CN101058552B - Double-functional group ionic liquid and preparation method - Google Patents
Double-functional group ionic liquid and preparation method Download PDFInfo
- Publication number
- CN101058552B CN101058552B CN2006100258080A CN200610025808A CN101058552B CN 101058552 B CN101058552 B CN 101058552B CN 2006100258080 A CN2006100258080 A CN 2006100258080A CN 200610025808 A CN200610025808 A CN 200610025808A CN 101058552 B CN101058552 B CN 101058552B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- functional group
- double
- liquid
- sulfonic 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a bifunctional group ion liquid, which comprises the following steps: hydroxy and its derivant group, quaternary ammonium salt cation of sulfonic group and anion of sulfonic acid group or sulfate radical. The ion liquid is stable to meet water with fitful viscosity and low cost, which creates condition for further modified or fixed ion liquid.
Description
Technical field
The invention belongs to chemical material and preparing technical field thereof, be specifically related to a kind of double-functional group ionic liquid.The invention still further relates to the synthetic method of such double-functional group ionic liquid.
Background technology
Ionic liquid at room temperature is meant the material that is in a liquid state and is made of ion under near temperature room temperature or the room temperature, be another class green solvent system behind water and supercritical co.Mostly the ionic liquid of early stage report is to contain organic drone salt of aluminum halide, and their shortcoming is to moisture-sensitive, meets water and can decompose.In twentieth century nineties, the ionic liquid stable to water and air synthesized to come out successively.These ionic liquids are mostly by being made up of with fluo anion respectively alkyl pyridine positively charged ion, alkyl imidazole positively charged ion, quaternary ammonium alkyl positively charged ion and alkyl quaternary phosphonium cations.Because they have good characteristic such as low-steam pressure, room-temperature ion electroconductibility, thermostability mostly and all are with a wide range of applications in fields such as chemosynthesis, sepn process, electrochemistry.As: Welton on the 99:2071-2083, has summarized ion liquid preparation, physico-chemical property and the application in organic synthesis, catalysis, polyreaction at " Chemical Reviews " 1999.CN1379005 has described iso-butylene at ionic liquid [HMIm]
+BF
4 -In oligomerisation make the method for the additive of high-quality oil product and senior aldehyde, alcohol etc.
Ionic liquid at room temperature is owing to the theoretic designability of its zwitterion, therefore by changing the ionic liquid at room temperature that positively charged ion and anion structure can obtain functionalization.The ionic liquid of some functionalization has been synthesized to come out in succession in recent years, James H.Davis, Jr and Deng You congruence are respectively at " Journal of American Chemical Society " 2002,124:5962-5963 and " Tetrahedron Letters " 2004 have reported the ion liquid synthetic and application in organic synthesis of sulfonic acid and carboxylic acid functional on the 45:265-268.CN1698929 has described a kind of synthetic method of functionalized ion liquid of alcoholamine carboxylate, and the application aspect acid gas absorption.CN1383921 has described a kind of L monoamino-acid hydrosulfate type chiral ionic liquid and preparation method thereof.Fei and Dyson have summarized the progress of ionic liquid at room temperature functionalization on " Chemistry-A European Journal " 200500581 recently.
The task-specific ionic liquid of having reported at present mainly concentrates on the alkyl imidazole ionic liquid at room temperature, and many functional groups that comprise a kind of functionalization, perhaps only be the ionic liquid " mixture " that contains more than one functional groups, but not have the single positively charged ion or the single anion of two functional groups.In addition, the ionic liquid large-scale application remains at some in industry problem to be solved is arranged at present, and wherein most critical is to reduce ion liquid production cost.
Summary of the invention
Technical problem to be solved by this invention provides a kind of double-functional group ionic liquid and preparation method, overcoming the functional group that existing ionic liquid material only comprises a kind of functionalization, the application that has limited further modification or non diffusible ion liquid, and the defective that existing method or expensive raw material price, preparation process complexity, reaction conditions are difficult to control, reaction efficiency is lower.
Technical scheme
One of technical scheme of the present invention comprises for a kind of double-functional group ionic liquid is provided:
A) contain hydroxyl and sulfonic quaternary ammonium salt cationic; With
B) negatively charged ion of sulfonate radical or bisulfate ion;
Wherein, R1 and R2 are independently selected from H, alcohol radical, alkyl, aryl, heteroaryl, and perhaps R1 and R2 can be combined together to form ring;
Wherein, R3 is selected from H, or connects replacement or unsubstituted alkyl or aromatic base through fat key, ehter bond;
Wherein, R4 is selected from replacement or unsubstituted alkyl, thiazolinyl, aryl, heteroaryl or HO.
In the above-mentioned double-functional group ionic liquid, one of preferred version is that said R1 and R2 can be combined together to form ring.
Technical scheme of the present invention two for the preparation method of above-mentioned double-functional group ionic liquid is provided, may further comprise the steps:
A) utilize the reaction of oxyamine or derivatives thereof and sultones to obtain corresponding interior salt compounds;
B) with steps A) the interior salt compounds that obtains mixes with organic acid or mineral acid and obtains double-functional group ionic liquid, and its structural formula is:
Wherein, R1 and R2 are independently selected from H, hydroxyl, halogen, cyano group, nitro, sulfydryl, replacement or not substituted alkyl or thiazolinyl; R1 and R2 also can be combined together to form ring.
Wherein, R3 is selected from replacement or unsubstituted alkyl, thiazolinyl, aryl, heteroaryl or H.
Those skilled in the art need not too much experiment can determine among the preparation method of above-mentioned double-functional group ionic liquid said in the consumption of reactant of salt compounds and organic acid or mineral acid, preferable preferred version is employing mol ratio 1: 1.
Two of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is that said oxyamine is N, N-dimethylethanolamine, diethanolamine or trolamine, perhaps its combination.
Three of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is that said organic acid or mineral acid are methylsulphonic acid, trifluoromethanesulfonic acid, tosic acid or sulfuric acid, perhaps its combination.
Four of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is that said interior salt compounds is a kind of or its combination among dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt, three ethanol based 3-sulfonic acid propyl ammonium inner salts or the diethyl alcohol radical sulfonic acid butyl ammonium inner salt.
Five of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is that said interior salt compounds is water miscible, can be crystal.
Six of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is said steps A) reaction solvent can adopt any conventional organic solvent well known by persons skilled in the art.These solvents are stable at normal temperatures organic solvents, a kind of or its combination among acetone, toluene, benzene, acetonitrile or the dimethylbenzene.
Seven of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is said step B) temperature of reaction is 50-85 ℃.
Eight of the preparation method's of above-mentioned double-functional group ionic liquid preferred version is said step B) reaction after, reaction product is carried out vacuum-drying.
Those skilled in the art need not too much experiment and can understand, according to technical scheme provided by the invention ionic liquid is carried out difunctionalization modification, and its purposes is many-sided.As: the functionalized acidic modification not only can also be applied to fuel cell and realize the electrochemical reduction of oxygen and the electrochemical oxidation of hydrogen as the ionogen of the conduction of the acid proton under the anhydrous condition as the catalyzer and the solvent of esterification.In ionic liquid, introduce hydroxyl, sulfydryl, silylation and then can realize the immobilization of ionic liquid phase respectively on different solid matter surfaces.
Beneficial effect
1. institute's synthetic possesses the quaternary ammonium salt ionic liquid of hydroxyl and sulfonic group functional group simultaneously, is the ionic liquid of a class novel texture.
2. utilize the functional group in the raw material organic amine to realize ion liquid double-functional groupization simply and easily.
3. double-functional group ionic liquid possesses hydroxyl and sulfonic group functional group simultaneously, for further modification or non diffusible ion liquid have been created condition.As: in ionic liquid, introduce hydroxyl, sulfydryl, silylation can be realized the ionic liquid phase respectively on different solid matter surfaces immobilization.
4. ionic liquid at room temperature is carried out the double-functional group design, can obtain being easy to immobilized acidic ionic liquid, thereby can when keeping the acidic ionic liquid volume property, reduce the loss of use intermediate ion liquid.
5. intermediate product is that water-soluble crystal is purified easily, can control the purity of the finished product effectively.
6. resulting double-functional group ionic liquid is met water and air-stable, viscosity is moderate.
7. cost is lower, can carry out large-scale industrial production, but and field such as widespread use and catalysis, extraction.
8. ionic liquid at room temperature is carried out the double-functional group design, certainly will be able to further regulate the function of room-temperature ion, thus the range of application of extension ion liquid.
As used herein, term " functional group " or claim " functional group " refers to the atom and the atomic group of decision compound property in compound.In this article, all be functional group as hydroxyl in the said double-functional group ionic liquid and sulfonic group.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.After having read above-mentioned teachings of the present invention, 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 institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt
Under ice bath, the agitation condition, with 8.8mL 1,3-propane sultone (0.1mol) slowly is added drop-wise to and contains 10.1mL N, in the 30mL acetone mixing solutions of N-dimethylethanolamine (0.1mol), promptly the mol ratio of reaction raw materials is 1: 1, and very fast adularescent solid is separated out, after 1 hour, white solid with acetone, ether washing 3 times, is filtered 50 ℃ of following vacuum-dryings.Reaction equation is:
Embodiment 2
[p-methyl benzenesulfonic acid] [dimethyl ethanol base 3-sulfonic acid propyl ammonium] ionic liquid
Under ice bath, the agitation condition,, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying with the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt and 1.81g tosic acid (0.01mol) mixing of 1.95g (0.01mol) embodiment 1 gained.Product is a colourless transparent liquid, and reaction equation is:
Embodiment 3
[trifluoromethane sulfonic acid] [dimethyl ethanol base 3-sulfonic acid propyl ammonium] ionic liquid
Under N2 atmosphere, ice bath, the electronic agitation condition, the trifluoromethanesulfonic acid (0.02mol) of 1.80mL slowly is added drop-wise in the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt of 4.23g (0.02mol) embodiment 1 gained, after 12 hours, be heated to 50 ℃ to all becoming liquid, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 4
[hydrogen sulfate] [dimethyl ethanol base 3-sulfonic acid propyl ammonium] ionic liquid
Under ice bath, the agitation condition, the vitriol oil (0.014mol) of 0.8mL slowly is added drop-wise in the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt (0.014mol) of resultant embodiment 1 gained of 3.04g, 3 hours post-heating to 85 ℃ all become liquid after 10 hours, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 5
Three ethanol based 3-sulfonic acid propyl ammonium inner salts
Under ice bath, the agitation condition, with 13.2mL 1,3-propane sultone (0.15mol) slowly is added drop-wise in toluene (30mL) mixing solutions that contains 25.5mL trolamine (0.15mol), after 1 day, the adularescent solid generates, after usefulness toluene, ether wash 3 times, filter 50 ℃ of vacuum-dryings.Reaction equation is:
Embodiment 6
[tosic acid] [three ethanol based 3-sulfonic acid propyl ammoniums] ionic liquid
Under ice bath, the agitation condition, will mix, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying by embodiment 5 resulting three ethanol based 3-sulfonic acid propyl ammonium inner salt 7.76g (0.028mol) and 5.16g tosic acid (0.028mol).Product is a colourless transparent liquid, and reaction equation is:
Embodiment 7
[trifluoromethane sulfonic acid] [three ethanol based 3-sulfonic acid propyl ammoniums] ionic liquid
N
2Under atmosphere, ice bath, the agitation condition, the trifluoromethanesulfonic acid (0.029mol) of 2.6mL slowly is added drop-wise to by in embodiment 5 resulting 7.8g (0.029mol) the three ethanol based 3-sulfonic acid propyl ammonium inner salts, after 12 hours, be heated to 50 ℃ to all becoming liquid, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 8
[methylsulphonic acid] [three ethanol based 3-sulfonic acid propyl ammoniums] ionic liquid
Under ice bath, the agitation condition, the methanesulfonic (0.03mol) of 2.0mL slowly is added drop-wise to 8.60g (0.03mol) by in the embodiment 5 resulting three ethanol based 3-sulfonic acid propyl ammonium inner salts, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying.Product is a colourless transparent liquid, and reaction equation is:
Embodiment 9
Diethyl alcohol radical sulfonic acid butyl ammonium inner salt
Under room temperature, the agitation condition, the diethanolamine (0.1mol) of 9.6mL is scattered in the 20mL toluene solution, slowly drip 1 of 10.23mL again, behind the 4-sultones (0.1mol), be heated to 50 ℃, the adularescent solid generates after 15 hours, with white solid washing with alcohol 3 times, filter 50 ℃ of following vacuum-dryings.Reaction equation is:
Embodiment 10
[hydrogen sulfate] [diethyl alcohol radical sulfonic acid butyl ammonium] ionic liquid
Under ice bath, the agitation condition, the vitriol oil (0.012mol) of 0.65mL slowly is added drop-wise to resulting 2.81g by in the embodiment 9 resulting diethyl alcohol radical sulfonic acid butyl ammonium inner salts (0.012mol), 3 hours post-heating to 70 ℃ all become liquid after 6 hours, cooling final vacuum drying.Product is a colourless transparent liquid, and reaction equation is:
Embodiment 11
Contain sulfydryl substituting group inner salt
Step 1: be scattered in the benzole soln of 5ml at Thiovanic acid with 10ml; drip equimolar N; the N-dimethylethanolamine; under the nitrogen protection condition, be heated to 90 ℃ of backflow 12-15 hours; remove solvent benzol; filter with ether and potash solid agitator treating the cooling back, and ether is removed in the solution rotating evaporation that obtains, and obtains product.Reaction equation is:
Step 2: ice bath nitrogen protection condition lower magnetic force stirs, and the product that the first step is obtained is scattered in the toluene solution, slowly drips equimolar 1; the 3-propane sultone, after 1 day, the adularescent solid generates; after toluene, ether washing 3 times, filter 50 ℃ of vacuum-dryings.Reaction equation is:
Embodiment 12
The ionic liquid that contains the sulfydryl double-functional group
Under the ice bath nitrogen protection condition, electronic stirring slowly is added drop-wise to trifluoromethayl sulfonic acid etc. in the white solid that mole obtains by embodiment 11, after 3 hours, is heated to 70 ℃ to the transparent thick liquids that all become colorless, cooling final vacuum drying.Reaction equation is:
Embodiment 13
The inner salt that contains unsaturated double-bond
Step 1: magnetic agitation, the vinylformic acid of 10ml is scattered in the benzole soln of 5ml, drip equimolar N, the N-dimethylethanolamine, be heated to 90 ℃ of backflow 12-15 hours, and removed solvent benzol and water, filter with ether and potash solid agitator treating the cooling back, ether is removed in the solution rotating evaporation that obtains, and obtains product.Reaction equation is:
Step 2: the ice bath lower magnetic force stirs, and the product that step 1 is obtained is scattered in the toluene solution, slowly drip equimolar 1, the 3-propane sultone, after 1 day, the adularescent solid generates, and behind toluene, ether washing 3 times, filters 50 ℃ of vacuum-dryings.Reaction equation is:
Embodiment 14
The ionic liquid that contains unsaturated double-bond
Electronic stirring under the ice bath nitrogen protection condition slowly is added drop-wise to methanesulfonic etc. in the white solid that mole obtains by embodiment 13, after 3 hours, is heated to 70 ℃ to the transparent thick liquids that all become colorless, cooling final vacuum drying.Reaction equation is:
Embodiment 15
Chloride inner salt
0.1mol 2-dimethylamino monochloroethane hydrochloride is dissolved in the aqueous solution of 20ml saturated sodium carbonate, stirred 30 minutes, and filtered, in filtrate, add the new ether that steams, extraction, upper solution is joined in the round-bottomed flask, and magnetic agitation slowly drips 1,3-sultones (0.1mol), very fast adularescent solid is separated out, and filters back ether repetitive scrubbing 3 times, and vacuum-drying obtains white solid.Reaction equation is:
Embodiment 16
Chloride ion-containing liquid
Electronic stirring under the ice bath nitrogen protection condition slowly is added drop-wise to methanesulfonic etc. in the white solid that mole obtains by embodiment 15, after 3 hours, is heated to 70 ℃ to the transparent thick liquids that all become colorless, cooling final vacuum drying.Reaction equation is:
Embodiment 17
The inner salt that contains aromatic nucleus
Step 1: 0.1mol 2-dimethylamino monochloroethane hydrochloride is dissolved in the aqueous solution of 20ml saturated sodium carbonate, stirred 30 minutes, filter, in filtrate, add the new ether that steams, extraction.
Step 2: with 0.1mol phenol, 0.15M KOH and excessive toluene boil off toluene water azeotrope in 135 ℃ of heating, slowly splash into the solution that is obtained by step 1, again 180 ℃ of reactions 8 hours.Regulate about pH=3 with dilute hydrochloric acid, add 50ml toluene extraction organism again, wash three times with water, and boil off toluene, obtain product.Reaction equation is:
Step 3: the ice bath lower magnetic force stirs, and the product that step 2 is obtained is scattered in the toluene solution, slowly drip equimolar 1, the 3-propane sultone, after 1 day, the adularescent solid generates, and behind toluene, ether washing 3 times, filters 50 ℃ of vacuum-dryings.Reaction equation is:
Embodiment 18
The ionic liquid that contains aromatic nucleus
Electronic stirring under the ice bath nitrogen protection condition slowly is added drop-wise to methanesulfonic etc. in the white solid that mole obtains by embodiment 15, after 3 hours, is heated to 70 ℃ to the transparent thick liquids that all become colorless, cooling final vacuum drying.Reaction equation is:
Claims (1)
1. double-functional group ionic liquid compound with following structure,
Wherein,
R1 is a methyl, and R2 is a methyl, and R3 is H, and R4 is a p-methylphenyl;
R1 is a methyl, and R2 is a methyl, and R3 is H, and R4 is a trifluoromethyl;
R1 is a methyl, and R2 is a methyl, and R3 is H, and R4 is OH;
R1 is an ethanol based, and R2 is an ethanol based, and R3 is H, and R4 is a p-methylphenyl;
R1 is an ethanol based, and R2 is an ethanol based, and R3 is H, and R4 is a trifluoromethyl; Or
R1 is an ethanol based, and R2 is an ethanol based, and R3 is H, and R4 is a methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100258080A CN101058552B (en) | 2006-04-18 | 2006-04-18 | Double-functional group ionic liquid and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100258080A CN101058552B (en) | 2006-04-18 | 2006-04-18 | Double-functional group ionic liquid and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058552A CN101058552A (en) | 2007-10-24 |
| CN101058552B true CN101058552B (en) | 2010-12-08 |
Family
ID=38864874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100258080A Expired - Fee Related CN101058552B (en) | 2006-04-18 | 2006-04-18 | Double-functional group ionic liquid and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101058552B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723528A (en) * | 2012-06-06 | 2012-10-10 | 中国科学院广州能源研究所 | Amphoteric ionic liquid electrolyte material, preparation method thereof and application thereof to lithium battery electrolyte |
| CN106496400A (en) * | 2016-11-07 | 2017-03-15 | 上海三瑞高分子材料股份有限公司 | A kind of phosphorous terpolymer and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973940B (en) * | 2010-09-28 | 2012-10-03 | 盐城师范学院 | Continuously synthesizing method of sulfonic acid alkyl group ionic liquid |
| CN103923695B (en) * | 2014-04-04 | 2016-01-13 | 青岛科技大学 | A kind of catalyzing iso-butane alkane and C 4olefine reaction prepares the method for gasoline alkylate |
| CN105439911B (en) * | 2015-11-27 | 2017-09-19 | 盐城师范学院 | A kind of eutectic material based on ethoxy inner salt |
| CN105419952B (en) * | 2015-12-04 | 2019-11-26 | 盐城师范学院 | A kind of method of biodiesel synthesis in eutectic system |
| CN105541670A (en) * | 2015-12-04 | 2016-05-04 | 江南大学 | Polyethylene glycol 400 functionalized binuclear acidic ionic liquid and preparation method |
| CN105349268B (en) * | 2015-12-04 | 2019-08-23 | 盐城师范学院 | The method of biodiesel synthesis in scene induction eutectic system |
| CN111001440A (en) * | 2019-12-26 | 2020-04-14 | 福州大学 | Polyacid site ionic liquid catalyst and preparation method and application thereof |
| CN113135846A (en) * | 2021-04-07 | 2021-07-20 | 吉和昌新材料(荆门)有限公司 | Preparation method of sulfobetaine type waterborne polyurethane chain extender |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712093A (en) * | 2004-06-22 | 2005-12-28 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
-
2006
- 2006-04-18 CN CN2006100258080A patent/CN101058552B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712093A (en) * | 2004-06-22 | 2005-12-28 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723528A (en) * | 2012-06-06 | 2012-10-10 | 中国科学院广州能源研究所 | Amphoteric ionic liquid electrolyte material, preparation method thereof and application thereof to lithium battery electrolyte |
| CN102723528B (en) * | 2012-06-06 | 2016-01-20 | 广州中科立新材料科技有限公司 | Amphion liquid electrolyte material and preparation thereof and application in lithium battery electrolytes |
| CN106496400A (en) * | 2016-11-07 | 2017-03-15 | 上海三瑞高分子材料股份有限公司 | A kind of phosphorous terpolymer and preparation method thereof |
| CN106496400B (en) * | 2016-11-07 | 2018-05-08 | 上海三瑞高分子材料股份有限公司 | A kind of phosphorous terpolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101058552A (en) | 2007-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101058552B (en) | Double-functional group ionic liquid and preparation method | |
| CN102120728B (en) | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof | |
| PT2150533E (en) | Process for the preparation of optically active ethenylphenyl alcohols | |
| CN100528839C (en) | Ionic liquid of alkyl guanidine salt and its preparation process | |
| CN101514375A (en) | Method for preparing reducing sugar by catalyzing hydrocellulose | |
| CN103265405B (en) | Method for preparing 1,2-cyclohexanediol through carrying out catalytic oxidation on cyclohexene by using phase transfer catalyst | |
| CN103193711A (en) | Three-ingredient eutectic ionic liquid and preparation method thereof | |
| CN101147877A (en) | Method for preparing supported ion liquid and its application in catalytic hydroxy acid esterifying | |
| CN101648894A (en) | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof | |
| CN109761851A (en) | A kind of preparation method of isophthalodinitrile | |
| CN115304518B (en) | Zwitterionic compound with biocompatibility and preparation method thereof | |
| CN105521825A (en) | Catalyst for preparing phenol by benzene oxidation, and preparation method and application thereof | |
| CN100415355C (en) | Polyoxyethylene chain three cation quaternary ammonium salt type surfactant and its sysnthesis method | |
| CN105833909B (en) | (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications | |
| CN105772085B (en) | (S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (1 ethoxy, 1 isopropyl), preparation method and applications | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN105854940B (en) | (R) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications | |
| US9062081B1 (en) | Preparation of phenol- or thiophenyl-sulfonic acid functionalized solid acids | |
| CN105854952B (en) | (S) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications | |
| CN105797770B (en) | (S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (phenylpropyl of 3 hydroxyl 1), preparation method and applications | |
| CN102069010B (en) | Montmorillonite catalyst used in preparation of cyclic carbonate | |
| CN105797769B (en) | (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications | |
| CN103910656B (en) | Functionalized acidic ionic liquid and preparation thereof and the application in ethyl lactate synthesizes | |
| CN111203272A (en) | Water-resistant sulfonic heteropoly acid salt catalyst and synthesis and application thereof | |
| CN106831583A (en) | N, N dialkyl group substituted pyrazolecarboxylic ionic liquid, preparation method and its method for catalyzing and synthesizing propene carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101208 Termination date: 20130418 |