CN102617700A - Preparation method of phytostanol ester by taking ionic liquid as catalyst - Google Patents
Preparation method of phytostanol ester by taking ionic liquid as catalyst Download PDFInfo
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- CN102617700A CN102617700A CN201210050865XA CN201210050865A CN102617700A CN 102617700 A CN102617700 A CN 102617700A CN 201210050865X A CN201210050865X A CN 201210050865XA CN 201210050865 A CN201210050865 A CN 201210050865A CN 102617700 A CN102617700 A CN 102617700A
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- acid
- ionic liquid
- stanol ester
- plant stanol
- phytostanols
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Abstract
The invention relates to a novel preparation method of a phytostanol ester by taking an ionic liquid as a catalyst. The technical scheme adopted by the invention is as follows: in the absence of solvents and in the presence of nitrogen, a fatty acid (saturated or unsaturated acid) and phytostanol are heated to 90 to 180 DEG C to be melted completely, and are added with a catalyst to be subjected to an esterification reaction for 1 to 15 hours by controlling the temperature between 90 DEG C and 180 DEG C; a hydroxy acid, the phytostanol and the catalyst are added to a benzene, toluene or xylene solvent, and are heated to 80 to 115 DEG C to be subjected to the esterification reaction for 5 to 20 hours at this temperature; and after the end of the reaction, the phytostanol ester is obtained by separation and purification. The ionic liquid used in the method does not pollute the environment, has no obvious corrodibility, and is easy to recycle and reuse; the conversion rate of the phytostanol is high; and the product is convenient to recover, and the operation is simple.
Description
Technical field
The present invention relates to the preparation method of plant stanol ester, particularly a kind of is the method for Preparation of Catalyst lipid acid (saturated or unsaturated acid) or alcohol acid plant stanol ester with the ionic liquid.
Background technology
Plant sterol and phytostanols are the plant Equivalents of animal SUV; They can form the competitive relation that absorbs with SUV in small intestine; Substitute the part SUV and be absorbed, and itself can not be utilized, thereby reach the effect that reduces low-density lipoprotein cholesterol level in the blood.Result of study in recent decades shows, plant sterol be one type to the human non-toxic spinoff, have the crude substance of high physiologically active, Food and Drug Administration (FDA) approved plant sterol and phytostanols can be used as a kind of foodstuff additive and use.
But phytostanols is fat-soluble and water-soluble all very poor, has limited its actual use range.Research shows; The plant stanol ester that the phytostanols esterification makes has the double effects of acid and phytostanols; And compare with phytostanols better solvability is arranged, dispersiveness and higher decreasing cholesterol effect, can be widely used in industries such as food, medicine and makeup.The food that the FDA approved adds phytostanols and plant stanol ester can use the label of " good for health ".
The key of phytostanols esterification reaction is to select appropriate catalyst, improves the transformation efficiency of esterification, avoids production of by-products as much as possible.Ionic liquid is the solvent of a kind of novelty, nonaqueous phase; Be again a kind of good catalyzer simultaneously; Have non-volatility, good stability and characteristic such as environmentally friendly; And ion liquid polarity, hydrophobicity, viscosity and solvability all can be regulated through its positively charged ion and anionic suitable modification, so claimed " green solvent " and " design solvent " simultaneously.In addition, ion liquid soluble end is wide, steam forces down, is easy to separate, can be recycled with reaction product, the ionic liquid of imidazolyl especially, and these characteristics are more outstanding.
Summary of the invention
The object of the present invention is to provide a kind of high catalytic activity, segregative with product, the ionic-liquid catalyst that can be repeatedly used, and with the method for this Preparation of Catalyst plant stanol ester.
The present invention adopts following technical scheme:
Under the condition of solvent-free and logical nitrogen, with lipid acid (saturated or unsaturated acid) and phytostanols, be heated to complete fusion, add catalyzer, carry out esterification, reaction finishes to get the lipid acid plant stanol ester through separation and purification; Or alcohol acid, phytostanols and catalyzer joined in benzene, toluene or the YLENE, be heated to certain temperature, carry out esterification, reaction finishes to get the alcohol acid plant stanol ester through separation and purification.
Phytostanols of the present invention is the mixture of one or more arbitrary proportions in sitostanol, stigmastanol, campestanol, the vegetable seed stanols.
Acid of the present invention is sfas (comprising tetradecanoic acid, LAURIC ACID 99 MIN, palmitinic acid, Triple Pressed Stearic Acid, eicosanoic acid and mountain Yu acid); Unsaturated fatty acids (comprising oleic acid, linolic acid, linolenic acid, arachidonic acid, timnodonic acid and docosahexenoic acid), alcohol acid (comprising lactic acid, oxysuccinic acid, tartrate and Hydrocerol A).
Catalyzer of the present invention is [bmim] Cl, [bmim] [HSO
4], [bmim] Cl-ZnCl
2In the mixture of one or more arbitrary proportions.
Acid of the present invention and phytostanols amount of substance ratio are 1: 1～8: 1, preferred 2: 1～6: 1.
Catalyst levels of the present invention is 1～12% of a phytostanols quality, preferred 3～9%.
Temperature of reaction of the present invention is following: be 90～180 ℃ during with fatty acid response, and preferred 120～160 ℃; When reacting be 80～115 ℃, preferred 100～115 ℃ with alcohol acid.
Reaction times of the present invention is following: be 1～15 hour during with fatty acid response, and preferred 2～6 hours; Be 5～20 hours when reacting with alcohol acid, preferred 7～14 hours.
Degree of esterification adopts high-efficient liquid phase color spectrometry, its HPLC analysis condition: Symmetry C18 post (4.6 * 250mm, 5 μ m) among the present invention; Column temperature: 35 ℃; Moving phase: contain the methanol solution of 1 ‰ trifluoroacetic acids, flow velocity: 0.8mL/min, the constant speed wash-out; Sample size: 10 μ L, light scattering detector (ELSD) condition is carrier gas: N
2, flow velocity: 1.6L/min, drift tube temperature: 70 ℃, WP: 20psi.
Compared with present technology, advantage of the present invention is:
(1) ionic liquid of employing glyoxaline cation structure, raw material sources are extensive, and preparation is convenient, and stable to water, the catalyzer non-inactivation can be recycled; (2) catalyzer and reaction product layering, lower floor's ionic liquid can reuse after separating mutually; (3) ionic liquid can biological degradation, environmental friendliness; (4) adopt solvent-free system in lipid acid (saturated or unsaturated acid) plant stanol ester synthetic, preparation, separation that route of synthesis is green, efficient, easy, be convenient to scale operation; (5) lipid acid (saturated or unsaturated acid) thing stanol ester has certain fat-solublely, and the alcohol acid plant stanol ester has certain water-soluble and fat-soluble, has enlarged the range of application of phytostanols.
Embodiment
Below in conjunction with object lesson, the present invention is set forth more specifically.Concrete parameter in the example only is used to the present invention is described and is not used in limited range that those skilled in that art can suitably revise parameter of the present invention.
Embodiment 1
2.08g phytostanols and 6.00g LAURIC ACID 99 MIN are added in the reaction tube of band mouthful, logical nitrogen, dissolving fully under 130 ℃, magnetic agitation condition adds 0.13g [bmim] Cl-ZnCl
2, esterification 6h under 130 ℃ of conditions of controlled temperature, separation and purification gets the LAURIC ACID 99 MIN plant stanol ester.
Embodiment 2
2.08g phytostanols and 4.05g myristic acid are added in the reaction tube of band mouthful, logical nitrogen, dissolving fully under 135 ℃, magnetic agitation condition adds 0.08g [bmim] [HSO
4], esterification 5h under 135 ℃ of conditions of controlled temperature, separation and purification gets the myristic acid plant stanol ester.
Embodiment 3
1.04g phytostanols and 3.50g linolic acid are added in the reaction tube of a band mouth; Logical nitrogen, dissolving fully under 160 ℃, magnetic agitation condition adds 0.05g [bmim] Cl; Esterification 4h under 160 ℃ of conditions of controlled temperature, separation and purification gets the linolic acid plant stanol ester.
Embodiment 4
1.04g phytostanols and 1.35g linolenic acid are added in the reaction tube of band mouthful, logical nitrogen, dissolving fully under 150 ℃, magnetic agitation condition adds 0.10g [bmim] [HSO
4], esterification 3h under 150 ℃ of conditions of controlled temperature, separation and purification gets the linolenic acid plant stanol ester.
Embodiment 5
0.37g [bmim] Cl is added in the there-necked flask, add 4.16g phytostanols and 6.70g oxysuccinic acid, adding benzene 20mL, esterification 15h under 100 ℃, magnetic agitation condition, separation and purification gets the oxysuccinic acid plant stanol ester.
Embodiment 6
With 0.46g [bmim] [HSO
4] add in the there-necked flask, add 4.16g phytostanols and 11.52g Hydrocerol A, adding toluene 20mL, esterification 11h under 110 ℃, magnetic agitation condition, separation and purification gets the Hydrocerol A plant stanol ester.
Claims (9)
1. one kind is the method for Preparation of Catalyst plant stanol ester with the ionic liquid, it is characterized in that this method is following:
1. under the condition of solvent-free and logical nitrogen, with lipid acid (saturated or unsaturated acid) and phytostanols, be heated to complete fusion, add catalyzer, carry out esterification, reaction finishes to get the lipid acid plant stanol ester through separation and purification.
2. alcohol acid, phytostanols and catalyzer are joined in benzene, toluene or the YLENE, be heated to certain temperature, carry out esterification, reaction finishes to get the alcohol acid plant stanol ester through separation and purification.
2. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that used ionic liquid is [bmim] Cl, [bmim] [HSO
4] and [bmim] Cl-ZnCl
2In the mixture of one or more arbitrary proportions, its structure as shown in the formula:
3. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that described ionic liquid consumption is 1～12% of a phytostanols quality.
4. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that described phytostanols is the mixture of sitostanol, stigmastanol, one or more arbitrary proportions of campestanol.
5. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1; It is characterized in that described acid is sfas (comprising tetradecanoic acid, LAURIC ACID 99 MIN, palmitinic acid, Triple Pressed Stearic Acid, eicosanoic acid and mountain Yu acid); Unsaturated fatty acids (comprising oleic acid, linolic acid, linolenic acid, arachidonic acid, timnodonic acid and docosahexenoic acid), alcohol acid (comprising lactic acid, oxysuccinic acid, tartrate and Hydrocerol A).
6. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that described acid and phytostanols amount of substance ratio are 1: 1～8: 1.
7. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that lipid acid (saturated or unsaturated acid) is 90～180 ℃ at controlled temperature and carried out esterification 1～15 hour; Alcohol acid is 80～115 ℃ at controlled temperature and carried out esterification 5～20 hours.
8. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that 1. under the condition of solvent-free and logical nitrogen, reacting; 2. under benzene, toluene or xylene solvent condition, react.
9. the ionic liquid-catalyzed method for preparing plant stanol ester as claimed in claim 1 is characterized in that lower floor's ionic liquid phase of producing behind the organic solvent dissolution reactant, and separation can reuse.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210050865XA CN102617700A (en) | 2012-02-28 | 2012-02-28 | Preparation method of phytostanol ester by taking ionic liquid as catalyst |
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| CN201210050865XA CN102617700A (en) | 2012-02-28 | 2012-02-28 | Preparation method of phytostanol ester by taking ionic liquid as catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106755252A (en) * | 2016-11-30 | 2017-05-31 | 江苏大学 | The method that one kettle way prepares hydrophilic plant sterol/stanol derivative |
| CN111631402A (en) * | 2020-04-16 | 2020-09-08 | 东北农业大学 | Amphiphilic soybean sterol ester product and rapid preparation method thereof |
| CN111995653A (en) * | 2020-09-28 | 2020-11-27 | 江苏大学 | Preparation method of phytosterol/stanol ferulic acid ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200754A (en) * | 2007-12-07 | 2008-06-18 | 中国农业科学院油料作物研究所 | Method for producing plant sterol ester by immobilized whole-cell enzyme catalysis in solvent-free system |
| CN101235067A (en) * | 2008-01-11 | 2008-08-06 | 浙江工业大学 | Process for preparing plant sterol ester |
| CN101538306A (en) * | 2009-04-28 | 2009-09-23 | 国家粮食储备局西安油脂科学研究设计院 | Preparation method of phytosterin ester rich in oleic acid |
| CN101845473A (en) * | 2010-06-03 | 2010-09-29 | 江南大学 | Method for effectively synthesizing phytosterol ester |
-
2012
- 2012-02-28 CN CN201210050865XA patent/CN102617700A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200754A (en) * | 2007-12-07 | 2008-06-18 | 中国农业科学院油料作物研究所 | Method for producing plant sterol ester by immobilized whole-cell enzyme catalysis in solvent-free system |
| CN101235067A (en) * | 2008-01-11 | 2008-08-06 | 浙江工业大学 | Process for preparing plant sterol ester |
| CN101538306A (en) * | 2009-04-28 | 2009-09-23 | 国家粮食储备局西安油脂科学研究设计院 | Preparation method of phytosterin ester rich in oleic acid |
| CN101845473A (en) * | 2010-06-03 | 2010-09-29 | 江南大学 | Method for effectively synthesizing phytosterol ester |
Non-Patent Citations (1)
| Title |
|---|
| YEBO YANG等: "Efficient synthesis of phytosteryl esters using the Lewis acidic ionic liquid", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 357, 28 January 2013 (2013-01-28), pages 39 - 43 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106755252A (en) * | 2016-11-30 | 2017-05-31 | 江苏大学 | The method that one kettle way prepares hydrophilic plant sterol/stanol derivative |
| CN106755252B (en) * | 2016-11-30 | 2019-09-17 | 江苏大学 | The method that one kettle way prepares hydrophilic plant sterol/stanol derivative |
| CN111631402A (en) * | 2020-04-16 | 2020-09-08 | 东北农业大学 | Amphiphilic soybean sterol ester product and rapid preparation method thereof |
| CN111995653A (en) * | 2020-09-28 | 2020-11-27 | 江苏大学 | Preparation method of phytosterol/stanol ferulic acid ester |
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Application publication date: 20120801 |