture, to obtain final product.Ionic liquid of the present invention, fusing point is extremely low, and viscosity is little, specific conductivity is high, and solubility property is good, and has the acid and catalytic performance of Lewis due to rare earth metal salt wherein, can organic synthesis be widely used in, nanometer and mesoporous material preparation, and gas absorption etc.; Preparation technology is simple, and raw material is easy to get, and cost is low, and in reaction process not with an organic solvent, also can not give off toxic substance, no coupling product, biodegradable, is suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to ionic liquid and preparation field thereof, particularly a kind of Three-ingredient eutectic ionic liquid and preparation method thereof.
Background technology
Rare earth element has special electronic structure, and the 4f electronics of its internal layer is shielded by outer field 5s and 5p electron institute, localization in atom.Outermost electron arrangement 4f and 5d of decision element character forms conduction band, localization and incomplete filling of 4f electronics make rare earth have unique optics and magnetism characteristic, these character make rare earth be used widely in catalytic field, application particularly in catalysis organic synthesis, as carboxylicesters synthesis, fatty alcohol amination, synthetic rubber, catalyticcombustion, automotive catalyst etc.China has abundant rare earth resources, rare earth chloride is that a kind of Lewis that is simple, cheap and that be easy to get is sour, there is the advantages such as light to equipment corrosion, pollution-free, that a kind of being expected, with solving the sour environmental friendliness Jue agent causing problem of environmental pollution of traditional Lewis, meets the tendency of the day of Green Chemistry.But because rare earth chloride is generally inoganic solids, solvability is in organic solvent poor, can only heterocatalysis be carried out, therefore catalytic efficiency and productive rate lower.Therefore how to increase the solvability of rare earth chloride or how system become the focus that homogeneous phase is becoming research.
Ionic liquid is the brand-new medium and soft functional materials that grow up under the framework of Green Chemistry in recent years.Because its steam forces down, Heat stability is good, specific conductivity is high, and can keep the advantages such as liquid state in longer temperature range, is subject to extensive concern in fields such as catalysis.2003, that Abbott reports the excellent in physical and chemical performance be mixed to form by neutral molecule and ionic compound, that there is ionic liquid character two component eutectic solvents (Deep Eutectic Solvents).This nontoxic solvent, biodegradable, and building-up process atom utilization reaches 100%, is-kind of novel green solvent.Konig reports Diels-Alder, Stille and Suzuki reaction in sugar (sugar alcohol)-urea-salt ternary system eutectic mixture.
Due to the fine solvent that eutectic solvent is inorganic salt, organism and macromolecular material, select suitable system, rare earth chloride is used to contain ionic liquid or the eutectic solvent of rare earth as the salt component synthesis in eutectic solvent, the solvability of rare earth chloride can not only be increased, can also rare earth catalyst be changed into homogeneous catalysis system, increase efficiency and the productive rate of catalysis.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Three-ingredient eutectic ionic liquid and preparation method thereof, and this inventive method is a kind of environmental friendliness, is suitable for the preparation method of the ionic liquid of large-scale industrial production; Preparation technology is simple, and raw material is easy to get, and cost is low, and in reaction process not with an organic solvent, also can not give off toxic substance, no coupling product, biodegradable.
A kind of Three-ingredient eutectic ionic liquid of the present invention, is characterized in that: consist of ILC, REC and HBD, and wherein ILC is take chlorion as anion ion liquid; REC is rare earth chloride metal-salt, and HBD is many hydrogen bonding compounds, and the mol ratio of ILC, REC and HBD three is 1:1:n, n=0.5 ~ 4.
The structure of described ionic liquid ILC is represented by following structural formula:
or
A=N or P
A is nitrogen or phosphorus atom;
Wherein, A is nitrogen-atoms, R
1~ R
4separately be selected from hydrogen, alkyl, aryl or aralkyl, but be hydrogen full time different; Or A is phosphorus atom, R
1~ R
4separately be selected from alkyl, aryl or aralkyl;
R
5, R
6separately be selected from alkyl, aryl or aralkyl.
Described rare earth chloride metal-salt REC is one or more in Scium trichloride, Yttrium trichloride, Lanthanum trichloride, Cerium II Chloride, praseodymium chloride, Neodymium trichloride, chlorination promethium, samarium trichloride, Europium trichloride, Gadolinium trichloride, terbium chloride, Dysprosium trichloride, Holmium trichloride, Erbium trichloride, thulium chloride, Ytterbium trichloride, lutecium chloride.
Described many hydrogen bonding compounds HBD is ethanamide, N-MU, N, one or more in N '-dimethyl urea, N, N-dimethyl urea, urea, thiocarbamide, hexanolactam, benzamide, trifluoroacetamide, ethylene glycol, glycerine, Xylitol, sorbyl alcohol, pyrocatechol, Resorcinol, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, tartrate, citric acid, fourth tetracid, phthalic acid, m-phthalic acid.
The preparation method of a kind of Three-ingredient eutectic ionic liquid of the present invention, comprising:
By ionic liquid ILC, rare earth chloride metal-salt REC and many hydrogen bonding compounds HBD 1:1:n in molar ratio, wherein n=0.5 ~ 4, mix, after being heated to 100 ~ 140 DEG C, keep 2 ~ 4h to melt the liquid forming homogeneous transparent completely to mixture, obtain Three-ingredient eutectic ionic liquid.
Described Three-ingredient eutectic ionic liquid is applied to electrochemical cell, ultracapacitor, the synthesis of nano material, the synthesis of mesoporous material, the dissolving of natural fiber, organic catalysis synthesis.
The present invention is with three kinds of components: take chlorion as anion ion liquid ILC, rare earth chloride metal-salt REC and many hydrogen bonding compounds HBD, synthesizing new ionic liquid ILC/REC/HBD.Because HBD molecule generally can form hydrogen bond with monovalence halide anion, increase steric restriction, the distance between zwitterion is increased, thus the ionic liquid of low melting point can be formed.
beneficial effect
(1) Preparation equipment of ionic liquid provided by the invention and synthesis step simple, purity is high, separating-purifying that need not be complicated; Raw materials cost is low, and in reaction process not with an organic solvent, also can not give off toxic substance, no coupling product, and biodegradable, environmental pollution is few, is suitable for suitability for industrialized production.In addition, can adopt microwave heating during preparation, the reaction times is shorter.
(2) in fact the present invention also provides a kind of novel three components hybrid inorganic-organic materials, multiple solid phase material is transformed into single " inorganic liquid phase ", for herein is provided new way prepared by a kind of hybrid inorganic-organic materials.
(3) feature of the present invention, it is the ionic liquid a kind of low melting point (room temperature or lower than room temperature) being prepared by the combination of multiple solid matter, can by changing the fusing point that difference forms, ratio regulates synthetic materials of these three kinds of components, specific conductivity and Acid-Base strengths;
(4) Three-ingredient eutectic ionic liquid prepared of the present invention is compared to traditional functionalized ion liquid, this Three-ingredient eutectic ionic liquid fusing point and viscosity lower, stability is higher, the placement several months can keep stable, can be used for organic synthesis and nano material preparation as novel dissolvent.
(5) Three-ingredient eutectic ionic liquid prepared of the present invention is compared to traditional rare earth catalyst, Three-ingredient eutectic ionic liquid not only has good solubility property to raw material, and the rare earth chloride metal-salt with catalytic performance exists in liquid form in ionic liquid, and reaction can be reacted in homogeneous phase, therefore considerably increase its catalytic effect, therefore in fields such as catalyzed reactions, there are great potentiality.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 1.18 grams of (0.02mol) ethanamides (AA), 2.45 grams of (0.01mol) LaCl
3mix with 1.74 grams of (0.01mol) chlorination 1-butyl-3-Methylimidazole [Bmim] Cl, be heated to 100 DEG C, and keep 3h, form colourless transparent liquid, obtain ionic liquid [Bmim] [La (AA)
2cl
4].Its at room temperature (20 DEG C) be colourless transparent liquid.
Embodiment 2
By 1.20 grams of (0.02mol) urea, 2.45 grams of (0.01mol) LaCl
3with 1.74 grams of (0.01mol) chlorination 1-butyl-3-Methylimidazole [Bmim] Cl Hybrid Heating, microwave heating to 100 DEG C, form colourless transparent liquid, keep 2h, obtain ionic liquid [Bmim] [La (Urea)
2cl
4].Its at room temperature (20 DEG C) be colourless transparent liquid.
Embodiment 3
By 1.20 grams of (0.02mol) urea, 2.57 grams of (0.01mol) SmCl
3, with 1.74 grams of (0.01mol) chlorination 1-butyl-3-Methylimidazole [Bmim] Cl Hybrid Heating, microwave heating to 110 DEG C, form light yellow transparent liquid, keep 2h, obtain ionic liquid [Bmim] [Sm (Urea)
2cl
4].Its at room temperature (20 DEG C) be light yellow transparent liquid.
Embodiment 4
By 1.76 grams of (0.02mol) N, N '-dimethyl urea (DMU), 2.51 grams of (0.01mol) NdCl
3, with 1.40 grams of (0.01mol) choline chloride 60 (ChCl) Hybrid Heating, be heated to 110 DEG C, form lavender transparent liquid, keep 4h, obtain ionic liquid [Ch] [Nd (DMU)
2cl
4].Its at room temperature (20 DEG C) be lavender transparent liquid.
Embodiment 5
By 1.24 grams of (0.02mol) ethylene glycol (EG), 2.74 grams of (0.01mol) ErCl
3, with 3.99 grams of (0.01mol) chlorinated butyl triphenylphosphine ([P
4,6,6,6] Cl) Hybrid Heating, microwave heating forms light red transparent liquid to 140 DEG C, keeps 2h, obtains ionic liquid [P
4,6,6,6] [Er (EG)
2cl
4].Its at room temperature (20 DEG C) be light red transparent liquid.
Embodiment 6
By 1.84 grams of (0.02mol) glycerine (gly), 3.73 grams of (0.01mol) CeCl
37H
2o, with 1.74 grams of (0.01mol) chlorination 1-butyl-3-Methylimidazole [Bmim] Cl Hybrid Heating, microwave heating to 120 DEG C forms colourless transparent liquid, keeps 2h, obtains ionic liquid [Bmim] [Ce (gly)
2cl
4].Its at room temperature (20 DEG C) be colourless transparent liquid.
Claims (4)
1. a Three-ingredient eutectic ionic liquid, is characterized in that: it consists of ILC, REC and HBD, and wherein ILC is take chlorion as anion ion liquid; REC is rare earth chloride metal-salt, and HBD is many hydrogen bonding compounds, and the mol ratio of ILC, REC and HBD three is 1:1:n, n=0.5-4; Wherein ILC is chlorination 1-butyl-3-Methylimidazole, choline chloride 60 or chlorinated butyl triphenylphosphine; Many hydrogen bonding compounds HBD is ethanamide, N-MU, N, one or more in N '-dimethyl urea, N, N-dimethyl urea, urea, thiocarbamide, hexanolactam, benzamide, trifluoroacetamide, ethylene glycol, glycerine, Xylitol, sorbyl alcohol, pyrocatechol, Resorcinol, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, tartrate, citric acid, fourth tetracid, phthalic acid, m-phthalic acid.
2. a kind of Three-ingredient eutectic ionic liquid according to claim 1, is characterized in that: described rare earth chloride metal-salt REC is one or more in Scium trichloride, Yttrium trichloride, Lanthanum trichloride, Cerium II Chloride, praseodymium chloride, Neodymium trichloride, chlorination promethium, samarium trichloride, Europium trichloride, Gadolinium trichloride, terbium chloride, Dysprosium trichloride, Holmium trichloride, Erbium trichloride, thulium chloride, Ytterbium trichloride, lutecium chloride.
3. a preparation method for the Three-ingredient eutectic ionic liquid as described in as arbitrary in claim 1-2, comprising:
By ionic liquid ILC, rare earth chloride metal-salt REC and many hydrogen bonding compounds HBD 1:1:n in molar ratio, wherein n=0.5 ~ 4, mix, and after being heated to 100 ~ 140 DEG C, keeping 2 ~ 4h, obtain Three-ingredient eutectic ionic liquid.
4. the application of a kind of Three-ingredient eutectic ionic liquid according to claim 1, is characterized in that: described Three-ingredient eutectic ionic liquid be applied to electrochemical cell, ultracapacitor, the synthesis of nano material, the synthesis of mesoporous material, natural fiber dissolving, catalyze and synthesize and gas absorption.
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| CN104087336A (en) * | 2014-07-16 | 2014-10-08 | 辽宁石油化工大学 | Method for removing sulfide from oil product by using choline chloride/oxalic acid type eutectic solvent by virtue of oxidation-extraction integrated process |
| CN104887723A (en) * | 2015-06-18 | 2015-09-09 | 天津理工大学 | Method for extracting flavonoids from ginkgo biloba leaves with deep eutectic solvent |
| CN106474873B (en) * | 2016-11-16 | 2019-04-23 | 浙江大学 | A method of the absorption and separation ammonia from ammonia-contaminated gas |
| CN110550616A (en) * | 2019-08-26 | 2019-12-10 | 河北科技大学 | Energy-containing eutectic solvent, application thereof, metal-doped carbon quantum dot prepared from energy-containing eutectic solvent and preparation method of metal-doped carbon quantum dot |
| CN110760552B (en) * | 2019-11-27 | 2021-04-09 | 湘潭大学 | Pretreatment method for improving saccharification efficiency of lignocellulose |
| CN115594778B (en) * | 2022-11-23 | 2023-04-11 | 中国海洋大学 | Method for extracting chitin by using acidic eutectic solvent |
| CN116283516B (en) * | 2023-03-27 | 2023-11-14 | 宁夏中星显示材料有限公司 | Eutectic solvent and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| US4051219A (en) * | 1975-07-25 | 1977-09-27 | Treibacher Chemische Werke Aktiengesellschaft | Method of preparing fluorine-free rare earth metal compounds from such compounds containing fluorine |
| CN101624206A (en) * | 2009-08-07 | 2010-01-13 | 南开大学 | Preparation method and application of rare earth metal hydroxide or vanadate nano material |
| CN102965099A (en) * | 2012-11-27 | 2013-03-13 | 河北工业大学 | Novel rare earth/terpyridyl functionalized ionic liquid luminescent material |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051219A (en) * | 1975-07-25 | 1977-09-27 | Treibacher Chemische Werke Aktiengesellschaft | Method of preparing fluorine-free rare earth metal compounds from such compounds containing fluorine |
| CN101624206A (en) * | 2009-08-07 | 2010-01-13 | 南开大学 | Preparation method and application of rare earth metal hydroxide or vanadate nano material |
| CN102965099A (en) * | 2012-11-27 | 2013-03-13 | 河北工业大学 | Novel rare earth/terpyridyl functionalized ionic liquid luminescent material |
Non-Patent Citations (2)
| Title |
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| 郑燕珍,等.[BMIM][BF4]-乙腈二元体系氢键作用规律的研究.《第十六届全国光散射学术会议论文摘要集》.2011,第272页. * |
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