CN102659607A - Preparation method of quaternary ammonium ionic liquid - Google Patents
Preparation method of quaternary ammonium ionic liquid Download PDFInfo
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- CN102659607A CN102659607A CN2012101205599A CN201210120559A CN102659607A CN 102659607 A CN102659607 A CN 102659607A CN 2012101205599 A CN2012101205599 A CN 2012101205599A CN 201210120559 A CN201210120559 A CN 201210120559A CN 102659607 A CN102659607 A CN 102659607A
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Abstract
The invention relates to a preparation method of quaternary ammonium ionic liquid, belongs to the field of chemical synthesis and solves the problems of complicated process and long reaction period in the conventional preparation method of the quaternary ammonium ionic liquid. The method comprises the following steps: reacting quaternary ammonium salt with alkali solution, generating anion exchange reaction to generate quaternary ammonium base and generating acid and alkali neutralization reaction with corresponding phosphonic acid anions or carboxylic acid anions to generate the quaternary ammonium ionic liquid. The method has the advantages of simple preparation process, short time, high product conversion rate and easiness in purification, an alcohol solvent can be recycled through distillation, extraction and other methods. The preparation method of the ionic liquid is wide in applicable scope. Compared with the prior art, the preparation method has briefer preparation steps, and the large-scale production is easy.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of quaternary amines preparation method of ionic liquid.
Technical background
Ionic liquid is the liquid functional materials of a type " can design ".They have the liquid temperature wide ranges.Steam forces down, not volatile, density big, some organism, inorganics are had advantages such as good dissolving ability, electrochemical window is wide, dissolving power is strong.In traditional industry, quaternary ammonium salt has certain surfactivity, biological activity and antimicrobial acivity, as the metal extraction agent, and phase-transfer catalyst, tensio-active agent and static inhibitor and widespread use.Compare with glyoxaline ion liquid with pyridine; With quaternary ammonium salt is that cationic ionic liquid has higher thermostability and chemicalstability, unique dissolving power and solvent property, and partial ion liquid has realized commercialization and has been widely used in phase-transfer catalyst; Solvent; Lubricant, gas trapping agent, coating material and chemical probing agent.[Bradaric?et?al.，2003；Weng?et?al.，2006；Pernak?et?al.，2006；Yuan?et?al.，2007；Fraser?&?MacFarlane，2009；Werner?et?al.，2010].
The following method of the general employing of the preparation of ion liquid of quaternaries
[R′PR
3]
+[X]
-+MA→[R′PR
3]
+[A]
-+MX
[R′NR
3]
+[X]
-+HA+MOH→[R′NR
3]
+[A]
-+MX+H
2O
For example: Mikkloa etc. [J.P.Mikkola, et al., Green Chem., 2006,8,250] are positively charged ion with methyl trioctylphosphine ammonium chloride, and corresponding sodium salts or ammonium salt are negatively charged ion, have obtained a series of hydrophobic ionic liquids through replacement(metathesis)reaction; [Robertson such as Robertson; A.L.Seddon; K.R.2002.WO 02/079212 A1] use tetradecyl three hexyl phosphorus chloride and two (2,4,4 tri-methyl-amyl) phosphonic acids (commodity are called CyphosIL104) and make pair quaternary phosphonium ionic liquids through anion exchange method.[Cassol C.C.et al. such as Cassol; Adv.Synth.Catal., 2006,348; 243.] use the N-alkyl imidazole and the alkyl sulfuric ester prepared in reaction has gone out the alkyl imidazole alkyl-sulphate, and generate multiple corresponding hydrophobic ionic liquid through ion exchange reaction.At present, the ionic liquid of method for preparing be mainly imidazoles, pyridines, quaternary amines and season phosphine class ionic liquid, but be based on the anionic bi-functional preparation method of ionic liquid report of quaternary ammonium salt cationic and organic phospho acid or organic carboxyl acid also seldom; And complex process is a kind of difunctionalization of quaternary ammonium preparation method of ionic liquid of CN200910217922.7 like number of patent application, and this technology is at first with quaternary ammonium salt and sodium alkoxide reaction; Hydrolysis again; Generate corresponding quaternary ammonium oxyhydroxide, further, generate corresponding bi-functional ionic liquid with the organic phospho acid reaction; This preparation method can obtain the very high product of purity; But complex process, reaction time is long, can't accomplish scale production.
Summary of the invention
The objective of the invention is in order to solve long defective of existing quaternary ammonium preparation method of ionic liquid complex process, reaction time, and a kind of quaternary amines preparation method of ionic liquid is provided.
A kind of quaternary amines preparation method of ionic liquid comprises the steps:
Step 1:, obtain clarified liq R with quaternary ammonium salt and alkali alcosol reaction
1R
2R
3R
4N
+OH
-The alkali in the described alkali alcosol and the mol ratio of quaternary ammonium salt are 1～4: 1, and the chemical formula of described quaternary ammonium salt is R
1R
2R
3R
4N
+Cl
-, positively charged ion is a methyl Xinji ammonium ion, negatively charged ion is a cl ions, wherein R
1Be methyl, R
2, R
3, R
4Be octyl group;
Step 2: the clarified liq R that step 1 is obtained
1R
2R
3R
4N
+OH
-With the HA reaction, obtain the quaternary amines ionic liquid; Described R
1R
2R
3R
4N
+OH
-With the mol ratio of HA be 1: 0.8, described HA is for containing the anionic compound of phosphonic acid based or carboxylic-acid.
The described reaction times of step 1 is 1-3 hour.
The described alkali of step 1 is Lithium Hydroxide MonoHydrate, Pottasium Hydroxide or sodium hydroxide.
The described alcohol of step 1 is ethanol or Virahol.
In the described alkali alcosol of step 1, the quality of alkali is 1g: 5～20ml with the volume ratio of alcohol.
The described reaction times of step 2 is 1-3 hour.
The described HA of step 2 is 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507); Di-(2-ethylhexyl)phosphoric acid (P204), two-(2; 4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), secondary octyl phenylium (CA-12), secondary nonylphenoxyacetic acid (CA-100).
Beneficial effect
A kind of quaternary amines preparation method of ionic liquid of the present invention is that anion exchange reaction generation quaternary ammonium hydroxide is taken place for quaternary ammonium salt and alkaline solution reaction, generates the quaternary amines ionic liquid with corresponding phosphonic acid based or the reaction of carboxylic-acid negatively charged ion generation acid-base neutralisation again.The present invention can synthesize the quaternary amines ionic liquid through two step replacement(metathesis)reactions, and the preparation process is simple, and the time is short, and energy consumption is low, and reaction conditions is gentle, under normal temperature, normal pressure, just can accomplish; Product yield is high, is prone to purifying, the R of ion exchange method preparation
1R
2R
3R
4N
+OH
-Productive rate is very high, and filtration can be removed the by product deposition fully, and acid-base neutralisation method process reaction speed is fast, and productive rate is high; Solvent alcohol can carry out recycle through methods such as distillation extractions, and such ionic liquid preparation method scope of application is extensive, compared with prior art has more succinct preparation process, is produced on a large scale.
Description of drawings
Fig. 1 is the embodiment of the invention 1 [C
25H
54N] [C
16H
34POO] nuclear magnetic spectrogram;
Fig. 2 is the embodiment of the invention 2 [C
25H
54N] [C
16H
34O
2POO] nuclear magnetic spectrogram.
Embodiment
A kind of quaternary amines preparation method of ionic liquid comprises the steps:
1, alkali MOH is dissolved in the alcoholic solution, obtains alkali alcosol, the quality of described alkali is 1g: 5～20ml with the volume ratio of alcohol; Quaternary ammonium chloride is added dropwise in the above-mentioned alkali alcosol; The alkali in the described alcoholic solution and the mol ratio of quaternary ammonium chloride are 1～4: 1, and at room temperature reaction 1-3 hour, product was through filtering; Filtering precipitate gets clarified liq R
1R
2R
3R
4N
+OH
-The chemical formula of described quaternary ammonium salt is R
1R
2R
3R
4N
+C1
-, positively charged ion is a methyl Xinji ammonium ion, negatively charged ion is a cl ions, wherein R
1Be methyl, R
2, R
3, R
4Be octyl group; Described alkali is for being Lithium Hydroxide MonoHydrate, Pottasium Hydroxide or sodium hydroxide, and alcohol is ethanol or Virahol;
2, the clarified liq R that step 1 is obtained
1R
2R
3R
4N
+OH
-With HA at stirring at room 1-3 hour, described R
1R
2R
3R
4N
+OH
-With the mol ratio of HA be 1: 0.8, get upper strata ionic liquid organic phase, wash 3 times with deionized water, solvent alcohol (ethanol or Virahol) remove is reclaimed in underpressure distillation then, product vacuum-drying obtains the quaternary amines ionic liquid; Described HA is for containing the anionic compound of phosphonic acid based or carboxylic-acid; Be 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507); Di-(2-ethylhexyl)phosphoric acid (P204), two-(2; 4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), secondary octyl phenylium (CA-12), secondary nonylphenoxyacetic acid (CA-100).
The ion liquid synthetic route of a kind of quaternary amines is following, the clarified liq R that (1) obtains for step 1 in the formula
1R
2R
3R
4N
+OH, (2) are final product quaternary amines ionic liquid.
The quaternary amines ionic liquid that obtains through present method is: methyl trioctylammonium di-(2-ethylhexyl)phosphoric acid ionic liquid ([C
25H
54N] [C
16H
34POO]), methyl trioctylammonium 2-ethylhexyl single 2-ethyl hexyl phosphonic acids ionic liquid ([C
25H
54N] [C
16H
34O
2POO]), methyl trioctylammonium two (2,4,4 ,-tri-methyl-amyl) phosphonic acids ([C
25H
54N] [C
16H
34POO]), methyl trioctylammonium secondary octyl phenylium ionic liquid [C
25H
54N] [C
15H
23OCOO], the secondary nonylphenoxyacetic acid ionic liquid of methyl trioctylammonium [C
25H
54N] [C
16H
25OCOO], the concrete structure formula is following:
Methyl trioctylammonium di-(2-ethylhexyl)phosphoric acid ionic liquid ([C
25H
54N] [C
16H
34POO]):
Methyl trioctylammonium 2-ethylhexyl single 2-ethyl hexyl phosphonic acids ionic liquid ([C
25H
54N] [C
16H
34O
2POO]):
Methyl trioctylammonium two (2,4,4 ,-tri-methyl-amyl) phosphonic acids ([C
25H
54N] [C
16H
34POO]):
Methyl trioctylammonium secondary octyl phenylium ionic liquid [C
25H
54N] [C
15H
23OCOO]:
The secondary nonylphenoxyacetic acid ionic liquid of methyl trioctylammonium [C
25H
54N] [C
16H
25OCOO]:
1, with 5.6g, 0.10mol Pottasium Hydroxide is dissolved in 56ml ethanol, obtains alkali alcosol, with 40g, and 0.1mol quaternary ammonium chloride [C
25H
54N] [Cl] be added dropwise in the above-mentioned alkali alcosol, in, stirring at room 1 hour, filtering Repone K deposition must be clarified ionic liquid [C
25H
54N] [OH], productive rate 99%, product detects through chromatography of ions, and recording wherein, chloride ion content is 336ppm;
2,0.08mol di-(2-ethylhexyl)phosphoric acid (P204) is added the 0.1mol [C that obtains
25H
54N] in [OH], stirring at room 1 hour is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains methyl trioctylammonium di-(2-ethylhexyl)phosphoric acid ionic liquid ([C
25H
54N] [C
16H
34POO]), productive rate 92.5%.
The product nuclear-magnetism characterization result that embodiment 1 obtains is:
1H?NMR?：0.856-0.894(m，21H)，1.269-1.335(m，46H)，1.431-1.455(m，2H)，1.524(m，2H)，1.647(m，4H)，3.289(s，3H)，3.366(m，6H)，3.757-3.765(m，4H).
13C?NMR：10.66(2C)，13.70，13.74，13.80，22.11(3C)，22.28(3C)，22.33(3C)，22.87(3C)，23.06(3C)，26.09(2C)，28.77，28.81(2C)，28.91(2C)，28.95，29.12，29.16，29.85，31.38，31.54，40.14，48.59，60.93，67.32，67.35(2C).
1, identical with embodiment 1 step 1;
2,0.08mol is gone into 2-ethylhexyl single 2-ethyl hexyl phosphonic acids (P507) and add the 0.1mol [C that obtains
25H
54N] in [OH], stirring at room 2 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains methyl trioctylammonium 2-ethylhexyl single 2-ethyl hexyl phosphonic acids ionic liquid ([C
25H
54N] [C
16H
34O
2POO]), productive rate 87.6%.
The product nuclear-magnetism characterization result that embodiment 2 obtains is:
1H?NMR：0.822-0.850(m，3H)，0.863-0.894(m，18H)，1.268-1.300(m，32H)，1.340-1.371(m，14H)，1.492(m，2H)，1.637(m，2H)，1.780(m，4H)，3.327(s，3H)，3.415-30443(m，6H)，3.694(m，4H).
13C?NMR?：65.87，61.00(3C)，48.82，40.55，34.80，33.75，31.65，31.49(2C)，30.0(2C)，29.26，29.22，29.07(2C)，29.02(2C)，28.99(2C)，28.87(2C)，28.58(2C)，26.42(2C)，26.22(2C)，23.26，23.06，22.46，22.40，22.21，14.06，13.95，13.87，13.83(2C)，10.86，10.25.
Embodiment 3
1, with 8.0g, 0.2mol sodium hydroxide is dissolved in the 160ml Virahol, obtains alkali alcosol, with 40g, and 0.1mol quaternary ammonium chloride [C
25H
54N] [Cl] be added dropwise in the above-mentioned alkali alcosol, stirring at room 3 hours, filtering sodium-chlor deposition must be clarified ionic liquid [C
25H
54N] [OH], productive rate 95%, product detects through chromatography of ions, and recording wherein, chloride ion content is 336ppm;
2,0.08mol two (2,4,4 ,-tri-methyl-amyl) phosphonic acids (Cyanex272) are added the 0.1mol [C that obtains
25H
54N] in [OH], stirring at room 3 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent Virahol then, product vacuum-drying obtains methyl trioctylammonium two (2,4,4 ,-tri-methyl-amyl) phosphonic acids ([C
25H
54N] [C
16H
34POO]), productive rate 85.7%.
The product nuclear-magnetism characterization result that embodiment 3 obtains is:
1H?NMR：0.86(t，J＝1.2Hz，9H)，1.18(s，3H)，1.26(s，30H)，1.33(s，16H)，1.61(s，6H)，3.26(s，3H)，3.378～3.419(t，J＝8.0Hz，6H)，4.44(s，2H)，6.892(d，J＝7.2Hz，2H)，7.125(m，2H).
13C?NMR：13.81，22.35，26.11，26.78，27.46，28.81，29.03，29.38，31.62，35.34，41.31，43.18，48.47，51.73，54.03，61.05，62.04，68.09，113.84，126.81，139.06，156.64，173.12.
1, identical with embodiment 3 steps 1;
2,0.08mol secondary octyl phenylium (CA-12) adds the 0.1mol [C that obtains
25H
54N] in [OH], stirring at room 2 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent Virahol then, product vacuum-drying obtains methyl trioctylammonium secondary octyl phenylium ionic liquid ([C
25H
54N] [C
15H
23OCOO]), productive rate 79.6%.
The product nuclear-magnetism characterization result that embodiment 4 obtains is:
1H?NMR：0.664-0.710(m，3H)，0.719-0.7640(m，9H)，1.057-1.175(m，28H)，1.185-1.251(m，10H)，1.341-1.465(m，2H)，1.633-1.712(m，6H)，3.400(s，3H)，3.602-3.611(m，6H)，4.793-4.847(m，2H)，6.868-6.986(m，1H)，7.031-7.054(m，1H)，7.088(s，1H)，7.150-7.163(m，1H).
13C?NMR：173.04，128.70，137.99，126.73，120.05，115.45，115.41，70.36，61.58(3C)，48.38，32.19，32.04(2C)，29.86，29.84(2C)，29.66(2C)，29.61(2C)，29.53(2C)，29.46(3C)，26.84(5C)，23.04(2C)，22.97(2C)，22.72，14.41，14.38，14.34.
1, with 9.6g, the 0.40mol Lithium Hydroxide MonoHydrate is dissolved in 48ml ethanol, obtains alkali alcosol, with 40g, and 0.1mol quaternary ammonium chloride [C
25H
54N] [Cl] be added dropwise in the above-mentioned alkali alcosol, stirring at room 2 hours, filtering lithium chloride deposition must be clarified [C
25H
54N] [OH] ionic liquid, productive rate 96%, product detects through chromatography of ions, and recording wherein, chloride ion content is 462ppm;
2, the secondary nonylphenoxyacetic acid of 0.08mol (CA-100) is added the 0.1mol [C that obtains
25H
54N] in [OH], stirring at room 3 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains the secondary nonylphenoxyacetic acid ionic liquid of methyl trioctylammonium ([C
25H
54N] [C
16H
25OCOO]), productive rate 82.4%.
The product nuclear-magnetism characterization result that embodiment 5 obtains is:
1H?NMR：0.86(t，J＝1.2Hz，9H)，1.18(m，3H)，1.26(m，30H)，1.33(m，16H)，1.61(m，6H)，3.26(s，3H)，3.378～3.419(t，J＝8.0Hz，6H)，4.44(s，2H)，6.892(d，J＝7.2Hz，2H)，7.125(m，2H).
13C?NMR：13.81，22.35，26.11，26.78，27.46，28.81，29.03，29.38，31.62，35.34，41.31，43.18，48.47，51.73，54.03，61.05，62.04，68.09，113.84，126.81，139.06，156.64，173.12。
Claims (7)
1. a quaternary amines preparation method of ionic liquid is characterized in that, comprises the steps:
Step 1:, obtain clarified liq R with quaternary ammonium salt and alkali alcosol reaction
1R
2R
3R
4N
+OH
-The alkali in the described alkali alcosol and the mol ratio of quaternary ammonium salt are 1～4: 1, and the chemical formula of described quaternary ammonium salt is R
1R
2R
3R
4N
+Cl
-, positively charged ion is a methyl Xinji ammonium ion, negatively charged ion is a cl ions, wherein R
1Be methyl, R
2, R
3, R
4Be octyl group;
Step 2: the clarified liq R that step 1 is obtained
1R
2R
3R
4N
+OH
-With the HA reaction, obtain the quaternary amines ionic liquid; Described R
1R
2R
3R
4N
+OH
-With the mol ratio of HA be 1: 0.8, described HA is for containing the anionic compound of phosphonic acid based or carboxylic-acid.
2. a kind of quaternary amines preparation method of ionic liquid according to claim 1 is characterized in that the described reaction times of step 1 is 1-3 hour.
3. a kind of quaternary amines preparation method of ionic liquid according to claim 1 is characterized in that the described alkali of step 1 is Lithium Hydroxide MonoHydrate, Pottasium Hydroxide or sodium hydroxide.
4. a kind of quaternary amines preparation method of ionic liquid according to claim 1 is characterized in that the described alcohol of step 1 is ethanol or Virahol.
5. a kind of quaternary amines preparation method of ionic liquid according to claim 1 is characterized in that, in the described alkali alcosol of step 1, the quality of alkali is 1g: 5～20ml with the volume ratio of alcohol.
6. a kind of quaternary amines preparation method of ionic liquid according to claim 1 is characterized in that the described reaction times of step 2 is 1-3 hour.
7. a kind of quaternary amines preparation method of ionic liquid according to claim 1; It is characterized in that; The described HA of step 2 is 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester; Di-(2-ethylhexyl)phosphoric acid, two-(2,4, the 4-tri-methyl-amyl) phosphonic acids, secondary octyl phenylium, secondary nonylphenoxyacetic acid.
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Cited By (5)
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| CN104946888A (en) * | 2015-05-25 | 2015-09-30 | 厦门稀土材料研究所 | Extractant for yttrium extraction separation and extraction separation method thereof |
| CN105655637A (en) * | 2014-10-24 | 2016-06-08 | 微宏动力系统（湖州）有限公司 | Lithium ion battery ion liquid and preparation method, and lithium ion battery electrolyte |
| CN109879909A (en) * | 2019-03-07 | 2019-06-14 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of big partial size dialkylphosphinic salts |
| CN112608241A (en) * | 2020-12-03 | 2021-04-06 | 江西理工大学 | Preparation method of trioctylmethylammonium oxalate |
| AU2016202668B2 (en) * | 2015-05-25 | 2021-05-13 | Xiamen Institute Of Rare Earth Materials | Extractant and method for extracting and separating yttrium |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655637A (en) * | 2014-10-24 | 2016-06-08 | 微宏动力系统（湖州）有限公司 | Lithium ion battery ion liquid and preparation method, and lithium ion battery electrolyte |
| CN104946888A (en) * | 2015-05-25 | 2015-09-30 | 厦门稀土材料研究所 | Extractant for yttrium extraction separation and extraction separation method thereof |
| AU2016202668B2 (en) * | 2015-05-25 | 2021-05-13 | Xiamen Institute Of Rare Earth Materials | Extractant and method for extracting and separating yttrium |
| CN109879909A (en) * | 2019-03-07 | 2019-06-14 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of big partial size dialkylphosphinic salts |
| CN112608241A (en) * | 2020-12-03 | 2021-04-06 | 江西理工大学 | Preparation method of trioctylmethylammonium oxalate |
| CN112608241B (en) * | 2020-12-03 | 2023-06-30 | 江西理工大学 | Preparation method of trioctyl ammonium methyl oxalate |
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Application publication date: 20120912 |