CN108893753B - Preparation method of imidazole dialkyl phosphate ionic liquid - Google Patents

Preparation method of imidazole dialkyl phosphate ionic liquid Download PDF

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CN108893753B
CN108893753B CN201810528669.6A CN201810528669A CN108893753B CN 108893753 B CN108893753 B CN 108893753B CN 201810528669 A CN201810528669 A CN 201810528669A CN 108893753 B CN108893753 B CN 108893753B
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imidazole
anode
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杜荣斌
刘涛
周峰
胡春潮
符成华
黄裕安
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Anqing Normal University
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Abstract

The invention discloses a preparation method of imidazole dialkyl phosphate ionic liquid, wherein at least one layer of perfluorinated cation exchange membrane is arranged in an electrolytic cellThe perfluorinated cation exchange membrane divides the electrolytic cell into a cathode chamber and an anode chamber, and the anode and the Ti-based PbO are dimensionally stabilized by DSA2Or graphite as anode and Pt as cathode, adding 1-1.5mol/L N-ethylimidazole acetonitrile solution into cathode chamber, adding 1.5-3mol/L trialkyl phosphate acetonitrile solution into anode chamber, switching on silicon rectifier power supply, electrolyzing at 75-80 deg.C and current density of 1.5-7A/dm2Electrolyzing for 6-9h under the condition of (1), taking out catholyte, separating and purifying to obtain the imidazole dialkyl phosphate ionic liquid. The method of the invention not only can effectively simplify the preparation procedure of the ionic liquid, but also the prepared ionic liquid has good application prospect in the aspects of catalysis, electrochemistry and the like.

Description

Preparation method of imidazole dialkyl phosphate ionic liquid
Technical Field
The invention relates to the technical field of ionic liquid preparation, in particular to a preparation method of imidazole dialkyl phosphate ionic liquid.
Background
The ionic liquid as a novel green solvent has excellent characteristics incomparable with a plurality of traditional organic reagents, has wide application prospect in the fields of chemical reaction and separation engineering, and particularly has wide application prospect in the separation technical fields of rectification, extraction, gas absorption and the like. In the ionic liquid variety which is most reported in the current research, trifluoromethyl sulfamide [ NTf2 ]]-Triflic acid [ OTf [ ]]-And trifluoroacetic acid [ TFA]-Ionic liquids as anions are unlikely to find industrial application in the chemical industry because of their high price. The ionic liquid taking dialkyl phosphate as anion is much cheaper, but the synthesis method has the defects of overlong reaction time, large amount of organic solvent, difficult removal of impurity ions, higher production cost and the like, and seriously restricts the large-scale production of the ionic liquid. Therefore, a method for quickly and efficiently preparing the ionic liquid is soughtThe method has very important practical significance and can greatly promote the industrial process of the ionic liquid.
In recent years, as the structure of an electrolytic cell and the material of a diaphragm are continuously improved, particularly the development and utilization of an ion exchange membrane, the current efficiency and the yield of ionic liquid are remarkably improved, and the efficiency of the electrolytic cell is greatly improved, more and more attention is paid to a method for preparing the ionic liquid by using an electrolysis technology, and particularly, the method for preparing the ionic liquid by using the electrolysis method has the advantages of mild conditions, low cost, environmental protection and the like which cannot be compared with other process routes, and becomes a hot spot for competitive development of various countries. Since not any kind of ionic liquid can be produced by an electrolytic method, how to prepare the ionic liquid taking dialkyl phosphate as anion by using the electrolytic method is a great challenge at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of imidazole dialkyl phosphate ionic liquid, which is simple in preparation process and high in yield, and the prepared ionic liquid has good application prospects in the aspects of catalysis, electrochemistry and the like.
The invention provides a preparation method of imidazole dialkyl phosphate ionic liquid, which is characterized in that at least one layer of perfluorinated cation exchange membrane is arranged in an electrolytic tank, the electrolytic tank is divided into a cathode chamber and an anode chamber by the perfluorinated cation exchange membrane, a DSA dimensionally stable anode and Ti-based PbO are adopted2Or graphite as anode, Pt as cathode, adding acetonitrile solution of N-ethylimidazole with concentration of 1-1.5mol/L into cathode chamber as catholyte, adding acetonitrile solution of trialkyl phosphate with concentration of 1.5-3mol/L into anode chamber as anolyte, switching on silicon rectifier power supply, electrolyzing at 75-80 deg.C and current density of 1.5-7A/dm2Electrolyzing for 6-9h under the condition of (1), taking out a cathode electrolyte after electrolysis is finished, and separating and purifying to obtain the imidazole dialkyl phosphate ionic liquid, wherein the trialkyl phosphate is trimethyl phosphate, triethyl phosphate or tributyl phosphate.
Preferably, the electrode reaction formula in electrolysis is as follows,
and (3) anode reaction:
Figure BDA0001676649820000021
and (3) cathode reaction:
Figure BDA0001676649820000022
r is CH3、C2H5And C4H9。
In the preparation method, trialkyl phosphate carries positive charge when the anode chamber is de-energized, and passes through a perfluorinated cation exchange membrane under the action of an electric field, so that target ionic liquid is generated between the cathode chamber and N-ethylimidazole under the catalytic action of a platinum electrode.
Preferably, the catholyte and anolyte concentrations in the cathode and anode compartments of the cell are maintained constant during electrolysis.
Preferably, in the electrolysis process, the two liquid storage tanks are respectively filled with acetonitrile solution of N-ethylimidazole with the concentration of 1-1.5mol/L as cathode supplementary solution and acetonitrile solution of trialkyl phosphate with the concentration of 1.5-3mol/L as anode supplementary solution, the cathode chamber of the electrolytic cell is respectively communicated with one liquid storage tank and the anode chamber of the electrolytic cell is communicated with the other liquid storage tank through two circulating pumps, and the two circulating pumps respectively and continuously exchange the catholyte and the anolyte with the cathode supplementary solution and the anode supplementary solution, so that the catholyte and the anolyte in the cathode chamber and the anode chamber of the electrolytic cell are kept at stable concentrations.
Preferably, the pump flow rate of the circulation pump is 1-3L/h, preferably, the pump flow rate of the circulation pump is 1.5L/h.
Preferably, the current efficiency of the electrolysis process is 30-40%.
Preferably, after the electrolysis is completed, taking out the cathode electrolyte, and putting the cathode electrolyte into a rotary evaporator for rotary evaporation to obtain the imidazole dialkyl phosphate ionic liquid.
The invention has the beneficial effects that:
(1) the preparation method has the advantages of simple process flow, low requirement on conditions, easy control of the preparation process, less time consumption, low cost, high yield of the obtained product and huge industrial application potential.
(2) Compared with other ionic liquids, the imidazole dialkyl phosphate ionic liquid prepared by the preparation method has better application prospects in the aspects of catalysis, electrochemistry and the like.
Drawings
FIG. 1 is a diagram of an apparatus for preparing imidazole dialkyl phosphate ionic liquid.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of imidazole dialkyl phosphate ionic liquid comprises the steps of electrolyzing in an electrolytic bath comprising a cathode chamber and an anode chamber, arranging a layer of perfluorinated cation exchange membrane between the cathode chamber and the anode chamber, adding 1.2mol/L N-ethylimidazole acetonitrile solution into the cathode chamber by taking a DSA dimensionally stable anode as an anode and Pt as a cathode, adding 1.6mol/L trimethyl phosphate acetonitrile solution into the anode chamber, switching on a silicon rectifier power supply, and carrying out electrolysis at 75 ℃ and at a current density of 2.5A/dm2Electrolyzing for 6.5H under the condition of (1), taking out catholyte after the electrolysis is finished, separating and purifying to obtain 1-ethyl-3-methylimidazol dimethyl phosphate ionic liquid with the purity of 83wt percent and H1NMR：8.706(s，1H)，7.485(s，1H)，7.419(s，1H)，4.211(q，2H)，3.885(s，3H)，3.581(s，3H)，3.554(s，3H)，1.491(t，3H)。
Example 2
A preparation method of imidazole dialkyl phosphate ionic liquid comprises the steps of carrying out electrolysis in an electrolytic cell comprising a cathode chamber and an anode chamber, arranging a layer of perfluorinated cation exchange membrane between the cathode chamber and the anode chamber, adding 1mol/L acetonitrile solution of N-ethylimidazole as a cathode electrolyte into the cathode chamber of the electrolytic cell by using graphite as an anode and Pt as a cathode, and dissolving 3mol/L triethyl phosphate in acetonitrileAdding the solution as anolyte into the anode chamber of the electrolytic cell, connecting with a silicon rectifier power supply, and electrolyzing at 75 deg.C and 7A/dm of current density2Electrolyzing for 6H under the condition of the current efficiency of 30 percent, taking out the cathode electrolyte after the electrolysis is finished, putting the cathode electrolyte into a rotary evaporator for rotary evaporation to obtain the 1-ethyl-3-ethylimidazole diethyl phosphate ionic liquid with the purity of 85 percent by weight and H1NMR：8.768(s，1H),7.495(s，1H)，7.495(s，1H)，4.237(t，2H)，4.201(s，2H)，3.933(m，4H)，1.503(t，6H)，1.266(t，6H)；
The electrolyte in the cathode chamber and the electrolyte in the anode chamber of the electrolytic cell are forcibly circulated by adopting circulating pumps respectively, specifically, 1mol/L acetonitrile solution of N-ethylimidazole is respectively filled in the two liquid storage tanks as a catholyte, 3mol/L acetonitrile solution of triethyl phosphate is used as an anolyte, the catholyte and the anolyte are respectively conveyed to the cathode chamber and the anode chamber of the electrolytic cell by the two circulating pumps, then the catholyte and the anolyte in the cathode chamber and the anode chamber are respectively returned to the original liquid storage tanks by the circulating pumps, so that the electrolytes in the cathode chamber and the anode chamber are respectively circulated repeatedly, and the pump flow of the circulating pumps is controlled to be 1L/h.
Example 3
A process for preparing imidazole dialkyl phosphate ionic liquid includes such steps as electrolyzing in an electrolyzer consisting of cathode and anode chambers, arranging a layer of perfluoro cation exchange membrane between said cathode and anode chambers, and preparing Ti-base PbO2Taking Pt as a cathode as an anode, adding 1.5mol/L acetonitrile solution of N-ethylimidazole as a catholyte into a cathode chamber of an electrolytic cell, adding 1.5mol/L acetonitrile solution of tributyl phosphate as an anolyte into an anode chamber of the electrolytic cell, switching on a silicon rectifier power supply, and carrying out electrolysis at the temperature of 80 ℃ and the current density of 1.5A/dm2Electrolyzing for 9H under the condition of 40 percent of current efficiency, taking out the cathode electrolyte after the electrolysis is finished, putting the cathode electrolyte into a rotary evaporator for rotary evaporation to obtain the 1-butyl-3-ethylimidazole dibutyl phosphate ionic liquid with the purity of 90 weight percent and H1NMR：8.777(s，1H)，7.506(s，1H)，7.490(s，1H)，4.240(m，4H)，3.887(q，4H)，1.857(m，2H)，1.636(t，4H)，1.525(t，3H)，1.418(m，6H)，0.943(s，3H)，0.925(s，3H)，0.906(s，3H)；
The electrolyte in the cathode chamber and the electrolyte in the anode chamber of the electrolytic cell are respectively forced to circulate by adopting circulating pumps, specifically, 1.5mol/L N-ethylimidazole acetonitrile solution is respectively filled in two liquid storage tanks as catholyte, 1.5mol/L tributyl phosphate acetonitrile solution is used as anolyte, the catholyte and the anolyte are respectively conveyed to the cathode chamber and the anode chamber of the electrolytic cell by two circulating pumps, and then the catholyte and the anolyte in the cathode chamber and the anode chamber are respectively returned to the original liquid storage tanks by the circulating pumps, so that the electrolytes in the cathode chamber and the anode chamber respectively circulate repeatedly and continuously, and the pump flow of the circulating pumps is controlled to be 3L/h.
Example 4
A preparation method of imidazole dialkyl phosphate ionic liquid comprises the steps of carrying out electrolysis in an electrolytic cell comprising a cathode chamber and an anode chamber, arranging a layer of perfluorinated cation exchange membrane between the cathode chamber and the anode chamber, adding N-ethylimidazole acetonitrile solution with the concentration of 1.5mol/L as catholyte into the cathode chamber of the electrolytic cell by taking a DSA dimensionally stable anode as an anode and Pt as a cathode, adding triethyl phosphate acetonitrile solution with the concentration of 2mol/L as anolyte into the anode chamber of the electrolytic cell, switching on a silicon rectifier power supply, and carrying out electrolysis at the temperature of 78 ℃ and at the current density of 7A/dm2Electrolyzing for 7 hours under the condition of (1), controlling the current efficiency to be 35%, taking out catholyte after the electrolysis is finished, putting the catholyte into a rotary evaporator for rotary evaporation to obtain 1-ethyl-3-ethylimidazole diethyl phosphate ionic liquid with the purity of 90 wt%;
the electrolyte in the cathode chamber and the electrolyte in the anode chamber of the electrolytic cell are respectively forced to circulate by adopting circulating pumps, specifically, 1.5mol/L N-ethylimidazole acetonitrile solution is respectively filled in two liquid storage tanks as a catholyte, 2mol/L triethyl phosphate acetonitrile solution is used as an anolyte, the catholyte and the anolyte are respectively conveyed to the cathode chamber and the anode chamber of the electrolytic cell by two circulating pumps, then the catholyte and the anolyte in the cathode chamber and the anode chamber are respectively returned to the original liquid storage tanks by the circulating pumps, so that the electrolytes in the cathode chamber and the anode chamber respectively circulate repeatedly and continuously, and the pump flow of the circulating pumps is controlled to be 1.5L/h.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The preparation method of the imidazole dialkyl phosphate ionic liquid is characterized in that at least one layer of perfluorinated cation exchange membrane is arranged in an electrolytic tank, the electrolytic tank is divided into a cathode chamber and an anode chamber by the perfluorinated cation exchange membrane, a DSA dimensionally stable anode and Ti-based PbO are adopted2Or graphite as anode, Pt as cathode, adding acetonitrile solution of N-ethylimidazole with concentration of 1-1.5mol/L into cathode chamber as catholyte, adding acetonitrile solution of trialkyl phosphate with concentration of 1.5-3mol/L into anode chamber as anolyte, switching on silicon rectifier power supply, electrolyzing at 75-80 deg.C and current density of 1.5-7A/dm2Electrolyzing for 6-9h under the condition of (1), taking out a cathode electrolyte after electrolysis is finished, and separating and purifying to obtain the imidazole dialkyl phosphate ionic liquid, wherein the trialkyl phosphate is trimethyl phosphate, triethyl phosphate or tributyl phosphate.
2. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 1, which is characterized in that an electrode reaction formula during electrolysis is as follows,
and (3) anode reaction:
Figure FDA0002108285240000011
and (3) cathode reaction:
Figure FDA0002108285240000012
r is CH3、C2H5And C4H9。
3. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 1 or 2, wherein the concentrations of the catholyte and the anolyte in the cathode chamber and the anode chamber of the electrolytic cell are kept stable during the electrolysis.
4. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 3, wherein in the electrolysis process, the two liquid storage tanks are respectively filled with 1-1.5mol/L acetonitrile solution of N-ethylimidazole as a cathode supplementary solution and 1.5-3mol/L acetonitrile solution of trialkyl phosphate as an anode supplementary solution, the cathode chamber of the electrolytic cell is respectively communicated with one liquid storage tank, the anode chamber of the electrolytic cell is communicated with the other liquid storage tank, and the two circulating pumps respectively and continuously exchange the catholyte and the anolyte with the cathode supplementary solution and the anode supplementary solution so as to keep the concentrations of the catholyte and the anolyte in the cathode chamber and the anode chamber of the electrolytic cell stable.
5. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 4, wherein the pump flow of a circulating pump is 1-3L/h.
6. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 5, wherein the pump flow of a circulating pump is 1.5L/h.
7. The preparation method of the imidazole dialkyl phosphate ionic liquid according to any one of claims 1 to 2, wherein the current efficiency in the electrolysis process is 30 to 40 percent.
8. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 3, wherein the current efficiency in the electrolysis process is 30-40%.
9. The preparation method of the imidazole-based dialkyl phosphate ionic liquid according to any one of claims 1 to 2, characterized in that after the electrolysis is completed, the catholyte is taken out and put into a rotary evaporator for rotary evaporation to obtain the imidazole-based dialkyl phosphate ionic liquid.
10. The preparation method of the imidazole dialkyl phosphate ionic liquid according to claim 3, wherein after the electrolysis is completed, the catholyte is taken out and put into a rotary evaporator for rotary evaporation, so as to obtain the imidazole dialkyl phosphate ionic liquid.
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Publication number Priority date Publication date Assignee Title
CN1675230A (en) * 2002-08-16 2005-09-28 Cytec加拿大股份有限公司 Phosphonium and imidazolium salts and methods of their preparation
CN100366799C (en) * 2001-11-21 2008-02-06 塞克姆公司 Electrochemical process for producing ionic liquids

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US9493882B2 (en) * 2010-07-21 2016-11-15 Ceramatec, Inc. Custom ionic liquid electrolytes for electrolytic decarboxylation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100366799C (en) * 2001-11-21 2008-02-06 塞克姆公司 Electrochemical process for producing ionic liquids
CN1675230A (en) * 2002-08-16 2005-09-28 Cytec加拿大股份有限公司 Phosphonium and imidazolium salts and methods of their preparation

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