CN111302935A - Ethyl linoleate synthesized by ionic liquid microemulsion catalysis and preparation method thereof - Google Patents
Ethyl linoleate synthesized by ionic liquid microemulsion catalysis and preparation method thereof Download PDFInfo
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- CN111302935A CN111302935A CN202010228406.0A CN202010228406A CN111302935A CN 111302935 A CN111302935 A CN 111302935A CN 202010228406 A CN202010228406 A CN 202010228406A CN 111302935 A CN111302935 A CN 111302935A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 107
- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 85
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 title claims abstract description 46
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229940031016 ethyl linoleate Drugs 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims abstract description 23
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims abstract description 23
- 235000020778 linoleic acid Nutrition 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 17
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 41
- WEZFRVSBUPJHFG-UHFFFAOYSA-N 3-hexyl-1-methyl-1,2-dihydroimidazol-1-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCCCN1C[NH+](C)C=C1 WEZFRVSBUPJHFG-UHFFFAOYSA-N 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- -1 1-decyl-3-methylimidazole bisulfate Chemical compound 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- PXAVGTWNUANSAK-UHFFFAOYSA-N 1-hexadecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+]1CN(C)C=C1 PXAVGTWNUANSAK-UHFFFAOYSA-N 0.000 claims description 2
- DHGRQWQXYRLION-UHFFFAOYSA-N S(=O)(=O)(O)O.C(CCCCCCCCCCC)N1CN(C=C1)C Chemical compound S(=O)(=O)(O)O.C(CCCCCCCCCCC)N1CN(C=C1)C DHGRQWQXYRLION-UHFFFAOYSA-N 0.000 claims description 2
- IZZXUYYYPZPVJF-UHFFFAOYSA-N S(O)(O)(=O)=O.CN1CN(C=C1)CCCCCCCC Chemical compound S(O)(O)(=O)=O.CN1CN(C=C1)CCCCCCCC IZZXUYYYPZPVJF-UHFFFAOYSA-N 0.000 claims description 2
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000012429 reaction media Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical group CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 4
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical group CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 239000008280 blood Substances 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000012430 organic reaction media Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of ethyl linoleate and discloses ethyl linoleate synthesized by catalysis of ionic liquid microemulsion and a preparation method thereof. The preparation process comprises the following steps: (1) adding a non-polar solvent into a conventional surfactant, uniformly mixing, then dripping imidazole ionic liquid, and fully mixing to obtain a single ionic liquid microemulsion; (2) adding linoleic acid and ethanol into the single ionic liquid microemulsion, heating for reaction, and performing rotary evaporation to obtain linoleic acid ethyl ester. The method of the invention uses the single ionic liquid microemulsion with good high-temperature stability as a reaction medium, increases the contact area of the catalyst and a reaction substrate, solubilizes the generated water in the core of the ionic liquid microemulsion, and accelerates the reaction rate; the catalyst has high activity, but has little corrosion to equipment and low requirement on the equipment, solves the problems of high cost, serious equipment corrosion, low reaction yield, poor product quality, harsh reaction conditions and the like of the catalyst in the prior art, and can be popularized and applied to catalytic esterification reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of ethyl linoleate, and particularly relates to ethyl linoleate synthesized by catalysis of ionic liquid microemulsion and a preparation method thereof.
Background
The ethyl linoleate is colorless to light yellow oily liquid, has the functions of reducing cholesterol and blood fat like the linoleic acid, and can effectively prevent or alleviate atherosclerosis. Ethyl linoleate is much lighter than linoleic acid for its side reactions. Can also be used as pharmaceutical raw material.
The esterification reaction for early synthesizing the ethyl linoleate mostly uses concentrated sulfuric acid as a catalyst, but the process flow has the problems of large discharge amount of acidic wastewater in the production process, serious corrosion of production equipment and the like. Subsequent researchers have replaced liquid acid with solid super acid, but solid super acid catalyst has limited its industrial application because of volatile activity and poor reusability.
The ionic liquid is an organic salt which is composed of organic cations and inorganic or organic anions and is liquid at room temperature, is used as a novel medium and material, has almost no vapor pressure, has excellent physicochemical properties such as non-flammability, non-volatility, good chemical stability and thermal stability, recyclability, environmental friendliness and the like, and has wide application prospect. The ionic liquid is relatively mature in research on catalytic esterification reaction, but most of the used ionic liquids are pyrrole ionic liquids (such as 20121017640.5 and 20071005217.5) with strong catalytic activity and sulfonic acid groups on anions, and the ionic liquids are complex to synthesize and high in extraction process cost.
Microemulsions are isotropic, thermodynamically stable systems composed of water, oil and surfactant. There are several advantages to using microemulsions as the organic reaction medium: overcomes the incompatibility of reagents and the specificity of reaction, and improves the reaction efficiency (microemulsion catalysis) and the induction area selectivity. The research of catalyzing esterification reaction by using microemulsion as a reaction medium has related reports, but the microemulsion in the research is aqueous microemulsion, and the catalytic esterification reaction of the aqueous microemulsion is not beneficial to industrial production under the condition of long time (more than 24 hours) and low temperature (30-60 ℃).
The ionic liquid, the surfactant and the nonpolar solvent are combined to form a transparent microemulsion system with stable thermodynamics and good high-temperature resistance. The ionic liquid microemulsion as a novel microemulsion has a plurality of excellent properties, and can carry out a plurality of chemical reactions in the ionic liquid microemulsion.
At present, the ionic liquid microemulsion has become a hot spot and a leading edge of green chemical research due to the advantages of thermodynamic stability, flexible composition, designability and the like. The ionic liquid microemulsion has the advantages of both ionic liquid and microemulsion, has unique advantages as a reaction medium, has relatively higher temperature independence than the traditional water microemulsion, can stably exist at higher temperature (80-160 ℃), and has no damage to the microemulsion structure.
In the catalytic esterification reaction process of the ionic liquid microemulsion, the ionic liquid with the functions of catalysis and surfactant can promote the formation of the ionic liquid microemulsion, increase the contact area of the catalyst and a reaction substrate, the water generated by the reaction enters the inner core of the ionic liquid microemulsion, and the hydrophilic ionic liquid in the inner core can form hydrogen bonds with the water generated by the reaction, thereby reducing the inhibition of reaction products on the reaction process and promoting the forward movement of the reaction. The ionic liquid microemulsion is applied to the catalytic esterification reaction, so that the application range of the ionic liquid microemulsion is widened to a great extent, and the ionic liquid microemulsion is developed into a novel research field with application prospect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an ethyl linoleate synthesized by catalysis of ionic liquid microemulsion and a preparation method thereof. The invention carries out esterification reaction on linoleic acid and ethanol in an ionic liquid microemulsion system, has mild reaction process conditions, light product color and easy separation, and is a green and environment-friendly synthesis method with application prospect.
The invention is realized by the following technical scheme:
a preparation method for synthesizing ethyl linoleate by catalysis of ionic liquid microemulsion comprises the following steps:
(1) adding imidazole ionic liquid into a surfactant, uniformly mixing, adding a non-polar solvent, and fully mixing to obtain ionic liquid microemulsion;
(2) adding linoleic acid and ethanol into the ionic liquid microemulsion, heating for reaction, and performing rotary evaporation to obtain linoleic acid ethyl ester;
the imidazole ionic liquid is at least one of 1-hexyl-3-methylimidazole bisulfate, 1-octyl-3-methylimidazole bisulfate, 1-decyl-3-methylimidazole bisulfate and 1-dodecyl-3-methylimidazole bisulfate;
the surfactant is octyl phenyl polyoxyethylene ether (TX-100, TX-45, TX-114), Cetyl Trimethyl Ammonium Bromide (CTAB), sodium bis (2-ethylhexyl) succinate sulfonate (AOT) and 1-hexadecyl-3-methylimidazole chloride salt ([ C)16mim]Cl);
the nonpolar solvent is at least one of cyclohexane, toluene and n-hexane.
In the step (1), the content of the surfactant is 32-72%, the content of the nonpolar solvent is 24-48%, and the content of the imidazole ionic liquid is 4-12%.
The mass ratio of the surfactant to the imidazole ionic liquid in the step (1) is 4: 1-10: 1. Before use, the surfactant and the imidazole ionic liquid are uniformly mixed, and the imidazole ionic liquid can play a catalytic role.
In the step (2), the molar ratio of the linoleic acid to the ethanol is 1: 4-1: 7.
The mass ratio of the linoleic acid in the step (2) to the ionic liquid microemulsion is 1: 1-1: 5.
The specific steps for obtaining the ethyl linoleate in the step (2) are as follows:
adding linoleic acid and ethanol into the ionic liquid microemulsion, and stirring for 5-10 minutes at a stirring speed of 300-1200 revolutions per minute; and then reacting for 4-10 h at the temperature of 30-50 ℃ and the stirring speed of 300-1200 rpm, and performing rotary evaporation to obtain the ethyl linoleate.
In the esterification reaction process, the imidazole ionic liquid can promote the formation of ionic liquid microemulsion and increase the contact area of the catalyst and a reaction substrate; the imidazole ionic liquid with strong hydrophilicity can form hydrogen bonds with water generated by the esterification reaction, and the water generated by the reaction is transferred to the kernel of the ionic liquid microemulsion in the esterification reaction process, so that the forward movement of the esterification reaction is promoted, and the conversion rate is improved.
The preparation process solves the problems of high catalyst cost, serious equipment corrosion, low reaction yield, poor product quality, harsh reaction conditions and the like in the prior art. The linoleic acid ethyl ester prepared by the method has higher yield, shows the application prospect of the ionic liquid microemulsion system in the esterification reaction, and can be popularized and applied to the catalytic esterification reaction.
Compared with the prior art, the invention has the following advantages and effects:
the ionic liquid microemulsion is used as a reaction medium, the catalyst has the function of a surfactant, the formation of the ionic liquid microemulsion can be promoted, the contact area of the catalyst and a reaction substrate is increased, water generated in the esterification reaction is solubilized in an ionic liquid microemulsion core, and the reaction rate is accelerated; the selected catalyst has strong catalytic activity, but has small corrosion to equipment and low requirements on processing materials of the equipment compared with the conventional strong acid and strong base catalyst, and can effectively reduce fixed assets.
The invention has the advantages of relatively low process cost, no environmental pollution and good industrial application prospect.
Drawings
FIG. 1 is a gas chromatogram of commercially available ethyl linoleate.
FIG. 2 is a gas chromatogram of ethyl linoleate obtained in example 1 of the present invention.
FIG. 3 is a mass spectrum of ethyl linoleate obtained by the preparation of example 1 of the invention.
FIG. 4 is a molecular structure diagram of ethyl linoleate in accordance with the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Hmim]HSO46 parts by weight (from the institute of chemico-physical, Lanzhou, academy of sciences of China), 5 parts by weight of cyclohexane, and 24 parts by weight of a conventional surfactant TX-100 (from Guangzhou glass instruments, Inc.).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-hexyl-3-methylimidazole bisulfate are uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, and the clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
7.6049g of ionic liquid microemulsion, 5.6256g of linoleic acid and 5.7181g of ethanol are taken, stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 700 r/min, the reaction temperature is 40 ℃, and the reaction time is 6 h. In the reaction process, the 1-hexyl-3-methylimidazole hydrogen sulfate can promote the formation of ionic liquid microemulsion, the contact area of the catalyst 1-hexyl-3-methylimidazole hydrogen sulfate with linoleic acid and ethanol is increased, a hydrogen bond can be formed with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The product obtained is identified to be ethyl linoleate (shown in figures 1-2) by a gas chromatograph, and the yield of the ethyl linoleate is 82.32%.
Example 2
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Hmim]HSO4(from the institute of chemico-physical research, Lanzhou, academy of Chinese sciences) 2 parts by weight, cyclohexane 1 part by weight, and4 parts by weight of a conventional surfactant TX-100 (available from Guangzhou Kokukushi glass instruments).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-hexyl-3-methylimidazole bisulfate are uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, and the clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
6.284g of ionic liquid microemulsion, 5.7845g of linoleic acid and 5.6226g of ethanol are taken, stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 700 r/min, the reaction temperature is 40 ℃, and the reaction time is 6 h. In the reaction process, the 1-hexyl-3-methylimidazole hydrogen sulfate can promote the formation of ionic liquid microemulsion, the contact area of the catalyst 1-hexyl-3-methylimidazole hydrogen sulfate with linoleic acid and ethanol is increased, a hydrogen bond can be formed with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The product obtained is identified to be ethyl linoleate by a gas chromatograph, and the yield of the ethyl linoleate is 81.54%.
Example 3
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Bmim ]]HSO46 parts by weight (from the institute of chemico-physical, Lanzhou, academy of sciences of China), 5 parts by weight of cyclohexane, and 24 parts by weight of a conventional surfactant TX-100 (from Guangzhou glass instruments, Inc.).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-butyl-3-methylimidazole bisulfate are uniformly mixed, the stirring speed is 1000 r/min, the stirring is carried out for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 1000 r/min, the stirring is carried out for 5 min, and the clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
7.5950g of ionic liquid microemulsion, 5.6230g of linoleic acid and 5.5346g of ethanol are taken, stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 1000 r/min, the reaction temperature is 30 ℃, and the reaction time is 6 h. In the reaction process, the 1-butyl-3-methylimidazole hydrogen sulfate can promote the formation of ionic liquid microemulsion, the contact area of the catalyst 1-butyl-3-methylimidazole hydrogen sulfate with linoleic acid and ethanol is increased, a hydrogen bond can be formed with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The product obtained is identified by a gas chromatograph to be linoleic acid ethyl ester, and the yield of the linoleic acid ethyl ester is 73.33 percent.
Example 4
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Bmim ]]BF46 parts by weight (from the institute of chemico-physical, Lanzhou, academy of sciences of China), 5 parts by weight of cyclohexane, and 24 parts by weight of a conventional surfactant TX-100 (from Guangzhou glass instruments, Inc.).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-butyl-3-methylimidazole tetrafluoroborate are uniformly mixed, the stirring speed is 700 r/min, the mixture is stirred for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 700 r/min, and the stirring is 5 min, so that clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
7.3397g of ionic liquid microemulsion, 5.6175g of linoleic acid and 4.6120g of ethanol are stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 700 r/min, the reaction temperature is 40 ℃, and the reaction time is 4 h. In the reaction process, the 1-butyl-3-methylimidazole tetrafluoroborate can promote the formation of ionic liquid microemulsion, increase the contact area of the catalyst 1-butyl-3-methylimidazole tetrafluoroborate with linoleic acid and ethanol, and can form hydrogen bonds with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The obtained product is identified to be ethyl linoleate by a gas chromatograph, and the yield of the ethyl linoleate is 45.89%.
Example 5
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Hmim]HSO 44 parts by weight (from the institute of chemico-physical, Lanzhou, academy of sciences of China), 5 parts by weight of cyclohexane, and 24 parts by weight of a conventional surfactant TX-100 (from Guangzhou glass instruments, Inc.).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-hexyl-3-methylimidazole bisulfate are uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, and the clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
7.5968g of ionic liquid microemulsion, 5.6923g of linoleic acid and 5.5217g of ethanol are stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 700 r/min, the reaction temperature is 40 ℃, and the reaction time is 4 h. In the reaction process, the 1-hexyl-3-methylimidazole hydrogen sulfate can promote the formation of ionic liquid microemulsion, the contact area of the catalyst 1-hexyl-3-methylimidazole hydrogen sulfate with linoleic acid and ethanol is increased, a hydrogen bond can be formed with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The obtained product is identified to be ethyl linoleate by a gas chromatograph, and the yield of the ethyl linoleate is 60.16%.
Example 6
The ionic liquid microemulsion comprises the following components in percentage by weight: hydrophilic ionic liquid [ Hmim]HSO4(purchased from Lanzhou institute of chemical and physical research, academy of sciences, China) 4 parts by weight and cyclohexane 5 parts by weightThe amount of the surfactant is 24 parts by weight of a conventional surfactant TX-100 (purchased from Guangzhou Kokugaku glass instruments).
Under the condition of 25 ℃, surfactant TX-100 and imidazole ionic liquid 1-hexyl-3-methylimidazole bisulfate are uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, a clear and transparent mixture is obtained, cyclohexane is added and uniformly mixed, the stirring speed is 700 r/min, the stirring is carried out for 5 min, and the clear and transparent ionic liquid microemulsion with good high-temperature stability is obtained.
7.7131g of ionic liquid microemulsion, 5.6112g of linoleic acid and 5.5653g of ethanol are taken, stirred and mixed, and esterification reaction is carried out under stirring, wherein the stirring speed is 700 r/min, the reaction temperature is 40 ℃, and the reaction time is 8 h. In the reaction process, the 1-hexyl-3-methylimidazole hydrogen sulfate can promote the formation of ionic liquid microemulsion, the contact area of the catalyst 1-hexyl-3-methylimidazole hydrogen sulfate with linoleic acid and ethanol is increased, a hydrogen bond can be formed with water generated in the esterification reaction, and the water generated in the esterification reaction is transferred to the inner core of the ionic liquid microemulsion to promote the forward movement of the esterification reaction.
And after the reaction is finished, transferring the product to a rotary evaporation instrument, starting a vacuum pump, and carrying out rotary evaporation for 1 hour at the vacuum temperature of 50 ℃ to obtain the product. The obtained product is identified to be ethyl linoleate by a gas chromatograph, and the yield of the ethyl linoleate is 91.07%.
FIG. 1 shows a gas chromatogram of a standard ethyl linoleate (. gtoreq.97% GC; product number E135184; CAS number 544-35-4; brand aladdin). Chromatographically pure (GC): the gas chromatographic analysis is special, and the quality index emphasizes impurities which interfere with the gas chromatographic peak, and the main component content is high.
Product evaluation
The product of example 1 was checked by gas chromatography to verify that the product was ethyl linoleate.
FIGS. 2-3 are gas chromatograms of the product of example 1. The product obtained is ethyl linoleate, as known by comparison. The products of other examples were verified to be ethyl linoleate.
The method of the invention uses the single ionic liquid microemulsion with good high-temperature stability as a reaction medium, increases the contact area of the catalyst and a reaction substrate, solubilizes the generated water in the core of the ionic liquid microemulsion, and accelerates the reaction rate; the catalyst has high activity, but has little corrosion to equipment and low requirement on the equipment, solves the problems of high cost, serious equipment corrosion, low reaction yield, poor product quality, harsh reaction conditions and the like of the catalyst in the prior art, and can be popularized and applied to catalytic esterification reaction.
As described above, the present invention can be preferably realized.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (6)
1. A preparation method for synthesizing ethyl linoleate by using ionic liquid microemulsion as a catalyst is characterized by comprising the following steps:
(1) adding imidazole ionic liquid into a surfactant, uniformly mixing, adding a non-polar solvent, and fully mixing to obtain ionic liquid microemulsion;
(2) adding linoleic acid and ethanol into the ionic liquid microemulsion, heating for reaction, and performing rotary evaporation to obtain linoleic acid ethyl ester;
the imidazole ionic liquid is at least one of 1-hexyl-3-methylimidazole bisulfate, 1-octyl-3-methylimidazole bisulfate, 1-decyl-3-methylimidazole bisulfate and 1-dodecyl-3-methylimidazole bisulfate;
the surfactant is at least one of octyl phenyl polyoxyethylene ether, hexadecyl trimethyl ammonium bromide, sodium bis (2-ethylhexyl) succinate sulfonate and 1-hexadecyl-3-methylimidazole chloride salt;
the nonpolar solvent is at least one of cyclohexane, toluene and n-hexane.
2. The preparation method for synthesizing the ethyl linoleate by catalyzing the ionic liquid microemulsion according to the claim 1 is characterized in that: in the step (1), the content of the surfactant is 32-72%, the content of the nonpolar solvent is 24-48%, and the content of the imidazole ionic liquid is 4-12%.
3. The preparation method for synthesizing ethyl linoleate by catalysis of ionic liquid microemulsion according to claim 2 is characterized in that: the mass ratio of the surfactant to the imidazole ionic liquid in the step (1) is 4: 1-10: 1.
4. The preparation method for synthesizing ethyl linoleate by catalysis of ionic liquid microemulsion according to claim 3 is characterized in that: in the step (2), the molar ratio of the linoleic acid to the ethanol is 1: 4-1: 7.
5. The preparation method for synthesizing ethyl linoleate by catalysis of ionic liquid microemulsion according to claim 4 is characterized in that: the mass ratio of the linoleic acid in the step (2) to the ionic liquid microemulsion is 1: 1-1: 5.
6. The preparation method for synthesizing ethyl linoleate by catalysis of ionic liquid microemulsion according to claim 5, wherein the specific steps of obtaining ethyl linoleate in step (2) are as follows:
adding linoleic acid and ethanol into the ionic liquid microemulsion, and stirring for 5-10 minutes at a stirring speed of 300-1200 revolutions per minute; and then reacting for 4-10 h at the temperature of 30-50 ℃ and the stirring speed of 300-1200 rpm, and performing rotary evaporation to obtain the ethyl linoleate.
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