CN1569801A - Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor - Google Patents
Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor Download PDFInfo
- Publication number
- CN1569801A CN1569801A CN 200410018045 CN200410018045A CN1569801A CN 1569801 A CN1569801 A CN 1569801A CN 200410018045 CN200410018045 CN 200410018045 CN 200410018045 A CN200410018045 A CN 200410018045A CN 1569801 A CN1569801 A CN 1569801A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- acetone
- catalytic synthesis
- diacetic acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an ionic liquid bis-ammonium acetate and catalytic synthesis process, wherein the acetate comprises small cationic inorganic ammonium NH4++ and rather big anion double acetate radical (CH#-[3]COO)#-[2]H#+[-], the catalytic method for synthesizing the ionic liquid consists of mixing acetic acid, mixing the solid acid catalyst and solvent, heating and stirring, reacting, neutralizing with acid and alkali, separating, decompression distilling.
Description
Technical field
The present invention relates to a kind of ionic liquid diacetic acid ammonium and process for catalytic synthesis thereof, belong to new chemical material and preparing technical field thereof.
Background technology
Ionic liquid is meant by the yin, yang ion to be formed, and fusing point is lower than 100 ℃ material.Because the temperature range that this class material has liquid state is wide, can reach 300 ℃; Steam forces down, and not volatile, density is big, Heat stability is good; Can regulate its physical and chemical performance by changing the yin, yang ion; Electrochemical window is wide, and be approximately characteristics such as 4V and be widely used in solvent and catalyzer in the organic synthesis, solvent in the chemical separation and extraction agent, ionogen in the electrochemistry and medium, and shown good performance.In recent years, the continuous deterioration of environmental quality is strong day by day to the requirement of the greenization of chemical process, thereby can make the ion liquid research of chemical process greenization obtain swift and violent development.The ionic liquid composition of being reported at present is mainly the little negatively charged ion of big positively charged ion and forms.Li Ruxiong etc. are in " chemical industry progress ", 2002 the 21st the 1st phases of volume, speak of in 43-48 page or leaf " green solvent-ion liquid preparation and application " literary composition, forming ion liquid positively charged ion at present has four classes: quaternary ammonium alkyl, season phosphine, alkyl imidazole and alkyl pyridine positively charged ion, negatively charged ion is: Cl
-, SO
4 2-, NO
3 -, Br
-, BF
4 -, PF
6 -, (CF
3SO
2)
2N
-, CF3COO
--Deng.By the various combination between these positively charged ions and the negatively charged ion, mix the ionic liquid that differs from one another.There are some weak points in existing ion liquid preparation: scarcity of raw material, cost are higher, are generally more than 2 times of common solvent; The step of preparation is more, difficult, and the purifying products difficulty is not suitable for large-scale industrial production and uses; Normally quaternary ammonium salt and aluminum chloride coupling pollute easily, influence its application aspect green chemical industry.
Summary of the invention
First technical problem that the present invention will solve is to propose a kind of ionic liquid diacetic acid ammonium, it is characterized in that this ionic liquid is by the inorganic ammonium NH of less positively charged ion
4 +With bigger negatively charged ion diacetic acid root (CH
3COO)
2H
-Form, molecular formula is (CH
3COO)
2HNH
4
Second technical problem that the present invention will solve provides the process for catalytic synthesis of ionic liquid diacetic acid ammonium.The present invention makes above technical problem be resolved by the following technical solutions: with glacial acetic acid, solid acid catalyst and solvent, and heated and stirred, a step catalytic synthesis, after acid-base neutralisation separates, underpressure distillation makes ionic liquid diacetic acid ammonium.
Now describe technical scheme of the present invention in detail.A kind of process for catalytic synthesis of ionic liquid diacetic acid ammonium is characterized in that, the concrete operations step:
The first step reaction mass is prepared
The solid acid catalyst of the glacial acetic acid of 100 parts of weight of reaction mass, 1～26 part of weight and the organic solvent of 35～160 parts of weight are joined in the reactor, and solid acid catalyst is solid super-strong acid SO
4 2-/ ZrO
2, SO
4 2-/ ZSM-5, HZSM-5, activated clay, montmorillonite and heteropolyacid such as phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid, tungsten acid, organic solvent are single solvent such as benzene, toluene, ethyl acetate, acetone, acetonitrile, ether, dimethylbenzene, vinyl cyanide, chloroform, hexanaphthene; Or by two kinds of single solvent blended mixed solvents such as acetone and vinyl cyanide, acetone and chloroform, ethyl acetate and vinyl cyanide, benzene and toluene, acetonitrile and benzene, acetone and acetonitrile, the mol ratio of two kinds of single solvents is (1～5): 1;
Second goes on foot catalytic synthesis
The reaction mass of the first step is at 40～90 ℃ and stirred next step catalytic synthesis 2～9 hours;
The 3rd step made product
After the catalytic synthesis in second step finishes, the cooling resultant of reaction, in ice-water bath, be neutralized to pH=7～8, remove by filter throw out, the filtrate air distillation with strong aqua, reclaim low boiler cut, 71～72 ℃ of cuts are collected in underpressure distillation under 1.47Kpa pressure then, are cooled to room temperature, get the white solid of 95.9 parts of weight, i.e. product ion liquid diacetic acid ammonium.
Being further characterized in that of technical scheme of the present invention, in the first step, solid acid catalyst is 3.33～20 parts of weight.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of acetone and vinyl cyanide, the mol ratio of acetone and vinyl cyanide is 2: 1.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of acetone and chloroform, the mol ratio of acetone and chloroform is 2.5: 1.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of ethyl acetate and vinyl cyanide, the mol ratio of ethyl acetate and vinyl cyanide is 1: 1.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of benzene and toluene, the mol ratio of benzene and toluene is 3: 1.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of acetonitrile and benzene, the mol ratio of acetonitrile and benzene is 4: 1.
Being further characterized in that of technical scheme of the present invention, in the first step, organic solvent is the mixed solvent of acetone and acetonitrile, the mol ratio of acetone and acetonitrile is 5: 1.
Compare with background technology, method of the present invention has following advantage:
1. one step of catalytic synthesis finishes, and technical process is simple, and productive rate is higher.
2. product is a kind of novel ionic liquid.
This ionic liquid has ion liquid general characteristic: temperature becomes liquid state when being 39 ℃; Good electrical conductivity and than the electrochemical window of broad; Specific conductivity is 9.8 * 10
3MS/cm.This ionic liquid is owing to be equivalent to introduce the acetate of a part in the molecule of ammonium acetate, and acetate is slightly acidic, they also are slightly acidic for formed salt, utilize this acidic character or be used to replace the formed acidic ion liquid of aluminum chloride, have bigger security with other solid acid.This ionic liquid has higher polarity, is insoluble to weakly polar organic solvent such as acetone etc., and specific conductivity is also very high.Therefore, this kind ionic liquid can be widely used in the ionogen and separating of the catalyzer that is used for organic synthesis etc. in the electrochemistry, has huge potential application foreground.
Embodiment
All embodiment operate by the operation steps of the process for catalytic synthesis of above-mentioned ionic liquid diacetic acid ammonium.
[embodiment 1]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone 80.2g adds 1.27g SO again
4 2-/ ZrO
2In second step, reacted 2 hours with stirring down in 40 ℃.The 3rd step, cooling, be neutralized to pH=7～8 with strong aqua in ice-water bath, remove by filter throw out, low boiler cut is reclaimed in the filtrate air distillation, underpressure distillation under 1.47Kpa pressure then, collect 71～72 ℃ of cuts, obtain white solid 95.9g under the room temperature, be the diacetic acid ammonium, productive rate is: 70%, usefulness IR,
1HNMR,
13The product of gained is confirmed in CNMR and ultimate analysis.
[embodiment 2]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and benzene 89.3g adds 2.54g SO again
4 2-/ ZrO
2In second step, reacted 2 hours with stirring down in 50 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 3]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and toluene 88.3g adds 3.81g SO again
4 2-/ ZrO
2In second step, reacted 2 hours with stirring down in 50 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 4]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and ethyl acetate 88.8g adds 5.08g SO again
4 2-/ ZrO
2In second step, reacted 2 hours with stirring down in 60 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 5]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and vinyl cyanide 82.2g adds the 6.35g phospho-molybdic acid again.In second step, reacted 2 hours with stirring down in 40 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 6]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and chloroform 150.2g adds the 10.2g tungstosilicic acid again.In second step, reacted 2 hours with stirring down in 70 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 7]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and ether 63.5g adds the 12.7g phospho-wolframic acid again.In second step, reacted 5 hours with stirring down in 50 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 8]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone and vinyl cyanide 80.8g (mol ratio 2: 1) add the 13.97g phospho-wolframic acid again.In second step, reacted 5 hours with stirring down in 70 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 9]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone and chloroform 101.6g (mol ratio 2.5: 1) add 15.2g SO again
4 2-/ ZrO
2In second step, reacted 6 hours with stirring down in 80 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 10]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and ethyl acetate and vinyl cyanide 82.9g (mol ratio 1: 1) add 6.3g SO again
4 2-/ ZrO
2In second step, reacted 6 hours with stirring down in 55 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 11]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, benzene and toluene 73.3g, and (mol ratio 3.0: 1) adds 16.5g HZSM-5 again.In second step, reacted 3 hours with stirring down in 40 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 12]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone 80.2g adds 20.3g SO again
4 2-/ ZSM-5.In second step, reacted 2 hours with stirring down in 40 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 13]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and dimethylbenzene 50.8g adds the 25.4g montmorillonite again.In second step, reacted 7 hours with stirring down in 60 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 14]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and ethyl acetate 81.6g adds the 12.7g activated clay again.In second step, reacted 3 hours with stirring down in 90 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 15]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone 80.2g adds the acid of 1g tungsten again.In second step, reacted 5 hours with stirring down in 70 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 16]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetonitrile 38.1g adds 6.3g SO again
4 2-/ ZrO
2In second step, reacted 8 hours with stirring down in 50 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 17]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetonitrile and benzene 89.5g (mol ratio 4: 1) add 8.9g SO again
4 2-/ ZrO
2In second step, reacted 9 hours with stirring down in 80 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 18]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and acetone and acetonitrile 82.5g (mol ratio 5: 1) add 6.4g SO again
4 2-/ ZSM-5.In second step, reacted 2 hours with stirring down in 60 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
[embodiment 19]
The first step in being furnished with the reactor of electronic stirring, adds glacial acetic acid 100g, and hexanaphthene 92.8g adds 10.2g SO again
4 2-/ ZrO
2In second step, reacted 8 hours with stirring down in 40 ℃.The 3rd step is identical with embodiment's 1, does not repeat here.
Claims (9)
1. an ionic liquid diacetic acid ammonium is characterized in that, this ionic liquid is by the inorganic ammonium NH of less positively charged ion
4 +With bigger negatively charged ion diacetic acid root (CH
3COO)
2H
-Form, molecular formula is (CH
3COO)
2HNH
4
2. the process for catalytic synthesis of the described ionic liquid diacetic acid of claim 1 ammonium is characterized in that, the concrete operations step:
The first step reaction mass is prepared
The solid acid catalyst of the glacial acetic acid of 100 parts of weight of reaction mass, 1～26 part of weight and the organic solvent of 35～160 parts of weight are joined in the reactor, and solid acid catalyst is solid super-strong acid SO
4 2-/ ZrO
2, SO
4 2-/ ZSM-5, HZSM-5, activated clay, montmorillonite and heteropolyacid such as phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid, tungsten acid, organic solvent are single solvent such as benzene, toluene, ethyl acetate, acetone, acetonitrile, ether, dimethylbenzene, vinyl cyanide, chloroform, hexanaphthene; Or by two kinds of single solvent blended mixed solvents such as acetone and vinyl cyanide, acetone and chloroform, ethyl acetate and vinyl cyanide, benzene and toluene, acetonitrile and benzene, acetone and acetonitrile, the mol ratio of two kinds of single solvents is (1～5): 1;
Second goes on foot catalytic synthesis
The reaction mass of the first step is at 40～90 ℃ and stirred next step catalytic synthesis 2～9 hours;
The 3rd step made product
After the catalytic synthesis in second step finishes, the cooling resultant of reaction, in ice-water bath, be neutralized to pH=7～8, remove by filter throw out, the filtrate air distillation with strong aqua, reclaim low boiler cut, 71～72 ℃ of cuts are collected in underpressure distillation under 1.47Kpa pressure then, are cooled to room temperature, get the white solid of 95.9 parts of weight, i.e. product ion liquid diacetic acid ammonium.
3. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, solid acid catalyst is 3.33～20 parts of weight.
4. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of acetone and vinyl cyanide, and the mol ratio of acetone and vinyl cyanide is 2: 1.
5. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of acetone and chloroform, and the mol ratio of acetone and chloroform is 2.5: 1.
6. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of ethyl acetate and vinyl cyanide, and the mol ratio of ethyl acetate and vinyl cyanide is 1: 1.
7. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of benzene and toluene, and the mol ratio of benzene and toluene is 3: 1.
8. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of acetonitrile and benzene, and the mol ratio of acetonitrile and benzene is 4: 1.
9. the process for catalytic synthesis of ionic liquid diacetic acid ammonium according to claim 2 is characterized in that, in the first step, organic solvent is the mixed solvent of acetone and acetonitrile, and the mol ratio of acetone and acetonitrile is 5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018045 CN1569801A (en) | 2004-04-29 | 2004-04-29 | Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018045 CN1569801A (en) | 2004-04-29 | 2004-04-29 | Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1569801A true CN1569801A (en) | 2005-01-26 |
Family
ID=34479320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410018045 Pending CN1569801A (en) | 2004-04-29 | 2004-04-29 | Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1569801A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381610C (en) * | 2005-05-30 | 2008-04-16 | 中国科学院过程工程研究所 | Electrochemical preparing method with [OH] ion liquid anion |
-
2004
- 2004-04-29 CN CN 200410018045 patent/CN1569801A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381610C (en) * | 2005-05-30 | 2008-04-16 | 中国科学院过程工程研究所 | Electrochemical preparing method with [OH] ion liquid anion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101050205A (en) | Compound containing cation radical of piperazidine, synthetic method, and application | |
| CN102614919B (en) | Sulfonated cross-linked chitosan resin type solid acid catalyst and preparation method thereof | |
| CN1203059C (en) | Novel processes for preparing torsemide intermediate | |
| CN1903419A (en) | Polyoxyethylene chain three cation quaternary ammonium salt type surfactant and its sysnthesis method | |
| CN1569801A (en) | Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor | |
| CN1891807A (en) | Guerbet anionic surfactant and preparation method and application thereof | |
| CN101050196A (en) | Bronsted acidic compound of containing L- proline radical, preparation method, and application | |
| CN1130330C (en) | Process for preparation of dialkyl succinylsuccinates | |
| CN1166608C (en) | Three-phase phase-transfer catalytic synthesis process of 9,9-dimethoxyl methyl) fluorene | |
| KR101421514B1 (en) | Method for preparing isosorbide from sorbitol using water-compatible lewis acid | |
| CN101054362A (en) | Method of synthesizing ion liquid at room temperature | |
| CN1176055C (en) | Process for producing 4-methoxyl methyl-2,3,5.6-tetrachlorophenmethylol | |
| CN1566064A (en) | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation | |
| CN1197836C (en) | Method for asymmetrically synthesizing secondary propiolic alcohol compound | |
| CN106475136B (en) | A kind of azochlorosulfonate acid ion catalyst, preparation method and its application | |
| CN1762946A (en) | Alkylcyclohexyl multiple-fluorine biphenyl derivative and its preparation method and uses | |
| CN1300117C (en) | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone | |
| CN1226250A (en) | Solvent extraction of 3-hydroxymethylcephalosporins | |
| CN100344794C (en) | In-tank type electrochemical synthesizing method of p-methoxy phenylacetone | |
| CN1206222C (en) | Process for preparing N-hydroxyalkyl compound and isocynauric acid tri (2-ethoyl) ester composition | |
| CN115368377B (en) | Preparation method of cyclic sulfate | |
| CN1036580C (en) | Process of producing N-alkylacetamides | |
| CN108117490B (en) | Preparation method of p-nitrobenzyl alcohol | |
| CN1566084A (en) | Novel optical pure water soluble diamine and derivative, preparation method and use thereof | |
| CN1294122C (en) | Process for microwave synthesis of 1,3-disubstituted imidazole-2-thioketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |