CN102766075A - Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof - Google Patents
Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof Download PDFInfo
- Publication number
- CN102766075A CN102766075A CN2012102263549A CN201210226354A CN102766075A CN 102766075 A CN102766075 A CN 102766075A CN 2012102263549 A CN2012102263549 A CN 2012102263549A CN 201210226354 A CN201210226354 A CN 201210226354A CN 102766075 A CN102766075 A CN 102766075A
- Authority
- CN
- China
- Prior art keywords
- acid
- ion
- quaternary ammonium
- ionic liquid
- ammonium salt
- 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
Abstract
The invention provides a double-acid-level contained quaternary ammonium salt ionic liquid and a preparation method thereof. The ionic liquid comprises positive ions of sulfonic Bronsted acid-level quaternary ammonium salt and negative ions of sulfate, phosphate, malonate or succinic acid, as well as Lewis acid level of copper iron or zinc iron. The ionic liquid provided by the invention has the advantages of stability in contact with water and air, simplicity in preparation, and low cost, is suitable for large-sized production, and can be widely used for the field of organic synthesis and organic catalysis.
Description
Technical field
The present invention relates to quaternary ammonium salt ionic liquid of a kind of bisgallic acid position and preparation method thereof, belong to new chemical material and preparing technical field thereof.
Background technology
Ionic liquid is playing more and more important effect aspect the alternative volatile organic solvent, and is having catalytic performance in some cases concurrently because of its distinctive physico-chemical property, meets the requirement of the cleaning technique of being advocated at present especially.Its range of application has expanded to fields such as functional materials, electric light and photovaltaic material, storage of solar energy, life science rapidly from chemical, be novel " soft " functional materials or the medium of one type of worth researchdevelopment.The ionic liquid that utilizes ion liquid designability to satisfy the specificity requirement through design is called the ionic liquid of functionalization, comprises functionalization that is directed against physical properties (for example: flowability, transmissibility, liquid scope) and the functionalization that is directed against chemical property (polarity, acidity, chirality, coordination ability, solvability).In ionic liquid, introducing different functional groups, realize ion liquid functionalization to satisfy specific demand, is one of emphasis of current ionic liquid research.Mostly the ionic liquid of early stage report is to contain the organic 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.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.Like: Welton at " Chemical Reviews ", 2011,111:3508-3576 is last, summarized ion liquid preparation, physico-chemical property and in organic synthesis as solvent and Application of Catalyst.In recent years, very active about ion liquid research, western countries government all invested considerable capital to carry out the research of ionic liquid aspect with relevant enterprise.Because ion liquid designability is promptly adjusted the suitable functional group of yin, yang ion population or grafting, can obtain the ionic liquid of " target is specific " or " cutting the garment according to the figure ".
As everyone knows, Lewis acid position and Br nsted acid position are to the acid catalyzed reaction no less important, and the catalyst that combines bisgallic acid position advantage can be more effective.
Synthetic Br nsted-Lewis bisgallic acid position ionic liquid in recent years, its structural formula is following:
And there is the shortcoming to air and water sensitive mostly in this Br nsted-Lewis bisgallic acid position ionic liquid, and preparation process reaction conditional request is relatively harsher, and mainly concentrates on the research to the imidazole type ionic liquid.
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.In the present invention we aim to provide that a kind of acidity is stronger, stable, low-cost to empty G&W, the bisgallic acid position quaternary ammonium type ionic liquid that is prone to synthetic, greenization and preparation method thereof.
Summary of the invention
One of the object of the invention is in order to solve existing bisgallic acid position ionic liquid poor stability, to have limited ion liquid modification or application; And expensive raw material price, reaction technical problem such as are difficult to control and the functionalized ion liquid of a kind of bisgallic acid position are provided; The functionalized ion liquid of a kind of bisgallic acid of the present invention position has been abandoned expensive imidazoles raw material, and selecting alkylamine cheap and easy to get is starting raw material; And avoid the use of metal chloride to water sensitive; But originate as tart with stable MOX, compare with the ionic liquid structure of reporting in the document and have remarkable advantages, comprising: stable, cheapness and preparation condition gentleness etc.。
Two of the object of the invention provides above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position.
Technical scheme of the present invention
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position; Lewis acid position and the sulfonic Br nsted acid position of containing cupric ion or zine ion; Described sulfonic Br nsted acid position is a positively charged ion with the quaternary ammonium salt, is negatively charged ion with sulfate radical, hydrogen phosphate, malonate or succinic;
Described quaternary ammonium salt cationic is triethylamine 4-sulfonic acid butyl ammonium cation, diethylamine 3-sulfonic acid propyl ammonium positively charged ion, tripropyl amine 4-sulfonic acid butyl ammonium cation, dipropyl amine 4-sulfonic acid butyl ammonium cation or n n dimetylaniline 3-sulfonic acid propyl ammonium positively charged ion.
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is methyl, ethyl, propyl group, butyl or the tertiary butyl;
R
2Be H or alkyl 2, described alkyl 2 is methyl, ethyl, propyl group, butyl or the tertiary butyl;
R
3Be H or alkyl 3, described alkyl 3 is methyl, ethyl, propyl group, butyl or the tertiary butyl;
N is 3 or 4;
B
-Be sulfate ion, phosphoric acid hydrogen radical ion, malonate ion or succinic ion;
M
2+Be cupric ion or zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), with alkylamine and sultones in solvent, controlled temperature be 60 ~ 80 ℃ down behind reaction 2 ~ 4h the reaction solution of gained obtain interior salt compounds through suction filtration, washing with alcohol, vacuum-drying;
Described alkylamine is Trimethylamine 99, triethylamine, tripropyl amine, n n dimetylaniline, diethylamine, dipropyl amine, n-Butyl Amine 99 or TERTIARY BUTYL AMINE;
Described sultones is 1,3-propane sultone or 1,4-butane sultones;
React the used alkylamine and the amount of sultones and calculate in molar ratio, be i.e. alkylamine: sultones is 1:1 ~ 1.2, is preferably 1:1;
Described solvent is organic solvent or inorganic solvent, and its consumption is 20mL solvent/0.1mol alkylamine; Described organic solvent is acetone, toluene, acetonitrile or ethanol, but is not limited thereto;
(2), interior salt compounds that step (1) is obtained and organic acid or mineral acid controlled temperature are under 60 ℃ the condition, to obtain containing Br nsted acidic ion liquid midbody behind reaction 3 ~ 10h;
Described organic acid is propanedioic acid or Succinic Acid;
Described mineral acid is sulfuric acid or phosphoric acid;
React the used interior salt compounds and the amount of organic acid or mineral acid and calculate in molar ratio, promptly in salt compounds: organic acid or mineral acid are 1:1;
(3), contain Br nsted acidic ion liquid midbody and the MOX that step (2) are obtained mix under the agitation condition in deionized water solution; The product that mixes the back gained carries out vacuum-drying under 60 ℃, promptly get the quaternary ammonium salt ionic liquid that contains the bisgallic acid position;
The ratio of mixture of the described Br of containing nsted acidic ion liquid midbody and MOX is calculated in molar ratio, and promptly contain Br nsted acidic ion liquid midbody: MOX is 1:0.3 ~ 2;
Described MOX is cupric oxide or zinc oxide.
Beneficial effect of the present invention
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position of the present invention; Owing to replaced the higher positively charged ion raw materials such as alkyl imidazole of price, therefore reduced ion liquid cost, and productive rate is high with alkylamine; The preparation method is simple and easy to do, can carry out large-scale industrial production.
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position of the present invention is because not containing metal muriate or cl ions are therefore stable to empty G&W.
In addition, a kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position of the present invention is owing to have Br nsted and two kinds of acidity of Lewis; Be particularly suitable for the solvent and the catalyzer of double as acid catalyzed reaction; The mineral acid and poisonous, the volatile organic solvent that replace severe corrosive improve activity of such catalysts and stability, improve the selectivity of reaction; Simplify the sepn process of product, promptly can reuse through simple process.Meet the requirement of Green Chemistry.
Embodiment
Through embodiment the present invention is further set forth below, but do not limit the present invention.
The used raw material of the present invention is analytical pure, and buying is Chemical Reagent Co., Ltd., Sinopharm Group from Shanghai.
Embodiment 1
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of cupric ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, with sulfate radical, be negatively charged ion;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be cupric ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position comprises the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.79g cupric oxide (0.01mol) and 3.35g step (2) resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Deionized water is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [cupric oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 2
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the hydrogen phosphate;
Wherein said quaternary ammonium salt cationic is a diethylamine 3-sulfonic acid propyl ammonium positively charged ion;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 3;
B
-Be phosphoric acid hydrogen radical ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,3-propane sultone (0.1mol) slowly is added drop-wise in the 10.0mL diethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain diethylamine propane sulfonic acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g phosphoric acid (0.05mol) of the resulting diethylamine propane sulfonic acid of 10.5g (0.05mol) step (1) inner salt are mixed; 60 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [phosphoric acid] [diethylamine 3-sulfonic acid propyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.81g zinc oxide (0.01mol) and 3.07g step (2) resulting [phosphoric acid] [diethylamine 3-sulfonic acid propyl ammonium] ionic liquid midbody (0.01 mol) are joined in the 5 mL deionized waters; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [phosphoric acid] [diethylamine 3-sulfonic acid propyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 3
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a tripropyl amine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is a propyl group;
R
2Be H or alkyl 2, described alkyl 2 is a propyl group;
R
3Be H or alkyl 3, described alkyl 3 is a propyl group;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition; With 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the ethanolic soln that contains 19.7mL tripropyl amine (0.1mol), and 70 ℃ are reacted 2h down; Be cooled to 25 ℃; Suction filtration, filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain tripropyl amine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting tripropyl amine butane of 13.9g (0.05mol) step (1) acid inner salt are mixed; React 10h under the room temperature; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [tripropyl amine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.81g zinc oxide (0.01mol) and 3.78g step (2) resulting [sulfuric acid] [tripropyl amine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5 mL deionized waters; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [tripropyl amine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 4
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of cupric ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the malonate;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be the malonate ion;
M
2+Be cupric ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), with the step among the embodiment 1 (1), triethylamine butane acid inner salt
(2), under ice bath, the agitation condition; The deionized water solution and the 5.2g propanedioic acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 70 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [propanedioic acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.79g cupric oxide (0.01mol) and 2.42g step (2) resulting [propanedioic acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, obtained [propanedioic acid] [triethylamine 4-sulfonic acid butyl ammonium] [cupric oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 5
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of cupric ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the succinic;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be the succinic ion;
M
2+Be cupric ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), with the step among the embodiment 1 (1), triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 5.9g Succinic Acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 70 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [Succinic Acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.79g cupric oxide (0.01mol) and 3.56g step (2) resulting [Succinic Acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01 mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [Succinic Acid] [triethylamine 4-sulfonic acid butyl ammonium] [cupric oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 6
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of cupric ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is for being triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be phosphoric acid hydrogen radical ion;
M
2+Be cupric ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), with the step among the embodiment 1 (1), triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g phosphoric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05 mol) step (1) acid inner salt are mixed; 70 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [phosphoric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid;
(3), under the agitation condition; 0.79g cupric oxide (0.01mol) and 3.35g step (2) resulting [phosphoric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [phosphoric acid] [triethylamine 4-sulfonic acid butyl ammonium] [cupric oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 7
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of cupric ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a dipropyl amine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H;
R
2Be H or alkyl 2, described alkyl 2 is a propyl group;
R
3Be H or alkyl 3, described alkyl 3 is a propyl group;
N is 4;
B
-Be sulfate ion;
M
2+Be cupric ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition; With 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the acetonitrile mixing solutions that contains 10.0mL dipropyl amine (0.1mol), and 70 ℃ are reacted 2h down; Be cooled to 25 ℃; Suction filtration, filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain dipropyl amine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting dipropyl amine butane of 10.5g (0.05mol) step (1) acid inner salt are mixed; 60 ℃ are reacted 5h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [dipropyl amine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.79g cupric oxide (0.01mol) and 3.07g step (2) resulting [sulfuric acid] [dipropyl amine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [dipropyl amine 4-sulfonic acid butyl ammonium] [cupric oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 8
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.81g zinc oxide (0.01mol) and 3.35g step (2) resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly got [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 9
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.81g zinc oxide (0.01mol) and 1.68g step (2) resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.005mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 10
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.40g zinc oxide (0.005mol) and 3.35g step (2) resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 11
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.26g zinc oxide (0.003mol) and 3.35g step (2) resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 12
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a triethylamine 4-sulfonic acid butyl ammonium cation positively charged ion;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is an ethyl;
R
2Be H or alkyl 2, described alkyl 2 is an ethyl;
R
3Be H or alkyl 3, described alkyl 3 is an ethyl;
N is 4;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,4-butane sultones (0.1mol) slowly is added drop-wise in the 13.9mL triethylamine (0.1mol); 80 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain triethylamine butane acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting triethylamine butane of 11.85g (0.05mol) step (1) acid inner salt are mixed; 50 ℃ are reacted 3h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 2.43 g zinc oxide (0.03mol) and 3.35g embodiment 2 resulting [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] ionic liquid midbody (0.01mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [triethylamine 4-sulfonic acid butyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
Embodiment 13
A kind of quaternary ammonium salt ionic liquid that contains the bisgallic acid position contains the Lewis acid position and sulfonic Br nsted acid position of zine ion, and described sulfonic Br nsted acid is positively charged ion with the quaternary ammonium salt, is negatively charged ion with the sulfate radical;
Wherein said quaternary ammonium salt cationic is a n n dimetylaniline 3-sulfonic acid propyl ammonium positively charged ion;
The above-mentioned ion liquid general structure of the quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H;
R
2Be H or alkyl 2, described alkyl 2 is a methyl;
R
3Be H or alkyl 3, described alkyl 3 is a methyl;
N is 3;
B
-Be sulfate ion;
M
2+Be zine ion.
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position may further comprise the steps:
(1), under the agitation condition, with 10.2mL 1,3-propane sultone (0.1mol) slowly is added drop-wise in the 4.5mL n n dimetylaniline (0.1mol); 60 ℃ are reacted 2h down, are cooled to 25 ℃, suction filtration; Filter cake with after the washing with alcohol 3 times at 50 ℃ of following vacuum-drying 3h, obtain n n dimetylaniline propane sulfonic acid inner salt;
(2), under ice bath, the agitation condition; The deionized water solution and the 4.9g sulfuric acid (0.05mol) of the resulting n n dimetylaniline propane sulfonic acid of 9.8g (0.05mol) step (1) inner salt are mixed; 40 ℃ are reacted 7h down; The cooling back is controlled under the condition that vacuum tightness is 0.02MPa and is carried out vacuum-drying 3h, obtains [sulfuric acid] [n n dimetylaniline 3-sulfonic acid propyl ammonium] ionic liquid midbody;
(3), under the agitation condition; 0.81g zinc oxide (0.01mol) and 2.93g step (2) resulting [sulfuric acid] [n n dimetylaniline 3-sulfonic acid propyl ammonium] ionic liquid midbody (0.01 mol) are joined in the 5mL deionized water; Stir the mixture and dissolve fully up to solid; Solvent is removed through Rotary Evaporators,, promptly obtained [sulfuric acid] [n n dimetylaniline 3-sulfonic acid propyl ammonium] [zinc oxide] ionic liquid then in 50 ℃ of following vacuum-drying 3h.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. quaternary ammonium salt ionic liquid that contains the bisgallic acid position; Lewis acid position and the sulfonic Br nsted acid position of containing cupric ion or zine ion; It is characterized in that described sulfonic Br nsted acid position is a positively charged ion with the quaternary ammonium salt, is negatively charged ion with sulfate radical, hydrogen phosphate, malonate or succinic;
Wherein said quaternary ammonium salt cationic is triethylamine 4-sulfonic acid butyl ammonium cation, diethylamine 3-sulfonic acid propyl ammonium positively charged ion, tripropyl amine 4-sulfonic acid butyl ammonium cation, dipropyl amine 4-sulfonic acid butyl ammonium cation or n n dimetylaniline 3-sulfonic acid propyl ammonium positively charged ion;
The described ion liquid general structure of quaternary ammonium salt that contains the bisgallic acid position is following:
Wherein, R
1Be H or alkyl 1, described alkyl 1 is methyl, ethyl, propyl group, butyl or the tertiary butyl;
R
2Be H or alkyl 2, described alkyl 2 is methyl, ethyl, propyl group, butyl or the tertiary butyl;
R
3Be H or alkyl 3, described alkyl 3 is methyl, ethyl, propyl group, butyl or the tertiary butyl
N is 3 or 4;
B
-Be sulfate ion, phosphoric acid hydrogen radical ion, malonate ion or succinic ion;
M
2+Be cupric ion or zine ion.
2. a kind of quaternary ammonium salt preparation method of ionic liquid that contains the bisgallic acid position as claimed in claim 1 is characterized in that may further comprise the steps:
(1), with alkylamine and sultones in solvent, controlled temperature be 60 ~ 80 ℃ down behind reaction 2 ~ 4h the reaction solution of gained obtain interior salt compounds through suction filtration, washing with alcohol, vacuum-drying;
Described alkylamine is Trimethylamine 99, triethylamine, tripropyl amine, n n dimetylaniline, diethylamine, dipropyl amine, n-Butyl Amine 99 or TERTIARY BUTYL AMINE;
Described sultones is 1,3-propane sultone or 1,4-butane sultones;
React the used alkylamine and the amount of sultones and calculate in molar ratio, be i.e. alkylamine: sultones is 1:1 ~ 1.2;
Described solvent is organic solvent or inorganic solvent, and its consumption is 20mL solvent/0.1mol alkylamine;
(2), interior salt compounds that step (1) is obtained and organic acid or mineral acid controlled temperature are under 60 ℃ the condition, to obtain containing Br nsted acidic ion liquid midbody behind reaction 3 ~ 10h;
Described organic acid is propanedioic acid or Succinic Acid;
Described mineral acid is sulfuric acid or phosphoric acid;
React the used interior salt compounds and the amount of organic acid or mineral acid and calculate in molar ratio, promptly in salt compounds: organic acid or mineral acid are 1:1;
(3), contain Br nsted acidic ion liquid midbody and the MOX that step (2) are obtained mix under the agitation condition in deionized water solution; The product that mixes the back gained carries out vacuum-drying under 60 ℃, promptly get the quaternary ammonium salt ionic liquid that contains the bisgallic acid position;
The ratio of mixture of the described Br of containing nsted acidic ion liquid midbody and MOX is calculated in molar ratio, and promptly contain Br nsted acidic ion liquid midbody: MOX is 1:0.3 ~ 2;
Described MOX is cupric oxide or zinc oxide.
3. a kind of bisgallic acid position quaternary ammonium salt preparation method of ionic liquid that contains as claimed in claim 2 is characterized in that the organic solvent described in the step (1) is acetone, toluene, acetonitrile or ethanol.
4. a kind of bisgallic acid position quaternary ammonium salt preparation method of ionic liquid that contains as claimed in claim 3 is characterized in that the vacuum-drying controlled temperature described in the step (1) is 50 ℃, and the time is 3h.
5. a kind of bisgallic acid position quaternary ammonium salt preparation method of ionic liquid that contains as claimed in claim 4, it is characterized in that the alkylamine that the reaction described in the step (1) is used and the amount of sultones calculate in molar ratio, i.e. alkylamine: sultones is 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102263549A CN102766075A (en) | 2012-07-03 | 2012-07-03 | Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102263549A CN102766075A (en) | 2012-07-03 | 2012-07-03 | Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102766075A true CN102766075A (en) | 2012-11-07 |
Family
ID=47093686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102263549A Pending CN102766075A (en) | 2012-07-03 | 2012-07-03 | Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766075A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923695A (en) * | 2014-04-04 | 2014-07-16 | 青岛科技大学 | Method for preparing gasoline alkylate by catalyzing reaction of isobutane and C4 olefin |
| CN105112397A (en) * | 2015-08-20 | 2015-12-02 | 天津科技大学 | Preparation method of polyquaternium ionic liquid enzyme reactor |
| CN105541670A (en) * | 2015-12-04 | 2016-05-04 | 江南大学 | Polyethylene glycol 400 functionalized binuclear acidic ionic liquid and preparation method |
| CN109796406A (en) * | 2019-01-31 | 2019-05-24 | 河北科技大学 | A kind of method Br*nsted-Lewis bis- acidic ion liquids and its catalyze and synthesize succinate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348448A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of ion liquid having B acid center and L acid center |
| CN102060738A (en) * | 2010-12-10 | 2011-05-18 | 绍兴文理学院 | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof |
| US20110233458A1 (en) * | 2010-03-19 | 2011-09-29 | EASTERN MICHIGAN UNIVERSITY Office of Research Development | Nanoparticle dispersions with ionic liquid-based stabilizers |
-
2012
- 2012-07-03 CN CN2012102263549A patent/CN102766075A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348448A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of ion liquid having B acid center and L acid center |
| US20110233458A1 (en) * | 2010-03-19 | 2011-09-29 | EASTERN MICHIGAN UNIVERSITY Office of Research Development | Nanoparticle dispersions with ionic liquid-based stabilizers |
| CN102060738A (en) * | 2010-12-10 | 2011-05-18 | 绍兴文理学院 | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| 《Catalysis Communications》 20110131 Liang Xuezheng等 "Synthesis of a novel ionic liquid with both Lewis and Br�nsted acid sites and its catalytic activities" 第808-812页 1-5 第12卷, 第9期 * |
| 《南京航空航天大学学报》 20070831 方东等 "新型功能化离子液体催化水相Mannich反应" 第1.2部分 2-5 第39卷, 第4期 * |
| 《石油学报(石油加工)》 20081031 刘秀梅等 "三甲胺基SO3H-功能化离子液体催化对苯二酚叔丁基化反应" 第534页, 1.1部分 2-5 第24卷, 第5期 * |
| LIANG XUEZHENG等: ""Synthesis of a novel ionic liquid with both Lewis and Brønsted acid sites and its catalytic activities"", 《CATALYSIS COMMUNICATIONS》, vol. 12, no. 9, 31 January 2011 (2011-01-31), pages 808 - 812, XP028164572, DOI: doi:10.1016/j.catcom.2011.01.018 * |
| 刘秀梅等: ""三甲胺基SO3H-功能化离子液体催化对苯二酚叔丁基化反应"", 《石油学报(石油加工)》, vol. 24, no. 5, 31 October 2008 (2008-10-31) * |
| 方东等: ""新型功能化离子液体催化水相Mannich反应"", 《南京航空航天大学学报》, vol. 39, no. 4, 31 August 2007 (2007-08-31), pages 1 - 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923695A (en) * | 2014-04-04 | 2014-07-16 | 青岛科技大学 | Method for preparing gasoline alkylate by catalyzing reaction of isobutane and C4 olefin |
| 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 |
| CN105112397A (en) * | 2015-08-20 | 2015-12-02 | 天津科技大学 | Preparation method of polyquaternium ionic liquid enzyme reactor |
| CN105112397B (en) * | 2015-08-20 | 2017-10-10 | 天津科技大学 | A kind of preparation method of polyquaternium ionic liquid enzyme reactor |
| CN105541670A (en) * | 2015-12-04 | 2016-05-04 | 江南大学 | Polyethylene glycol 400 functionalized binuclear acidic ionic liquid and preparation method |
| CN109796406A (en) * | 2019-01-31 | 2019-05-24 | 河北科技大学 | A kind of method Br*nsted-Lewis bis- acidic ion liquids and its catalyze and synthesize succinate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kar et al. | Chelating ionic liquids for reversible zinc electrochemistry | |
| Shamsuri et al. | Ionic liquids: Preparations and limitations | |
| Chang et al. | Shifting redox potential of nitroxyl radical by introducing an imidazolium substituent and its use in aqueous flow batteries | |
| CN107629032B (en) | A kind of preparation method of cyclic sulfates | |
| CN103930405B (en) | Prepare the method for five rings anion salt | |
| CN107215853A (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| CN101182300B (en) | Quaternary ammonium ionic liquid as well as preparation and application method thereof | |
| CN107447228A (en) | Method for electrocatalytic reduction of carbon dioxide | |
| CN102120728B (en) | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof | |
| CN107312172B (en) | A kind of preparation method of micro-nano structure polyaniline material | |
| CN102766075A (en) | Double-acid-level contained quaternary ammonium salt ionic liquid and preparation method thereof | |
| CN102295603A (en) | Peroxy heteropoly acid based ionic liquid and preparation method thereof | |
| CN101633641B (en) | Preparation method of imidazole type ionic liquid | |
| CN101654438A (en) | Imidazole ionic liquid production technology | |
| CN101941986A (en) | Y aromatic ligand ionic liquid and preparation method thereof | |
| CN102850223B (en) | Method for synthesizing methylethyl carbonate | |
| US20230272541A1 (en) | A method of continuous electrochemical dinitrogen reduction | |
| CN102977031A (en) | Method for synthesizing ionic liquid | |
| CN102225899A (en) | Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof | |
| CN104829813B (en) | A kind of ionomeric polymer containing phosphine, preparation method and anion-exchange membrane | |
| CN101153018A (en) | Br*nsted acidity ion liquid containing N-alkyl pyrrolidone group, producing method and use of the same | |
| CN115286543B (en) | Process for preparing 4,4' -dichloro diphenyl sulfone by utilizing perfluoroalkyl sulfonic acid ionic liquid | |
| CN101870658B (en) | Keggin polyoxometallate-based ion liquid and synthesis method thereof | |
| CN103834197A (en) | Preparation method of organic montmorillonite modified by supermolecular liquid crystal polymer | |
| CN110724107A (en) | Preparation method and application of diallyl ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121107 |