CN106632568B - A kind of phytosterin ester and its low temperature preparation method - Google Patents
A kind of phytosterin ester and its low temperature preparation method Download PDFInfo
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- CN106632568B CN106632568B CN201611225392.7A CN201611225392A CN106632568B CN 106632568 B CN106632568 B CN 106632568B CN 201611225392 A CN201611225392 A CN 201611225392A CN 106632568 B CN106632568 B CN 106632568B
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- phytosterol
- fatty acid
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- phytosterin ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of phytosterin ester and its low temperature preparing methods, the low temperature preparation method includes the following steps: (1) esterification: using phytosterol and fatty acid as raw material, solvent dissolution phytosterol and fatty acid is added, it adds catalyst and removes water reflux after solvent evaporative condenser in 30~65 DEG C of progress esterifications, reaction process；(2) acid-base neutralization: neutralizer catalyst neutralisation and extra fatty acid are added after the step (1) esterification, filtering removal insoluble solid object, solvent evaporated in vacuo is up to phytosterin ester.The present invention overcomes the unicity of enzyme process preparation by the low-temperature catalyzed mild reaction conditions reacted obtained phytosterin ester, the highly effective reaction time of existing chemical synthesis, and have enzyme process to prepare, and reduces energy consumption, is conducive to industrialized production.The phytosterin ester purity that the present invention is prepared is up to 95% or more.
Description
Technical field
The present invention relates to biomedicine technical field more particularly to a kind of phytosterin esters and its low temperature preparation method.
Background technique
Phytosterol, also known as phytosterol belong to steroid, are using cyclopentanoperhy drophenanthrene as skeleton (also known as steroid nucleus)
A kind of natural active matter is widely present in each vegetable oil, nut and vegetable seeds, exists in other plant foods
It is many kinds of in vegetable and fruit, it mainly include cupreol, stigmasterol, campesterol and brassicasterol, wherein cupreol
Content highest accounts about the 50~90% of total sterol, is the main component of grease unsaponifiable matter.
Phytosterol is one of the big functional nutrient ingredient of future ten that international Nutrition Society is recommended.As a kind of natural plant
Physical property food additives, in human small intestine, phytosterol is able to suppress the absorption of cholesterol, so as to which blood is effectively reduced
The content of middle total cholesterol concentration and low density lipoprotein cholesterol, but do not reduce the high-density lipoprotein beneficial to human body
The content of cholesterol, and without any side effect is recognized as by U.S.'s food and Drug Administration (FDA) " reducing blood lipid, pre-
The natural health care new raw material of preventing arteriosclerosis " is prevention cardiovascular and cerebrovascular disease " key of life ".But phytosterol is in water
In almost insoluble, the also very little of solubility in the oil, under normal circumstances in 40 DEG C of its solubility less than 2%, and when additive amount is big
It is just relatively difficult when 2%, can only take in, therefore be applied as food additives form in the form of tablets or capsules, or
Person is ineffective.
Phytosterin ester is the plant that phytosterol is formed by chemical combination such as its C-3 hydroxyl and fatty acid or fatty acid methyl esters
Object sterol derivative has physiological active functions identical with phytosterol.Phytosterin ester is more preferable than phytosterol oil-soluble,
Fusing point is lower, is able to solve restricted problem of the phytosterol in food applications, improves bioavailability, and it can be changed
Service performance is processed, is a kind of ideal new type functional food base-material.
Currently, having been carried out many researchs to the synthetic method of phytosterin ester, mainly there is chemical catalysis synthetic method (chemistry
Method) and biocatalysis synthetic method (enzyme process):
US0015347 discloses a kind of method for preparing phytosterin ester using rape-oil methyl ester and phytosterol, reacts
Journey is using sodium methoxide as catalyst, and by-product carbinol in the strong corrosive and preparation process of sodium methoxide makes it cannot be used for food
Additive；
US0068425 discloses a kind of manufacturing method of phytosterin ester rich in oleic acid, but it is answered in the fabrication process
It uses the biggish thionyl chloride of pollution and makees catalyst, and its operating condition is harsh, it is difficult to industrialized production；
EP195311 describes the method for lipase-catalyzed fatty acid, phytosterol direct esterification synthesis sterol ester, anti-
Answering system is aqueous organic solvent.Direct esterification advantage is that single fat acid sterol ester can be obtained, and easily adjusts product
The characteristics such as fusing point, and can realize the synergistic function of functional polyunsaturated fatty acid and sterol；
US0020098536 is disclosed using soybean oil deodorization object as raw material, and lipase-catalyzed phytosterol, triglycerides turn
The method of esterification generation fatty acid mixed sterol ester.The method can produced in situ (deodorization object can be directly as without separation
Reaction raw materials do not need pure sterol, fatty acid does raw material), it is at low cost.Generally speaking, biocatalyst specificity is strong, reaction
Mild condition, product property is good, environmental-friendly.But catalytic activity is not high, is easy inactivation, and higher cost is not able to satisfy industry still
Change and needs.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of phytosterin ester low temperature preparing methods, to overcome chemistry to urge
It is combined to the excessively high influence to phytosterol of method (chemical method) reaction temperature, while biocatalysis synthetic method (enzyme process) being overcome to prepare
When unicity problem.The highly effective reaction time of the existing chemical catalysis synthetic method (chemical method) of present invention process, and there is biology to urge
The mild reaction conditions of method (enzyme process) preparation are combined to, energy consumption is reduced, are conducive to industrialized production.
The technical problems to be solved by the invention, which also reside in, provides phytosterin ester made from the above method, to overcome chemistry
The excessively high influence to phytosterol of catalysis synthesis process (chemical method) reaction temperature, while biocatalysis synthetic method (enzyme process) being overcome to make
Unicity problem when standby.The phytosterin ester purity that the present invention is prepared is up to 95% or more.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of low temperature preparation method of phytosterin ester, includes the following steps:
(1) esterification: using phytosterol and fatty acid as raw material, being added solvent dissolution phytosterol and fatty acid, then
Catalyst is added and carries out esterification, removes water reflux in reaction process after solvent evaporative condenser；
(2) neutralizer catalyst neutralisation and extra rouge acid-base neutralization: are added after the step (1) esterification
Fat acid, filtering removal insoluble solid object, solvent evaporated in vacuo is up to phytosterin ester；
In the step (1), the phytosterol includes one in cupreol, stigmasterol, campesterol, brassicasterol
Kind is a variety of, and wherein total 90% or more the sterol content of plant；
In the step (1), the solvent is the organic solvent for meeting the following conditions: the readily soluble phytosterol of A. and fat
Acid, and do not react with phytosterol or fatty acid；B. azeotropic is formed with water energy and the azeotropic of the solvent and water is mixed
The boiling point for closing object is 30~65 DEG C；C. it is condensed into after liquid and forms immiscible two-phase with water stratification；D. not with product plant
Sterol ester forms azeotropic and will not influence catalyst activity.
In the step (1), the esterification carries out under the boiling point of the azeotropic mixture, and the solvent exists
It is evaporated when the solvent azeotrope with water.
Preferably, in the step (1), the phytosterol phytosterol commodity commercially available using business, and quotient
The total sterol content of plant is 90% or more in product.
It is highly preferred that the material plant sterol is limited using China Oil and Food Import and Export Corporation day section's bioengineering (Tianjin) in the step (1)
The commodity of company's production, wherein the total sterol content of plant has 90% and 95% two kind of specification.
Preferably, in the step (1), the fatty acid is C14~C20Saturated fatty acid or unsaturated fatty acid in
It is one or more.
It is highly preferred that in the step (1), the fatty acid is soya bean fatty acid, linoleic acid, one in rape oil fatty acid
Kind is a variety of.
Most preferably, in the step (1), the fatty acid is the soybean fat of benefit Hai Jiali Investment Co., Ltd production
Acid, linoleic acid, rape oil fatty acid it is one or more.
Preferably, in the step (1), the inventory molar ratio of phytosterol and fatty acid is 1:1~1.2.
Preferably, in the step (1), the solvent is methylene chloride, petroleum ether, hexane, any one in pentane.
The petroleum ether boiling range is selected as 30~60 DEG C.
It is highly preferred that the solvent is methylene chloride or petroleum ether in the step (1).The petroleum ether boiling range selection
It is 30~60 DEG C.
Preferably, in the step (1), solvent inventory is 3~8 times (v/m) of phytosterol.
In above-mentioned technical proposal, " 1 times (v/m) that solvent inventory is phytosterol " refers to that 1g phytosterol puts into 1ml
Solvent.
Preferably, in the step (1), the catalyst is p-methyl benzenesulfonic acid or the concentrated sulfuric acid.
Preferably, in the step (1), catalyst inventory is 0.1~5% (m/m) of phytosterol.
Preferably, in the step (1), the esterification reaction temperature is 30~65 DEG C, and the reaction time is 6~15h.
Preferably, in the step (2), the neutralizer is calcium oxide or calcium carbonate.
Since the activation energy of esterification is higher, while also having micro fuel factor, it is therefore desirable to catalyst appropriate and
Certain temperature improves reaction speed, shortens the time for reaching balance, to improve esterification speed.Catalyst for esterification reaction
Following a few classes can be substantially divided into, first is that general acid type catalyst, second is that solid acid catalyst, third is that homogeneous heteropolyacid catalyst,
Fourth is that super acidic catalyst.The catalytic mechanism of all kinds of catalyst is also imperfectly understood at present, the use of partial catalyst is also not
It can industrialize completely, all these problems are all up for the further exploration and research of people.Improve the another of esterification efficiency
A kind of technical solution be exactly increase the temperature of reaction system, but temperature of reaction system increase after side reaction can be promoted to generate again, such as
Dehydration, ester hydrolysis of alcohol etc., so temperature is excessively high unfavorable to esterification.
The principle that chemically balances it is found that in esterification system the increase of the concentration of product water and ester esterification is turned
Rate has detrimental effect, is the another of raising esterification efficiency so product water and ester are shifted from reaction system in time
A kind of means.For the water that timely continuous constantly elimination reaction generates, there are molecular sieve absorption, UF membrane to inhale at present
The technologies such as water, negative pressure azeotropic, but these technical measures are in some defects.Molecular sieve adsorption is convenient and easy, and effect is obvious,
It usually uses in laboratory research, but since the regeneration of the molecular sieve after adsorption saturation needs dedicated equipment and technique, throws
It is very high to provide cost, thus can not be applied in large-scale industrial production.It is feasible on UF membrane water suction law theory, but due to existing
The problem of blocking, aging and service life of film etc., thus implement and still have any problem.Using tert-pentyl alcohol, the tert-butyl alcohol it
Class does not influence catalyst activity, and the organic solvent that can form azeotropic mixture with the water of generation does reaction media and water entrainer,
Water is taken away in a manner of negative pressure azeotropic distillation, is a kind of good selection, but regrettably, it is cold to be formed by azeotropic mixture
Not stratified after solidifying, thus cannot achieve the continuous circulating and recovering of the continuous separation and solvent of water, the aqueous solvent steamed must be through
Crossing special drying process could reuse.The drying process cost of aqueous solvent greatly limits the application of technique.
Synthesizing phytosterol ester of the present invention has both the effect of water entrainer using low boiling point organic solvent as reaction media,
Azeotropic can be formed with water to make it possible to take water out of reaction system under lower temperature (30~65 DEG C), so that balancing continuous court
The direction of synthesizing phytosterol ester carries out, and reaction condition is again more mild while guaranteeing phytosterol high conversion, is not necessarily to
It is passed through the protective gas such as nitrogen in the reaction system.The selection of one of innovative point of the present invention reaction dissolvent is based on considered below:
Readily soluble phytosterol and fatty acid, do not react, and (phytosterol is oxidizable when being higher than 80 DEG C, therefore for low boiling point
The solvent boiling point of selection is as low as possible, such as the present invention methylene chloride or 30~60 DEG C of boiling range of petroleum ether selected, with water energy
Azeotropic is formed, is condensed into after liquid with water stratification, forms immiscible two-phase, while not formed altogether with product phytosterin ester
It boils and will not influence catalyst activity.
Compared with prior art, technical solution of the present invention has the advantages that
(1) mild condition, entire reaction carry out under low temperature (30~65 DEG C), and side reaction is few, and product color is good, simultaneously
Solvent and water form azeotropic at this temperature, and with the evaporation of solvent, the water in system is pulled away therewith, ensure that phytosterol
High conversion；
(2) technique applicability is wide, and raw material is general chemical raw material, easily purchases, and process flow is short, at low cost, easily realizes
Industrialization；
(3) solvent for use low boiling point, easy to be recycled, energy consumption is small, low in the pollution of the environment；
(4) neutralizer calcium oxide or calcium carbonate used in, itself does not dissolve in solvent, can to catalyst and superabundant fats acid into
Row neutralizes, and catalyst in reaction system and extra can be removed as long as the insoluble solid object for filtering out neutralization reaction generation
Fatty acid will not impact product.Technical process is short, easy to operate, is suitble to industrialized production.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
The commodity that the phytosterol used in following embodiment produces for COFCO Tianke Bioengineering (Tianjin) Co., Ltd.,
Wherein the total sterol content of plant has 90% and 95% two kind of specification；Fatty acid is the quotient of benefit Hai Jiali Investment Co., Ltd production
Product.
Embodiment 1
It takes material plant sterol 100g (the total sterol content 95% of plant), soya bean fatty acid 70g, methylene chloride is added
300ml dissolves material plant sterol, adds catalyst p-methyl benzenesulfonic acid 1g, and esterification reaction temperature is 42 DEG C, reacts 6h, instead
In 42 DEG C of evaporation solvents during answering, reflux is removed water after condensation.2g calcium oxide catalyst neutralisation and extra is added after reaction
Fatty acid, filtering removal insoluble solid, solvent evaporated in vacuo obtains phytosterin ester 163g, measures plant steroid through GC-MS
Alcohol ester purity reaches 97.3%.
Embodiment 2
It takes material plant sterol 100g (the total sterol content 90% of plant), soya bean fatty acid 70g, solvent petroleum ether is added
800ml dissolves material plant sterol, adds catalyst p-methyl benzenesulfonic acid 1g, and esterification reaction temperature is 30 DEG C, reacts 10h, instead
In 30 DEG C of evaporation solvents during answering, reflux is removed water after condensation.2g calcium oxide catalyst neutralisation and extra is added after reaction
Fatty acid, filtering removal insoluble solid, solvent evaporated in vacuo obtains phytosterin ester 164g, measures plant steroid through GC-MS
Alcohol ester purity reaches 96.6%.
Embodiment 3
It takes material plant sterol 100g (the total sterol content 90% of plant), linoleic acid 70g, methylene chloride is added
500ml dissolves material plant sterol, adds catalyst p-methyl benzenesulfonic acid 0.1g, and esterification reaction temperature is 42 DEG C, reacts 15h,
In 42 DEG C of evaporation solvents in reaction process, reflux is removed water after condensation.2g calcium oxide catalyst neutralisation and more is added after reaction
Remaining fatty acid, filtering removal insoluble solid, solvent evaporated in vacuo obtain phytosterin ester 163g, measure plant through GC-MS
Sterol ester purity reaches 96.7%.
Embodiment 4
It takes material plant sterol 100g (the total sterol content 95% of plant), rape oil fatty acid 70g, solvent petroleum ether is added
300ml dissolves material plant sterol, adds catalyst concentrated sulfuric acid 1g, and esterification reaction temperature is 40 DEG C, reacts 8h, reacted
In 40 DEG C of evaporation solvents in journey, reflux is removed water after condensation.2g calcium carbonate catalyst neutralisation and extra rouge are added after reaction
Fat acid, filtering removal insoluble solid, solvent evaporated in vacuo obtain phytosterin ester 161g, measure phytosterin ester through GC-MS
Purity reaches 98.1%.
Embodiment 5
It takes material plant sterol 100g (the total sterol content 95% of plant), soya bean fatty acid 70g, methylene chloride is added
300ml dissolves material plant sterol, adds catalyst p-methyl benzenesulfonic acid 0.5g, and esterification reaction temperature is 42 DEG C, reacts 12h,
In 42 DEG C of evaporation solvents in reaction process, reflux is removed water after condensation.2g calcium carbonate catalyst neutralisation and more is added after reaction
Remaining fatty acid, filtering removal insoluble solid, solvent evaporated in vacuo obtain phytosterin ester 165g, measure plant through GC-MS
Sterol ester purity reaches 97.7%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of low temperature preparation method of phytosterin ester, which comprises the steps of:
(1) esterification: using phytosterol and fatty acid as raw material, solvent dissolution phytosterol and fatty acid is added, adds
Catalyst removes water reflux in 30~65 DEG C of progress esterifications, reaction process after solvent evaporative condenser；
(2) neutralizer catalyst neutralisation and extra fat acid-base neutralization: are added after the step (1) esterification
Acid, filtering removal insoluble solid object, solvent evaporated in vacuo is up to phytosterin ester；
In the step (1), the phytosterol include one of cupreol, stigmasterol, campesterol, brassicasterol or
It is a variety of, and wherein total 90% or more the sterol content of plant；
In the step (1), the solvent is the organic solvent for meeting the following conditions: the readily soluble phytosterol of A. and fatty acid, and
And it does not react with phytosterol or fatty acid；B. azeotropic and the azeotropic mixture of the solvent and water are formed with water energy
Boiling point is 30~65 DEG C；C. it is condensed into after liquid and forms immiscible two-phase with water stratification；D. not with product phytosterin ester
It forms azeotropic and will not influence catalyst activity；
In the step (1), the solvent is specially methylene chloride, petroleum ether, hexane, any one in pentane；
In the step (1), the catalyst is p-methyl benzenesulfonic acid or the concentrated sulfuric acid.
2. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that the fatty acid is C14
~C20Saturated fatty acid or one of unsaturated fatty acid or a variety of.
3. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that in the step (1),
The inventory molar ratio of phytosterol and fatty acid is 1: 1~1.2.
4. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that in the step (1),
Solvent inventory is 3~8 times (v/m) of phytosterol.
5. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that catalyst inventory is
0.1~5% (m/m) of phytosterol.
6. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that in the step (1),
Reaction time of esterification is 6~15h.
7. a kind of low temperature preparation method of phytosterin ester as described in claim 1, which is characterized in that in the step (2),
The neutralizer is calcium oxide or calcium carbonate.
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