CN101838198A - Method for preparing carboxylic ester - Google Patents
Method for preparing carboxylic ester Download PDFInfo
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- CN101838198A CN101838198A CN201010171143A CN201010171143A CN101838198A CN 101838198 A CN101838198 A CN 101838198A CN 201010171143 A CN201010171143 A CN 201010171143A CN 201010171143 A CN201010171143 A CN 201010171143A CN 101838198 A CN101838198 A CN 101838198A
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Abstract
The invention provides a method for preparing carboxylic ester. After liquid-phase ionic liquid at room temperature is taken as a catalyst and an extracting agent at the same time to catalyze the reaction of olefin and carboxylic acid to generate carboxylic ester, the generated carboxylic ester is separated from carboxylic acid which does not react. During the whole reaction, the molar ratio of carboxylic acid to ionic liquid to olefin in a reaction system is always kept at 0.2-5:1:0.1-10; absolute pressure is controlled between 0.05 and 5.0 MPa; reaction temperature is controlled between 10 and 110 DEG C; and the space velocity of the carboxylic acid added during the reaction is controlled between 0.1 and 500. The method has the advantages of further rasing the conversion rate of carboxylic acid, reducing production cost and reducing pollution caused for environment.
Description
Technical field
The present invention relates to a kind of preparation method of carboxylicesters of green high-efficient.
Background technology
Carboxylic acid esters is a kind of very important organic chemical industry's product, can be used as spices, foodstuff additive, softening agent, defoamer and good organic solvent, is widely used in many chemical processs.The acid alcohol esterification method is adopted in the preparation of carboxylicesters mostly, this method expense of raw materials height, and can generate a certain amount of water.Because the acid alcohol esterification itself belongs to reversible balanced reaction, reach than higher transformation efficiency in order to make raw material carboxylic acid and alcohol, need to consume lot of energy the water that generates in the reaction process is shifted out reaction system.In addition, traditional esterification process adopts strong acid (as vitriol oil etc.) to realize as catalyzer mostly.After esterification finishes, be trapped in protonic acid in the reaction system in the reaction product separating process, cause final product by partial oxidation easily, side reaction takes place, resulting ester products color and luster is dark, and productive rate also can be influenced.Protonic acid is understood etching apparatus in addition, and a large amount of spent acid discharge then contaminate environment.For solid catalysts such as solid acid, the ion exchange resin catalyst for esterification reaction of new generation of protonic acid as an alternative, all be successful exploration, but deficiency is also arranged, as solid super-strong acid as catalyzer, by product is more, and lose easily in the active centre, the reaction process more complicated; The use temperature that resin cation (R.C.) allowed is lower, and the scope of application also is subjected to certain restriction.The formation reaction that no matter utilizes solid acid or ion exchange resin to come the catalysis ester all must solve the problem of the resistance to mass transfer in the heterogeneous catalytic reaction process, and corresponding technology and reactor design be more complicated all also.Therefore, development of new carboxylicesters production technique has favorable industrial application prospect.
In recent years, eco-friendly catalyst system provided more wide space to ionic liquid at room temperature for people explore.Room-temperature ion liquid itself has excellent chemistry and thermodynamic stability, many materials is all had good solvency power, and at room temperature have vapour pressure hardly, and this makes to be applied in and has had the characteristic of being convenient to product separation and catalyst recovery in the catalyzed reaction concurrently.The characteristic that ionic liquid is different from general molecular solvent also has its plasticity-, and the length, the function key kind that change ion liquid zwitterion and alkyl group side chain can in very large range be regulated ion liquid physicochemical property.For example, acidic-group (comprising sulfonic group, dihydrogen phosphoric acid base etc.) is chemically bonded on the ion liquid positively charged ion, can makes it to show very strong acidity.Particularly in the system of carboxylic esterification, reasonably control ion liquid polarity by suitable means, can be so that ionic liquid can dissolve the stronger carboxylic acid of polarity selectively, can guarantee to have less solubleness at ionic liquid in mutually simultaneously as the carboxylicesters of product.Since the ionic liquid of this functionalization have can flow, non-volatile, non-aggressive and with the immiscible special performance of carboxylicesters product, can be used as alkene and carboxylic acid addition and prepare catalyzer and extraction agent in this combination process of carboxylicesters.
The present invention proposes a kind of preparation method of new carboxylicesters under above-mentioned technical background, in the hope of the transformation efficiency that further improves carboxylic acid, reduce production costs and reduce pollution on the environment.
Summary of the invention
The objective of the invention is to: a kind of preparation method of new carboxylicesters is provided, further improve carboxylic acid transformation efficiency, reduce production costs and reduce pollution on the environment.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of carboxylicesters is provided, be with the ionic liquid that is liquid phase under the room temperature simultaneously as catalyzer and extraction agent, after catalyzed alkene generates carboxylicesters with carboxylic acid reaction, the carboxylicesters of generation is separated with unreacted carboxylic acid; In the entire reaction course, mol ratio in the reaction system between each material remains at carboxylic acid: ionic liquid: alkene is 0.2～5: 1: 0.1～10, pressure (absolute pressure) is controlled at 0.05MPa～5.0MPa, temperature of reaction is controlled at 10～110 ℃, and the air speed of the carboxylic acid that adds in the reaction process is controlled at 0.1～500.
The preferred 1-Methylimidazole of described ionic liquid ionic liquid, pyrrolidone ionic liquid or their mixture.
Negatively charged ion in the described ionic liquid can be selected from a kind of in methanesulfonic root, bisulfate ion, dihydrogen phosphate, tetrafluoroborate, hexafluoro-phosphate radical or the trifluoromethanesulfonic acid root.
Further preferred ionic liquid structure is as follows:
Wherein m is 0～4 integer, preferred 1～2 integer.
Further preferred ionic liquid can also be a structure ionic liquid as follows:
Described ionic liquid is existing material, can obtain by the reference prior art for preparing, for example can prepare in accordance with the following methods:
1. synthesis of pyrrolidine ketone ionic liquid
1) getting equimolar pyrrolidone and lactone compound, is solvent with the anhydrous diethyl ether, stirs 10～20 hours down in normal temperature, and after filtration, methanol wash after the vacuum-drying, promptly gets white solid powder ionic liquid precursor; Described lactone compound can be 1,3-propane sultone or 1,4-butane sultone;
2) in the ionic liquid precursor that concentrated acid to the step 1) of dropping equimolar amount obtains, 60～100 ℃ were stirred 6～10 hours down, with the ethyl acetate washing, after under 80 ℃ of vacuum dry 1～3 hour, promptly got the pyrrolidone ionic liquid then; Described concentrated acid is selected from a kind of in methanesulfonic, sulfuric acid, phosphoric acid, Tetrafluoroboric acid, phosphofluoric acid or the trifluoromethanesulfonic acid.
2. synthetic 1-Methylimidazole ionic liquid
In the there-necked flask of agitator is housed, add the 1-Methylimidazole, under condition of ice bath, slowly drip the concentrated acid of equimolar amount, after being added dropwise to complete, form a large amount of white solids with dropping funnel, at room temperature stir 20～24h, along with the carrying out that under agitation reacts, solid fades away, and washs with ethyl acetate then, at 0.01MPa, 80 ℃ of following vacuum-drying 8h, final product is a 1-Methylimidazole ionic liquid at last; Described concentrated acid is selected from a kind of in methanesulfonic, sulfuric acid, phosphoric acid, Tetrafluoroboric acid, phosphofluoric acid or the trifluoromethanesulfonic acid.
Described alkene is that carbon chain lengths is C
2To C
18Straight chain, side chain or cyclic olefin.
Described carboxylic acid is that carbon number is C
1To C
18Aliphatic or aromatic acid.
Described temperature of reaction preferably is controlled at 10～80 ℃.
After described reaction finishes, can also with used ionic liquid after extracting in 80～100 ℃ of following evacuation processes, turn back in the reaction system again and reuse.
The preparation method of a kind of preferred carboxylicesters of the present invention is the process of the synthetic ester of pyrrolidone sulfonate ion liquid catalyst, and it may further comprise the steps:
In being lined with the stainless steel autoclave of Glass tubing, the airtight and inwall of being furnished with magnetic agitation adds alkene, acid, ionic liquid and magneton successively, and in reaction process in continuous supplementation alkene and the carboxylic acid whole reaction system, the mol ratio between each material remains at carboxylic acid: ionic liquid: alkene is 0.2～5: 1: 0.1～10; The air speed of the carboxylic acid that adds in the reaction process is controlled between 0.1～500; Under the condition of 10～110 ℃ (preferred 10～80 ℃), pressure 0.1～2.0Mpa, react, when the interface between ionic liquid layer and the top ester layer does not change, think that reaction has reached stable state, take out the upper strata esterification products this moment, can obtain having the thick product of higher carboxylicesters content.
The method for preparing carboxylicesters of the present invention, since the homo-ion liquid of formed ester insoluble and with the ionic liquid natural layering, make in the entire reaction course, there are 2 immiscible liquid phases in the reaction system, ionic liquid and the unreacted carboxylic acid of part become heavier one mutually, be designated as the ionic liquid phase, the carboxylicesters that this reaction that also can dissolve some amount in mutually generates; What the reaction system upper strata was lighter one mainly comprises the carboxylicesters that reaction generates in mutually and also has the unreacted carboxylic acid of part, is designated as the carboxylicesters phase.In the above-mentioned two-phase, the carboxylicesters concentration (quality percentage composition) of middle carboxylicesters mutually is higher than the ionic liquid concentration (quality percentage composition) of middle carboxylicesters mutually.
Compared with prior art, the present invention's method of preparing carboxylicesters has following beneficial effect:
1. with in the prior art compare, can significantly improve the transformation efficiency and the esterification selectivity of acid.
Because what the present invention adopted is ionic-liquid catalyst, but not inorganic solid catalyst, institute is so that reaction raw materials can contact more fully with catalyzer, and the esterification better effects and if the selectivity of acquisition are higher.
2. with in the prior art compare, can significantly reduce production costs.
On the one hand, method of the present invention has constituted continuous reaction and has separated the technological process that is coupled owing to adopted ionic liquid as catalyzer, has strengthened reaction process, and ester content is higher in the product that obtains; With the preparation tert.-butyl acetate is example, when using preparation method of the present invention, in the reaction system carboxylicesters mutually in the concentration of tert.-butyl acetate can reach more than 50%, and by conventional catalyzed reaction (use solid catalyst) when method prepares, the concentration of tert.-butyl acetate is the highest in mutually can only reach 35% for carboxylicesters in the reaction system.When therefore using method of the present invention to prepare carboxylicesters, can improve the concentration of target product in the thick product, simplify the complicacy of follow-up treating process, thereby significantly reduce the production cost for the treatment of process.
On the other hand because the present invention adopts alkene as raw material, with in the prior art with sour be that raw material is compared with alcohol, can significantly reduce cost.
Again on the one hand, owing to there is not the generation of water in the reaction of the present invention, therefore also avoided in the alcohol/sour technology owing to the increase that divides the water energy consumption cost that difficulty causes.
Generally speaking, the method for preparing carboxylicesters of the present invention, its cost is less than half of art methods.
3. with in the prior art compare, can significantly reduce influence environment.
Because method of the present invention is acid/alkene technology, itself belong to typical green chemical industry technology, do not use in addition that toxicity is big, the catalyzer of severe corrosive, be an eco-friendly reaction process therefore.
Embodiment
2-butyl acetate is synthetic in embodiment 1.1-(3-sulfonic group)-propyl group-2-Pyrrolidone hydrosulfate ionic liquid
1) get equimolar 2-Pyrrolidone and 1,3-propane sultone is a solvent with the anhydrous diethyl ether, stirs 20 hours down in normal temperature, and after filtration, methanol wash after the vacuum-drying, promptly gets white solid powder ionic liquid precursor; The vitriol oil that drips equimolar amount is to the ionic liquid precursor, and 80 ℃ were stirred 8 hours down, with the ethyl acetate washing, after under 80 ℃ of vacuum dry 1 to 3 hour, promptly get tawny thickness ionic liquid [C then
3SO
3Hnhp] HSO
4
2) get 1-(3-sulfonic group)-propyl group-2-Pyrrolidone hydrosulfate ionic liquid 100mmol that step 1) prepares, add 50mmol acetic acid under the room temperature, place autoclave.Flow according to 150mmol/h replenishes acetic acid in still then, flow according to 450mmol/h adds 1-butylene in still simultaneously, in 105 ℃, 0.8MPa following reaction after 3 hours in the still liquid level no longer change, extract a small amount of upper strata organic liquid, use the HP6890 chromatogram to analyze, use the 2-butyl acetate standard to carry out interior mark, can obtain quantitative results: acetic acid transformation efficiency 92%, 2-butyl acetate selectivity 100%.73% the situation of only reaching with acetic acid transformation efficiency in the conventional procedure is compared, and the acetic acid transformation efficiency increases substantially.
Wickenol 116 is synthetic in embodiment 2.1-(4-sulfonic group)-butyl-2-Pyrrolidone hydrosulfate ionic liquid
1) get equimolar 2-Pyrrolidone and 1, the 4-butane sultone is a solvent with the anhydrous diethyl ether, stirs 20 hours down in normal temperature, and after filtration, methanol wash after the vacuum-drying, promptly gets white solid powder ionic liquid precursor; The strong phosphoric acid that drips equimolar amount is to the ionic liquid precursor, and 80 ℃ were stirred 8 hours down, with the ethyl acetate washing, after under 80 ℃ of vacuum dry 1 to 3 hour, promptly get tawny thickness ionic liquid [C then
4SO
3Hnhp] H
2PO
4
2) get 1-(4-sulfonic group)-butyl-2-Pyrrolidone hydrosulfate ionic liquid 100mmol that step 1) prepares, add the 50mmol hexanodioic acid under the room temperature, place autoclave.Flow according to 150mmol/h replenishes hexanodioic acid in still then, flow according to 700mmol/h adds propylene in still simultaneously, in 120 ℃, 1.0MPa following stirring reaction is after 3.5 hours, liquid level no longer changes in the still, extracts a small amount of upper strata organic liquid, use the HP6890 chromatogram to analyze, use the Wickenol 116 standard to carry out interior mark, can obtain quantitative results: hexanodioic acid transformation efficiency 78%, Wickenol 116 selectivity 100%.47% the situation of only reaching with hexanodioic acid transformation efficiency in the conventional procedure is compared, and the hexanodioic acid transformation efficiency increases substantially.
The pentanedioic acid diisopropyl ester is synthetic in the embodiment 3:1-Methylimidazole hydrosulfate ionic liquid
1) in the there-necked flask of agitator is housed, add 75ml 1-Methylimidazole, under condition of ice bath, slowly drip the vitriol oil of equimolar amount with dropping funnel, after being added dropwise to complete, form a large amount of white solids, at room temperature stir 22h, along with the carrying out that under agitation reacts, solid fades away, wash with ethyl acetate then, at 0.01MPa, 80 ℃ of following vacuum-drying 8h, final product is the thick liquid of little yellow transparent shape at last, is final synthetic 1-Methylimidazole hydrosulfate ionic liquid.
2) get the 1-Methylimidazole hydrosulfate ionic liquid 100mmol that step 1) prepares, add the 50mmol pentanedioic acid under the room temperature, place autoclave.Flow according to 150mmol/h replenishes pentanedioic acid in still then, flow according to 700mmol/h adds propylene in still simultaneously, in 100 ℃, 1.0MPa following stirring reaction is after 2 hours, liquid level no longer changes in the still, extracts a small amount of upper strata organic liquid, use the HP6890 chromatogram to analyze, use pentanedioic acid diisopropyl ester standard to carry out interior mark, can obtain quantitative results: pentanedioic acid transformation efficiency 82%, pentanedioic acid diisopropyl ester selectivity 100%.56% the situation of only reaching with pentanedioic acid transformation efficiency in the conventional procedure is compared, and the pentanedioic acid transformation efficiency increases substantially.
Claims (10)
1. the preparation method of a carboxylicesters is characterized in that: be with the ionic liquid that is liquid phase under the room temperature simultaneously as catalyzer and extraction agent, after catalyzed alkene generates carboxylicesters with carboxylic acid reaction, the carboxylicesters of generation is separated with unreacted carboxylic acid; In the entire reaction course, mol ratio in the reaction system between each material remains at carboxylic acid: ionic liquid: alkene is 0.2～5: 1: 0.1～10, absolute pressure is controlled at 0.05MPa～5.0MPa, temperature of reaction is controlled at 10～110 ℃, and the air speed of the carboxylic acid that adds in the reaction process is controlled at 0.1～500.
2. the preparation method of the described carboxylicesters of claim 1, it is characterized in that: described ionic liquid is 1-Methylimidazole ionic liquid, pyrrolidone ionic liquid or their mixture.
3. the preparation method of the described carboxylicesters of claim 2 is characterized in that: the negatively charged ion in the described ionic liquid is selected from a kind of in methanesulfonic root, bisulfate ion, dihydrogen phosphate, tetrafluoroborate, hexafluoro-phosphate radical or the trifluoromethanesulfonic acid root.
4. the preparation method of the described carboxylicesters of claim 3 is characterized in that, described ionic liquid structure is as shown in the formula shown in (I):
(I)
Wherein m is 0～4 integer.
5. the preparation method of the described carboxylicesters of claim 4, it is characterized in that: m is 1～2 integer in the described structure.
6. the preparation method of the described carboxylicesters of claim 3 is characterized in that, described ionic liquid is a structure as shown in the formula the ionic liquid shown in (II):
(II)
Wherein n is 0～6 integer.
7. the preparation method of the described carboxylicesters of claim 6, it is characterized in that: n is 3～4 integer in the described structure.
8. the preparation method of the described carboxylicesters of claim 1, it is characterized in that: described alkene is that carbon chain lengths is C
2To C
18Straight chain, side chain or cyclic olefin.
9. the preparation method of the described carboxylicesters of claim 1, it is characterized in that: described carboxylic acid is that carbon number is C
1To C
18Aliphatic or aromatic acid.
10. the preparation method of the described carboxylicesters of claim 1, it is characterized in that: described temperature of reaction is controlled at 10～80 ℃.
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| CN201010171143A CN101838198A (en) | 2010-05-13 | 2010-05-13 | Method for preparing carboxylic ester |
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| CN201010171143A CN101838198A (en) | 2010-05-13 | 2010-05-13 | Method for preparing carboxylic ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304398A (en) * | 2013-05-11 | 2013-09-18 | 万华化学集团股份有限公司 | Purification method of carboxylic acid aqueous solution |
| CN105585485A (en) * | 2014-10-21 | 2016-05-18 | 中国科学院过程工程研究所 | Production method for low-carbon acetate |
| US20170174857A1 (en) * | 2015-12-16 | 2017-06-22 | Industrial Technology Research Institute | Porous hydrophobic fluorine-containing polymer membrane and production methods thereof |
| CN107954874A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of method for preparing benzoic ether |
| CN109576020A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of Lubricity of Low-Sulfur Diesel Fuels modifier is synthesized in a kind of ionic liquid |
| CN113788775A (en) * | 2021-09-03 | 2021-12-14 | 南昌大学 | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN1600773A (en) * | 2003-09-25 | 2005-03-30 | 中国科学院兰州化学物理研究所 | Method for esterifying olefin and organic acid |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN1600773A (en) * | 2003-09-25 | 2005-03-30 | 中国科学院兰州化学物理研究所 | Method for esterifying olefin and organic acid |
Non-Patent Citations (2)
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|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304398A (en) * | 2013-05-11 | 2013-09-18 | 万华化学集团股份有限公司 | Purification method of carboxylic acid aqueous solution |
| CN105585485A (en) * | 2014-10-21 | 2016-05-18 | 中国科学院过程工程研究所 | Production method for low-carbon acetate |
| US20170174857A1 (en) * | 2015-12-16 | 2017-06-22 | Industrial Technology Research Institute | Porous hydrophobic fluorine-containing polymer membrane and production methods thereof |
| US10000617B2 (en) * | 2015-12-16 | 2018-06-19 | Industrial Technology Research Institute | Method of manufacturing porous fluorine-containing polymer membrane |
| CN107954874A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of method for preparing benzoic ether |
| CN109576020A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of Lubricity of Low-Sulfur Diesel Fuels modifier is synthesized in a kind of ionic liquid |
| CN109576020B (en) * | 2017-09-28 | 2021-02-05 | 中国石油化工股份有限公司 | Method for synthesizing low-sulfur diesel lubricity improver in ionic liquid |
| CN113788775A (en) * | 2021-09-03 | 2021-12-14 | 南昌大学 | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst and preparation method and application thereof |
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Application publication date: 20100922 |