CN102321138A - A kind of novel preparation method of fatty acid phytosterin ester - Google Patents
A kind of novel preparation method of fatty acid phytosterin ester Download PDFInfo
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- CN102321138A CN102321138A CN201110154693A CN201110154693A CN102321138A CN 102321138 A CN102321138 A CN 102321138A CN 201110154693 A CN201110154693 A CN 201110154693A CN 201110154693 A CN201110154693 A CN 201110154693A CN 102321138 A CN102321138 A CN 102321138A
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Abstract
The present invention relates to a kind of novel preparation method who utilizes the efficient synthetic fatty acid plant sterol ester of nicellar catalysis agent.The technical scheme that the present invention adopts is: earlier a certain amount of lipid acid is joined be furnished with stirring, in the reaction flask of oil bath temperature control; Feed nitrogen; Heat, add the nicellar catalysis agent of a certain amount of plant sterol and 0.5～3.0mol% again, control reaction temperature is at 80～160 ℃; Reaction 2～6h, separation and purification obtain fatty acid plant sterol ester.Present method technology is simple, and efficient is high, is convenient to scale operation.
Description
Technical field
The present invention relates to the preparation method of fatty acid phytosterin ester, particularly a kind of no-solvent process that utilizes nicellar catalysis agent synthetic fatty acid plant sterol ester.
Background technology
Plant sterol is a kind of activeconstituents in the plant, extensively is present in each vegetable oil, nut and plant seed and plant food and the vegetable and fruit.Plant sterol has and reduces cholesterol level in the blood, prevention prostatosis, anti-inflammatory, physiological action such as anticancer and anti-oxidant.Plant sterol is extensively added in the varieties of food items as functional food additives.In September, 2000, the food that plant sterol and plant sterol ester have been added in FDA (FDA) approval can use the label of " good for health ".At present, European Union, the U.S. and Japan and other countries are widely used for it in butter, milk-product, chocolate, bread and the margarine oil's wet goods food.
Because of the most plants sterol is to exist with crystalline form, so in application, there is following problem: the crystalline form makes it poor in intravital solvability of people and bioavailability; Water insoluble, the solubleness in oil is also very little, has greatly limited it in Application in Food.Plant sterol and lipid acid can improve the fat-soluble of plant sterol greatly, thereby can solve the difficult problem of its inconvenience in Applications in Food Industry through the fatty acid phytosterin ester that esterification generates.
The synthetic enzyme catalysis synthesis method and the chemical synthesis of mainly containing at present of fatty acid phytosterin ester.The enzyme catalysis synthesis method is to adopt lypase to make catalyzer mostly, and this method can't realize large-scale industrial production because its cost is higher.Traditional chemical method mainly uses catalyzer such as mineral acid, tosic acid, strong-acid ion exchange resin, pyridine, sodium ethylate and Natural manganese dioxide, and required temperature of reaction is high, the time is long, productive rate is low, corrodibility is big and environmental pollution is serious.
For example, CN101200754 has described a kind of method of in solvent-free system, utilizing producing plant sterol ester by immobilized whole-cell enzyme catalysis.This method reaction conditions is gentle, need not add organic solvent.The problem that exists is that enzyme catalysis efficient is lower, and consumption is big, reach 60% esterification yield, required reaction times 48h.Simultaneously, this method also is inappropriate for large-scale production.
CN1982326 discloses a kind of preparation method of multiple unsaturated fatty acid phytosterin ester.The catalyzer that this method is used is common an acidic catalyst (like tosic acid, the vitriol oil, sodium hydrogencarbonate) and basic catalyst (diethylamine, triethylamine, sodium methylate, sodium ethylate).Though this method is not used poisonous and hazardous organic solvent, be fit to foodstuffs industry production, complex steps needs severe condition such as high temperature and vacuum.
CN1458918A discloses sterol, stanols, 4-methylsterol and their hydrogenated homologue, triterpene alcohol and their hydrogenated homologue, and the method for the mixture of these materials and fatty substance (capric acid, LAURIC ACID 99 MIN, myristic acid, palmitinic acid and composition thereof) generation esterification generation corresponding esters.The used catalyzer of this method is a lanthanide oxide, and the reaction times is longer, and product colour is dark.
US6413571 discloses conjugated linolic acid and methyl esters thereof, plant steroid (alkane) alcohol passes through esterification or transesterification generates conjugated linolic acid steroid (alkane) alcohol ester.The esterification catalyst system therefor is sulfonic acid and tin chloride, and the transesterification catalyst system therefor is sodium methylate and sodium hydroxide.The catalyzer that adopts has strong corrodibility, and reaction needs is under reduced pressure carried out.
CN1245810 discloses with the method for sodium sulfite anhy 96 as catalyst unsaturated fatty acids, the synthetic sterol ester of plant sterol.This method reaction conditions is gentle, and reaction process is not added mineral acid and organic solvent.The shortcoming of this method is that transformation efficiency is not high, and catalyst levels is bigger, needs the transformation efficiency more than 95% to need 18h.
WO0061694 discloses a kind of preparation method of polyunsaturated acid plant sterol ester, and the preparation process needs with methylene dichloride dissolving plant sterol and lipid acid, so method should not be used for foodstuffs industry.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and a kind of preparation method who in solvent-free system, utilizes the dodecyl sulphate transition metal salt as the efficient synthetic fatty acid plant sterol ester of catalyzer is provided.Present method technology is simple, and cost is lower, and route of synthesis is efficient, succinct and green, is convenient to large-scale production.
The present invention adopts following technical scheme:
A certain amount of lipid acid joined be furnished with stirring, in the reaction flask of oil bath temperature control; Feed nitrogen, heat, add the nicellar catalysis agent of a certain amount of plant sterol and 0.5～3.0mol% again; Control reaction temperature is at 80 ℃～160 ℃; The monitoring reaction process is reacted 2～6h, separation and purification obtain fatty acid plant sterol ester in real time.
The preparation method of said fatty acid phytosterin ester is characterized in that described plant sterol is the mixed phytosterin of one or more arbitrary proportions in Stigmasterol, β-Gu Zaichun, campesterol and the brassicasterol.
The preparation method of said fatty acid phytosterin ester is characterized in that described lipid acid is caproic acid, sad, capric acid, LAURIC ACID 99 MIN, myristic acid, palmitinic acid, linolic acid, oleic acid, Triple Pressed Stearic Acid, arachidonic acid, eicosanoic acid, erucic acid or mountain Yu acid.
The preparation method of said fatty acid phytosterin ester; It is characterized in that described nicellar catalysis agent is the dodecyl sulphate transition metal salt, like dodecyl sulphate copper, dodecyl sulphate zinc, dodecyl sulphate iron, dodecyl sulphate silver or dodecyl sulphate cerium.
The preparation method of said fatty acid phytosterin ester is characterized in that described nicellar catalysis agent dodecyl sulphate transition metal salt preparation method is: with 0.15mol/L sodium dodecyl sulfate solution and 0.16mol/L transition metal chloride solution 2: 1 by volume, in the time of 70 ℃, mix; Vigorous stirring reaction 0.5 hour; Be cooled to 0 ℃, generate the dodecyl sulfate deposition, filter; Wash 3 times, make through recrystallization.
The preparation method of said fatty acid phytosterin ester is characterized in that preferred 1: 1～2: 1 of the mol ratio of described lipid acid and plant sterol.
The preparation method of said fatty acid phytosterin ester is characterized in that preferred 90～120 ℃ of described temperature of reaction.
The preparation method of said fatty acid phytosterin ester is characterized in that the preferred 0.5～2.0mol% of described nicellar catalysis agent consumption.
The preparation method of said fatty acid phytosterin ester is characterized in that preferred 3～5h of described reaction times.
The preparation method of said fatty acid phytosterin ester is characterized in that said separation and purification utilizes plant sterol ester and the plant sterol dissolubility difference in alkane to realize, the steps include: to add normal heptane or normal hexane (solid-liquid ratio 1: 1 to the plant sterol ester mixture; W/v); 70 ℃ of dissolvings, 7000 leave heart 10min, produce deposition; Get supernatant, add 1mol/L NaHCO
3Solution, vibration 10min 7000 leaves heart 10min again, gets upper solution, and rotary evaporation removes and desolvates, and obtains plant sterol ester.
Real time reaction monitoring the process method described in the present invention is a thin layer chromatography.
Degree of esterification adopts high-efficient liquid phase color spectrometry, its HPLC analysis condition: SymmetryC18 post (4.6 * 250mm, 5 μ m) among the present invention; Column temperature: 30 ℃, moving phase: normal hexane/Virahol=1: 1, flow velocity: 0.7mL/min; The constant speed wash-out, sample size: 15 μ L; Light scattering detector ELSD condition: carrier gas is N
2, flow velocity: 1.7L/min, drift tube temperature: 60 ℃, WP: 20psi.
The present invention with respect to its beneficial effect of prior art is: the effective catalyst dodecyl sulfate has been adopted in (1), and required time shortens greatly, has improved efficient, has reduced energy consumption, and it is high to have esterification efficient, characteristics such as easy to operate and easy purification of products; (2) technology is simple, and is lower to the reaction conditions requirement, is prone to realize suitability for industrialized production; (3) do not use poisonous and hazardous organic solvent, be suitable for foodstuffs industry production.
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
The caproic acid that takes by weighing 17.4g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, and heating adds the dodecyl sulphate copper of 50g plant sterol and 1.0mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 80 ℃, and every separated 0.5h sampling is once reacted 3h.Separation and purification gets the caproic acid plant sterol ester.
Embodiment 2
Sad the joining that takes by weighing 19.5g is furnished with stirring, in the reaction flask of oil bath temperature control, feeds nitrogen, and heating adds the dodecyl sulphate zinc of 50g plant sterol and 1.2mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 90 ℃, and every separated 0.5h sampling is once reacted 3h.Separation and purification gets sad plant sterol ester.
Embodiment 3
The LAURIC ACID 99 MIN that takes by weighing 30g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, and heating adds the dodecyl sulphate copper of 50g plant sterol and 1.5mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 100 ℃, and every separated 0.5h sampling is once reacted 4h.Separation and purification gets the LAURIC ACID 99 MIN plant sterol ester.
Embodiment 4
The Triple Pressed Stearic Acid that takes by weighing 42.6g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, and heating adds the dodecyl sulphate copper of 50g plant sterol and 2.0mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 115 ℃, and every separated 0.5h sampling is once reacted 5h.Separation and purification gets the Triple Pressed Stearic Acid plant sterol ester.
Embodiment 5
The mountain Yu acid that takes by weighing 51g joins is furnished with stirring, in the reaction flask of oil bath temperature control, feeds nitrogen, and heating adds the dodecyl sulphate iron of 50g plant sterol and 2.5mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 120 ℃, and every separated 0.5h sampling is once reacted 6h.Separation and purification gets mountain Yu acid plant sterol ester.
Embodiment 6
The linolic acid that takes by weighing 42g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, and heating adds the dodecyl sulphate zinc of 50g plant sterol and 2.0mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 100 ℃, and every separated 0.5h sampling is once reacted 4h.Separation and purification gets the linolic acid plant sterol ester.
Embodiment 7
The arachidonic acid that takes by weighing 46.5g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, heating, and the dodecyl sulphate that adds 50g plant sterol and 2.0mol% again is silver-colored.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 105 ℃, and every separated 0.5h sampling is once reacted 4h.Separation and purification gets the arachidonic acid plant sterol ester.
Embodiment 8
The erucic acid that takes by weighing 50.7g joins to be furnished with stirring, in the reaction flask of oil bath temperature control, to feed nitrogen, and heating adds the dodecyl sulphate cerium of 50g plant sterol and 2.0mol% again.Control reaction temperature is utilized the real-time monitoring reaction process of tlc at 110 ℃, and every separated 0.5h sampling is once reacted 5h.Separation and purification gets the erucic acid plant sterol ester.
Claims (8)
1. preparation method who utilizes nicellar catalysis agent synthetic fatty acid plant sterol ester is characterized in that described method is: a certain amount of lipid acid is joined be furnished with stirring, in the reaction flask of oil bath temperature control, feed nitrogen; Heating; The nicellar catalysis agent that adds a certain amount of plant sterol and 0.5～3.0mol% again, control reaction temperature be at 80～160 ℃, in real time the monitoring reaction process; Reaction 2～8h, separation and purification obtain fatty acid plant sterol ester.
2. the preparation method of fatty acid phytosterin ester according to claim 1 is characterized in that described plant sterol is the mixed phytosterin of one or more arbitrary proportions in Stigmasterol, β-Gu Zaichun, campesterol and the brassicasterol.
3. the preparation method of fatty acid phytosterin ester according to claim 1 is characterized in that described lipid acid is caproic acid, sad, capric acid, LAURIC ACID 99 MIN, myristic acid, palmitinic acid, linolic acid, oleic acid, Triple Pressed Stearic Acid, arachidonic acid, eicosanoic acid, erucic acid or mountain Yu acid.
4. the preparation method of fatty acid phytosterin ester according to claim 1; It is characterized in that described nicellar catalysis agent is the dodecyl sulphate transition metal salt; Like dodecyl sulphate copper, dodecyl sulphate zinc, dodecyl sulphate iron, dodecyl sulphate silver or dodecyl sulphate cerium, catalyst levels is 0.5～3.0mol%.
5. the preparation method of fatty acid phytosterin ester according to claim 1 is characterized in that described nicellar catalysis agent dodecyl sulphate transition metal salt preparation method is: with 0.15mol/L sodium dodecyl sulfate solution and 0.16mol/L transition metal chloride solution 2: 1 by volume, in the time of 70 ℃, mix; Vigorous stirring reaction 0.5 hour; Be cooled to 0 ℃, generate the dodecyl sulfate deposition, filter; Wash 3 times, make through recrystallization.
6. the preparation method of fatty acid phytosterin ester according to claim 1, the mol ratio that it is characterized in that described lipid acid and plant sterol is 1: 1～5: 1.
7. the preparation method of fatty acid phytosterin ester according to claim 1 is characterized in that temperature of reaction carries out esterification 2～6h at 80～160 ℃.
8. like the preparation method of the said fatty acid phytosterin ester of claim 1～7, it is characterized in that said separation and purification utilizes plant sterol ester and the plant sterol dissolubility difference in alkane to realize, the steps include: to add normal heptane or normal hexane (solid-liquid ratio 1: 1 to the plant sterol ester mixture; W/v); 70 ℃ of dissolvings, 7000 leave heart 10min, produce deposition; Get supernatant, add 1mol/L NaHCO
3Solution, vibration 10min 7000 leaves heart 10min again, gets upper solution, and rotary evaporation removes and desolvates, and obtains plant sterol ester.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603846A (en) * | 2012-02-03 | 2012-07-25 | 江南大学 | Preparation method of phytosterol in ionic liquid |
| CN103122020A (en) * | 2011-11-19 | 2013-05-29 | 江南大学 | Method for preparing phytostanol ester under solvent-free condition |
| CN106810588A (en) * | 2017-01-18 | 2017-06-09 | 江南大学 | A kind of method for efficiently synthesizing lipoic acid sterol ester |
| CN109295150A (en) * | 2018-09-23 | 2019-02-01 | 江苏天美健大自然生物工程有限公司 | One plant sterols polymeric micelle preparation process |
| CN112279882A (en) * | 2020-10-28 | 2021-01-29 | 江苏科鼐生物制品有限公司 | Method for synthesizing linoleic acid beta-sitosterol ester by magnetic induction heating |
| CN112552366A (en) * | 2020-12-28 | 2021-03-26 | 江苏禾丰粮油工业有限公司 | Synthetic method of ferulic acid sterol ester |
| CN115286677A (en) * | 2022-10-10 | 2022-11-04 | 海南浙江大学研究院 | Preparation method of feeding phytosterol ester, phytosterol ester and application of phytosterol ester |
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| WO2000061694A1 (en) * | 1999-04-13 | 2000-10-19 | Eugene Science, Inc. | Method for manufacturing fat-soluble phytosterol or phytostanol ester of unsaturated fatty acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122020A (en) * | 2011-11-19 | 2013-05-29 | 江南大学 | Method for preparing phytostanol ester under solvent-free condition |
| CN102603846A (en) * | 2012-02-03 | 2012-07-25 | 江南大学 | Preparation method of phytosterol in ionic liquid |
| CN106810588A (en) * | 2017-01-18 | 2017-06-09 | 江南大学 | A kind of method for efficiently synthesizing lipoic acid sterol ester |
| CN109295150A (en) * | 2018-09-23 | 2019-02-01 | 江苏天美健大自然生物工程有限公司 | One plant sterols polymeric micelle preparation process |
| CN112279882A (en) * | 2020-10-28 | 2021-01-29 | 江苏科鼐生物制品有限公司 | Method for synthesizing linoleic acid beta-sitosterol ester by magnetic induction heating |
| CN112552366A (en) * | 2020-12-28 | 2021-03-26 | 江苏禾丰粮油工业有限公司 | Synthetic method of ferulic acid sterol ester |
| CN115286677A (en) * | 2022-10-10 | 2022-11-04 | 海南浙江大学研究院 | Preparation method of feeding phytosterol ester, phytosterol ester and application of phytosterol ester |
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