CN109678703A - A kind of synthetic method of monoglyceride - Google Patents
A kind of synthetic method of monoglyceride Download PDFInfo
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- CN109678703A CN109678703A CN201910085486.6A CN201910085486A CN109678703A CN 109678703 A CN109678703 A CN 109678703A CN 201910085486 A CN201910085486 A CN 201910085486A CN 109678703 A CN109678703 A CN 109678703A
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- monoglyceride
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- eutectic solvent
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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Abstract
The invention belongs to glycerol Lipase absobed fields, provide a kind of synthetic method of monoglyceride, comprising the following steps: after mixing sweet three ester, glycerol and amino acidic group eutectic solvent, carry out ester exchange reaction, obtain monoglyceride；The amino acidic group eutectic solvent is prepared by amino acid and quaternary ammonium base.The present invention provides a kind of synthetic methods of monoglyceride, the present invention is using amino acidic group eutectic solvent as catalyst, it efficiently solves using inorganic base as equipment etching problem caused by catalyst, and the compatibility of catalyst provided by the invention and reaction substrate is preferable, effectively increases reaction yield and product purity.Embodiment the result shows that, the yield of the synthetic method of monoglyceride provided by the invention is 37~64.84%, and purity is 97.61~99.92%.
Description
Technical field
The present invention relates to glycerol Lipase absobed field more particularly to a kind of synthetic methods of monoglyceride.
Background technique
Monoglyceride (monoacylglycerol, MAG) is two in a quasi-glycerol three-ester (Triacylglycerol, TAG)
Fatty acid, which is optionally substituted by a hydroxyl group, is formed by structured lipid, and lipophilicity Long carbon chain alkyl and hydrophily hydroxyl are contained in molecular structure
Base, hydrophilic lipophilic balance are 3~4, have good emulsification property, are widely used in frequently as nonionic surface active agent
The industries such as food, medicine, chemical industry.
Currently, main prepare monoglyceride by enzyme process and chemical method progress grease glycerol rhizolomy.Wherein, enzyme process glycerol rhizolomy uses
Mainly lipase, the immobilized lipase being mostly commercialized.The benefit of Production by Enzymes is that reaction condition is mild, is catalyzed
Specificity is strong, is easy to get high purity product etc., but lower reaction temperature can make reaction system have higher viscosity, reaction
System is easily divided into hydrophobic oil phase, hydrophilic glycerol phase and immobilised enzymes phase, this can reduce reaction efficiency.Further, since the price of enzyme
With recycling problem, production cost is higher, this limits enzymatic grease glycerol rhizolomy to a certain extent and prepares monoglyceride
Industrialized production.
For enzyme process, chemical method prepares monoglyceride and is not limited by reaction temperature, and production cost is low, is easy real
Existing large-scale production.But existing chemical method, which prepares monoglyceride, often makees catalyst with inorganic base (KOH/NaOH), in high temperature
It is reacted under (220~260 DEG C), vacuum or inert gas shielding, monoglyceride yield is 30%, urging in above-mentioned chemical method
The problem of agent easily causes equipment to corrode.
Summary of the invention
The present invention provides a kind of synthetic method of monoglyceride, method provided by the invention is with amino acidic group eutectic solvent
It for catalyst, efficiently solves using inorganic base as equipment etching problem caused by catalyst, and synthesis side provided by the invention
The monoglyceride efficiency of pcr product and purity that method is prepared are higher.
The present invention provides a kind of synthetic methods of monoglyceride, comprising the following steps:
After sweet three ester, glycerol and amino acidic group eutectic solvent are mixed, ester exchange reaction is carried out, monoglyceride is obtained；Institute
Amino acidic group eutectic solvent is stated to be prepared by amino acid and quaternary ammonium base.
Preferably, the temperature of the ester exchange reaction is 80~120 DEG C, and the time is 5~240min.
Preferably, the mass ratio of sweet three ester and glycerol is 1:4.82~38.60.
Preferably, the mass ratio of the amino acidic group eutectic solvent and sweet three ester is 0.01~0.2:1.
Preferably, amino acid includes arginine, lysine, histidine, tryptophan in the amino acidic group eutectic solvent
With one of glutamic acid or a variety of.
Preferably, quaternary ammonium base includes bursine, tetramethylammonium hydroxide hydration in the amino acid eutectic solvent
One of object and tetrabutylammonium hydroxide hydrate are a variety of.
Preferably, the amino acidic group eutectic solvent include [tetramethylammonium hydroxide pentahydrate] [arginine],
[tri- decahydrate of tetrabutylammonium hydroxide] [arginine], [bursine] [arginine].
Preferably, the amino acidic group eutectic solvent preparation method the following steps are included:
(1) water is removed after reacting quaternary ammonium aqueous alkali and amino acid solution in water, obtains product mixtures；
(2) product mixtures are mixed with organic solvent, is precipitated after impurity composition and precipitation is carried out to filtrate, obtains ammonia
Base acidic group eutectic solvent.
Preferably, in step (1) the quaternary ammonium aqueous alkali in quaternary ammonium base and amino acid solution amino acid molar ratio
For 1:1~1.5.
Preferably, organic solvent includes acetonitrile, methanol, dehydrated alcohol, normal propyl alcohol, isopropanol, positive fourth in the step (2)
It is one or more of in alcohol, the tert-butyl alcohol, acetone, tetrahydrofuran, ethyl acetate, ether, methylene chloride, chloroform and n-hexane.
The present invention provides a kind of synthetic methods of monoglyceride, comprising the following steps: by sweet three ester, glycerol and amino acidic group
After eutectic solvent mixing, ester exchange reaction is carried out, monoglyceride is obtained；The amino acidic group eutectic solvent is by amino acid and season
Ammonium alkali is prepared.The present invention provides a kind of synthetic method of monoglyceride, the present invention is to urge with amino acidic group eutectic solvent
Agent is efficiently solved using inorganic base as equipment etching problem caused by catalyst, and used catalyst of the present invention with react
The compatibility of substrate is preferable, effectively increases reaction yield and product purity.Embodiment the result shows that, list provided by the invention is sweet
The yield of the synthetic method of rouge is 37~64.84%, and purity is 97.61~99.92%.
Detailed description of the invention
Fig. 1 is the GC chromatogram that the embodiment of the present invention 1 prepares product.
Specific embodiment
The present invention provides a kind of synthetic methods of monoglyceride, comprising the following steps:
After sweet three ester, glycerol and amino acidic group eutectic solvent are mixed, ester exchange reaction is carried out, monoglyceride is obtained；Institute
Amino acidic group eutectic solvent is stated to be made of amino acid and quaternary ammonium base.
After the present invention mixes sweet three ester, glycerol and amino acidic group eutectic solvent, ester exchange reaction is carried out, is obtained single sweet
Rouge.
In the present invention, sweet three ester preferably includes vegetable oil, and the vegetable oil further preferably includes soybean oil, certain herbaceous plants with big flowers
One or more of flower seed oil, palm oil, olive oil, corn oil, peanut oil and coconut oil.The present invention is to sweet three ester and glycerol
Source do not specially require, using commercial goods.In the present invention, the mass ratio of sweet three ester and glycerol is preferably
1:4.82~38.60, further preferably 1:9.64~28.92, more preferably 1:19.28.
The present invention preferably first mixes sweet three ester and glycerol, then mixes again with amino acidic group eutectic solvent.In this hair
In bright, the temperature of the ester exchange reaction is preferably 80~120 DEG C, and further preferably 90~110 DEG C, the time is preferably 5~
240min, further preferably 10~200min, more preferably 20~100min, most preferably 30~60min.
During the reaction, ester exchange reaction occurs the present invention for sweet three ester and glycerol, prepares monoglyceride, the ester is handed over
It is shown in formula I to change reactive mode, wherein sweet three ester uses " TAG expression ", glycerol uses " G expression ", and diglyceride is indicated with " DAG ", single
Sweet rouge is indicated with " MAG ":
In the present invention, sweet three esters TAG passes through glycerolysis reaction formation Primary product diglyceride DAG, diglyceride DAG into one
It walks glycerol rhizolomy and forms monoglyceride MAG.
The present invention preferably carries out molecular distillation processing to product of transesterification reaction, to purify from product of transesterification reaction
To monoglyceride.The present invention does not specially require the specific embodiment that the molecular distillation is handled, using those skilled in the art
The method of monoglyceride is purified known to member from monoglyceride, diglyceride and sweet three ester.In a specific embodiment of the invention
In, the molecular distillation preferably includes the level-one successively carried out distillation, secondary distillation and three-stage distillation；The temperature of the level-one distillation
Preferably 150~172 DEG C of degree, vacuum degree is preferably 51.2~54.5Pa, and the light component that level-one is distilled is that monoglyceride slightly produces
Product；The monoglyceride crude product is subjected to secondary distillation, the temperature of the secondary distillation is preferably 115~125 DEG C, and vacuum degree is excellent
It is selected as 25.6~27.8Pa, the light component that secondary distillation obtains is monoglyceride purified；The monoglyceride purified is carried out three
Grade distillation, the temperature of the three-stage distillation is preferably 140~162 DEG C, and vacuum degree is preferably 19.0~21.2Pa, after three-stage distillation
Monoglyceride can be obtained.
In the present invention, the ester exchange reaction carries out under conditions of amino acidic group eutectic solvent is as catalyst；
The amino acidic group eutectic solvent is prepared by amino acid and quaternary ammonium base；The amino acid preferably includes arginine, relies ammonia
One of acid, histidine, tryptophan and glutamic acid are a variety of；The quaternary ammonium base preferably includes bursine, tetramethyl hydrogen
One of amine-oxides hydrate and tetrabutylammonium hydroxide hydrate are a variety of；The amino acidic group eutectic solvent preferably wraps
Include [tetramethylammonium hydroxide pentahydrate] [arginine] (being abbreviated as [TMA] [Arg]), [tetrabutylammonium hydroxide 30
Hydrate] [arginine] (being abbreviated as [TBA] [Arg]), [bursine] [arginine] (being abbreviated as [CHOH] [Arg]).?
In the present invention, the molar ratio of quaternary ammonium base and amino acid is preferably 1:0.8~1.2 in the amino acidic group eutectic solvent, into one
Step is preferably 1:1.In the present invention, the mass ratio of the amino acidic group eutectic solvent and sweet three ester is preferably 0.01~0.2:
1, further preferably 0.05~0.15:1, more preferably 0.1~0.15:1.
In the present invention, the preparation method of the amino acid eutectic solvent preferably includes following steps:
(1) water is removed after reacting quaternary ammonium aqueous alkali and amino acid solution in water, obtains product mixtures；
(2) product mixtures are mixed with organic solvent, is precipitated after impurity composition and precipitation is carried out to filtrate, obtains ammonia
Base acidic group eutectic solvent.
The present invention removes water after reacting quaternary ammonium aqueous alkali and amino acid solution in water, obtains product mixing
Object.Quaternary ammonium aqueous alkali is preferably added dropwise in amino acid solution by the present invention, and present invention preferably employs above-mentioned mixing sides
Formula is conducive to the two sufficiently reaction, obtains more homoamino acid base eutectic solvent yield and catalytic effect.In the present invention, institute
The reaction for stating quaternary ammonium aqueous alkali and amino acid solution is preferably room temperature, and the time of the reaction is preferably 12~48h, this hair
Bright acid-base neutralization reaction occurs for amino acid and quaternary ammonium base during the reaction, generates amino acidic group eutectic solvent.The present invention is excellent
Choosing is removed water by the way of revolving, and the temperature of revolving is preferably 70~90 DEG C, and further preferably 80 DEG C；The revolving is excellent
Choosing carries out under vacuum conditions.
In the present invention, the product mixtures preferably include quaternary ammonium base and amino acid reaction product and extra amino
The mixture of acid.
The present invention mixes product mixtures organic solvent, is precipitated after impurity composition and carries out precipitation to filtrate, obtains amino
Acidic group eutectic solvent.In the present invention, the organic solvent preferably includes acetonitrile, methanol, dehydrated alcohol, normal propyl alcohol, isopropyl
It is a kind of or several in alcohol, n-butanol, the tert-butyl alcohol, acetone, tetrahydrofuran, ethyl acetate, ether, methylene chloride, chloroform and n-hexane
Kind, further preferably acetonitrile and methanol volume ratio are the mixed solvent of 7:3；The organic solvent and amino acidic group eutectic are molten
The volume ratio of agent is preferably 1:1~5, further preferably 1:2~4.The present invention is made in mixed solution by the way that organic solvent is added
The excessive amino acid for having neither part nor lot in reaction is precipitated in the form of impurity composition.The present invention will preferably be precipitated in such a way that decompression filters
Impurity composition separation, collect filtrate.Present invention preferably employs the modes of revolving to carry out precipitation to filtrate, obtains light yellow liquid
Body；The temperature of the revolving is preferably 50~70 DEG C, further preferably 60 DEG C, when revolving can not steam solvent again, is stopped
Revolving.
After revolving, the weak yellow liquid that the present invention preferably obtains revolving is dried, and obtains amino acidic group
Eutectic solvent.In the present invention, the temperature of the drying process is preferably 80~100 DEG C, and further preferably 90 DEG C, the time
Preferably 0.5~2h；The drying process preferably carries out under vacuum conditions.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, is turned in the oil bath pan that temperature is 80 DEG C with 300rpm
After speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for soybean oil quality 10% is added, starts anti-
It answers, after reacting 1h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing are as follows:
160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through further again
Purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can be obtained
13.52g monoglyceride product.The yield of monoglyceride (MAG) is 54.08% in product, is carried out to the monoglyceride that separating-purifying obtains
GC analysis, purity 98.31%.
In all embodiments of the invention, the calculation method of yield is the sweet three esters quality of monoglyceride product quality g/ reactant
G) × 100%.
As shown in Figure 1, MAG represents monoglyceride in Fig. 1, TAG represents sweet the spectrogram result that the progress of embodiment 1 GC is analyzed
Three esters, DAG represent diglyceride.
Embodiment 2
In the round-bottomed flask of 150mL, be added 25g (0.0028mol) soybean oil (average molecular weight 888.78) and
5.080g (0.056mol) glycerine, is put into stirrer, open magnetic stirring apparatus, in the oil bath pan that temperature is 100 DEG C with
After the revolving speed stirring preheating 5min of 300rpm, [TMA] [the Arg] (molar ratio of TMA and Arg for accounting for soybean oil quality 10% is added
1:0.8), start to react, after reacting 0.5h, take out product, product handles through molecular distillation, monoglyceride is obtained, at molecular distillation
The experiment parameter of reason are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；It is thick to monoglyceride
Product be further purified again (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree
20.0Pa), 16.21g monoglyceride product can be obtained.Monoglyceride yield is 64.84% in product, the list obtained to separating-purifying
Sweet rouge carries out GC analysis, purity 99.15%.
Embodiment 3
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 120 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1.2 of TMA and Arg) for accounting for oily heavy amount 10% is added, starts
Reaction after reacting 0.5h, takes out product, and product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 15.94g monoglyceride product.Monoglyceride yield is 63.76% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 99.28%.
Embodiment 4
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 2.590g is added
(0.028mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 10% is added, starts anti-
It answers, after reacting 0.5h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 15.47g monoglyceride product.Monoglyceride yield is 61.88% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 97.91%.
Embodiment 5
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080 is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 8% is added, starts anti-
It answers, after reacting 1h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing are as follows:
160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through further again
Purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can be obtained
16.07g monoglyceride product.Monoglyceride yield is 64.28% in product, carries out GC analysis to the monoglyceride that separating-purifying obtains,
Purity is 98.90%.
Embodiment 6
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 110 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 10% is added, starts anti-
It answers, after reacting 0.5h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 15.89g monoglyceride product.Monoglyceride yield is 63.56% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 99.52%.
Embodiment 7
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 8% is added, starts anti-
It answers, after reacting 0.5h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 14.82g monoglyceride product.Monoglyceride yield is 59.28% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 97.90%.
Embodiment 8
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 10% is added, starts anti-
It answers, after reacting 1h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing are as follows:
160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through further again
Purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can be obtained
15.68g monoglyceride product.Monoglyceride yield is 62.72% in product, carries out GC analysis to the monoglyceride that separating-purifying obtains,
Purity is 97.61%.
Embodiment 9
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [TMA] [Arg] (the molar ratio 1:1 of TMA and Arg) for accounting for oily heavy amount 10% is added, starts anti-
It answers, after reacting 0.5h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 15.98g monoglyceride product.Monoglyceride yield is 63.92% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 99.92%.
Embodiment 10
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, is turned in the oil bath pan that temperature is 80 DEG C with 300rpm
After speed stirring preheating 5min, [TBA] [Arg] (the molar ratio 1:1 of TBA and Arg) for accounting for soybean oil quality 10% is added, starts anti-
It answers, after reacting 1h, takes out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing are as follows:
160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through further again
Purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can be obtained
9.25g monoglyceride product.The yield of monoglyceride (MAG) is 37% in product, carries out GC points to the monoglyceride that separating-purifying obtains
Analysis, purity 98.31%.
Embodiment 11
In the round-bottomed flask of 150mL, 25g (0.028mol) soybean oil (average molecular weight 888.78) and 5.080g is added
(0.056mol) glycerine is put into stirrer, opens magnetic stirring apparatus, with 300rpm's in the oil bath pan that temperature is 100 DEG C
After revolving speed stirring preheating 5min, [CHOH] [Arg] (the molar ratio 1:1 of CHOH and Arg) for accounting for soybean oil quality 10% is added, opens
Begin to react, after reacting 4h, take out product, product is handled through molecular distillation, obtains monoglyceride, the experiment parameter of molecular distillation processing
Are as follows: 160 DEG C of level-one vapo(u)rizing temperature, vacuum degree 53.2Pa, light component is monoglyceride crude product；Monoglyceride crude product is passed through again into one
Step purifying (120 DEG C of secondary distillation temperature, vacuum degree 26.60Pa；150 DEG C of three-stage distillation temperature, vacuum degree 20.0Pa), can obtain
To 11.65g monoglyceride product.Monoglyceride yield is 46.6% in product, carries out GC analysis to the monoglyceride that separating-purifying obtains,
Purity is 99.15%.
To sum up, method provided by the invention prepare monoglyceride yield be 37~64.84%, purity be 97.61~
99.92%, the reaction time is 0.5~1h.In preparation method provided by the invention, with [TMA] [Arg] be catalyst yield most
It is 54.08~64.84% that height, which is the yield that catalyst preparation obtains monoglyceride with [TMA] [Arg],.It can be seen that the present invention with
Amino acidic group eutectic solvent is catalyst, the good biocompatibility of catalyst and reaction substrate, so that being swift in response, product obtains
Rate and purity are higher, and in process of production without discovery emulsification and saponification phenomenon, product clarification.
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, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of monoglyceride, comprising the following steps:
After sweet three ester, glycerol and amino acidic group eutectic solvent are mixed, ester exchange reaction is carried out, monoglyceride is obtained；The ammonia
Base acidic group eutectic solvent is prepared by amino acid and quaternary ammonium base.
2. synthetic method according to claim 1, which is characterized in that the temperature of the ester exchange reaction is 80~120 DEG C,
Time is 5~60min.
3. synthetic method according to claim 1 or 2, which is characterized in that the mass ratio of sweet three ester and glycerol is 1:
4.82~38.60.
4. synthetic method according to claim 1 or 2, which is characterized in that the amino acidic group eutectic solvent and sweet three
The mass ratio of ester is 0.01~0.2:1.
5. synthetic method according to claim 1, which is characterized in that amino acid packet in the amino acidic group eutectic solvent
Include one of arginine, lysine, histidine, tryptophan and glutamic acid or a variety of.
6. synthetic method according to claim 1, which is characterized in that quaternary ammonium base includes in the amino acid eutectic solvent
One of bursine, tetramethylammonium hydroxide hydrate and tetrabutylammonium hydroxide hydrate are a variety of.
7. according to claim 1, synthetic method described in 5 or 6, which is characterized in that the amino acidic group eutectic solvent includes
[tetramethylammonium hydroxide pentahydrate] [arginine], [three decahydrate of tetrabutylammonium hydroxide] [arginine], [hydrogen-oxygen
Change choline] [arginine].
8. according to claim 1, synthetic method described in 5 or 6, which is characterized in that the system of the amino acidic group eutectic solvent
Preparation Method the following steps are included:
(1) water is removed after reacting quaternary ammonium aqueous alkali and amino acid solution in water, obtains product mixtures；
(2) product mixtures are mixed with organic solvent, is precipitated after impurity composition and precipitation is carried out to filtrate, obtains amino acid
Base eutectic solvent.
9. synthetic method according to claim 8, which is characterized in that quaternary ammonium base in step (1) the quaternary ammonium aqueous alkali
Molar ratio with amino acid in amino acid solution is 1:1~1.5.
10. synthetic method according to claim 8, which is characterized in that in the step (2) organic solvent include acetonitrile,
Methanol, dehydrated alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, acetone, tetrahydrofuran, ethyl acetate, ether, dichloromethane
It is one or more of in alkane, chloroform and n-hexane.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033286A (en) * | 1987-11-21 | 1989-06-07 | 金华第二制药厂 | The combine production method of monoglyceride and fatty acid ester of low-carbon alcohol |
| CN1327472A (en) * | 1999-10-20 | 2001-12-19 | 西格福莱德·彼得 | Method for reesterification of fat and/or oil of biological origin by means of alcoholysis |
| CN1496398A (en) * | 2001-07-06 | 2004-05-12 | ¡ | Method for transesterification of fats and/or oils by means of alcoholysis |
| CN101486661A (en) * | 2009-02-27 | 2009-07-22 | 南京大学 | Method for preparing tetraalkyl quaternary ammonium type amino acid ion liquid |
| CN102417865A (en) * | 2010-09-28 | 2012-04-18 | 江苏中鼎化学有限公司 | Method for continuously producing mono-and-di-glyceride |
| CN103525561A (en) * | 2013-10-12 | 2014-01-22 | 盐城师范学院 | Method for preparing biodiesel in eutectic system |
| CN106480114A (en) * | 2015-08-25 | 2017-03-08 | 丰益(上海)生物技术研发中心有限公司 | The method of preparation biodiesel |
| CN107254494A (en) * | 2017-06-22 | 2017-10-17 | 华南理工大学 | A kind of glycerine ester type PUFA preparation method |
| CN108654689A (en) * | 2018-06-22 | 2018-10-16 | 南京大学 | A kind of non-corrosive acidic catalyst of eutectic, preparation method and its usage |
| CN108837847A (en) * | 2018-06-13 | 2018-11-20 | 青岛科技大学 | The catalyst and method of alcohol polylactic acid |
-
2019
- 2019-01-29 CN CN201910085486.6A patent/CN109678703B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033286A (en) * | 1987-11-21 | 1989-06-07 | 金华第二制药厂 | The combine production method of monoglyceride and fatty acid ester of low-carbon alcohol |
| CN1327472A (en) * | 1999-10-20 | 2001-12-19 | 西格福莱德·彼得 | Method for reesterification of fat and/or oil of biological origin by means of alcoholysis |
| CN1496398A (en) * | 2001-07-06 | 2004-05-12 | ¡ | Method for transesterification of fats and/or oils by means of alcoholysis |
| CN101486661A (en) * | 2009-02-27 | 2009-07-22 | 南京大学 | Method for preparing tetraalkyl quaternary ammonium type amino acid ion liquid |
| CN102417865A (en) * | 2010-09-28 | 2012-04-18 | 江苏中鼎化学有限公司 | Method for continuously producing mono-and-di-glyceride |
| CN103525561A (en) * | 2013-10-12 | 2014-01-22 | 盐城师范学院 | Method for preparing biodiesel in eutectic system |
| CN106480114A (en) * | 2015-08-25 | 2017-03-08 | 丰益(上海)生物技术研发中心有限公司 | The method of preparation biodiesel |
| CN107254494A (en) * | 2017-06-22 | 2017-10-17 | 华南理工大学 | A kind of glycerine ester type PUFA preparation method |
| CN108837847A (en) * | 2018-06-13 | 2018-11-20 | 青岛科技大学 | The catalyst and method of alcohol polylactic acid |
| CN108654689A (en) * | 2018-06-22 | 2018-10-16 | 南京大学 | A kind of non-corrosive acidic catalyst of eutectic, preparation method and its usage |
Non-Patent Citations (4)
| Title |
|---|
| HELDA NIAWANTI等: "Effect of Extraction Time on Unreacted Oil Removal in Biodiesel Purification Using Deep Eutectic Solvent", 《REAKTOR》 * |
| JOHNATHAN T. GORKE等: "Hydrolase-catalyzed biotransformations in deep eutectic solvents", 《CHEMCOMM》 * |
| LONG XU等: "Deep Eutectic Solvents Enable the Enhanced Production of n-3 PUFA-Enriched Triacylglycerols", 《EUR. J. LIPID SCI. TECHNOL.》 * |
| SHANGDE SUN: "A novel caffeic acid-based deep eutectic solvent as caffeoyl donor to enhance glycerol caffeates synthesis", 《JOURNAL OF MOLECULAR LIQUIDS》 * |
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