CN109678703B - Synthetic method of monoglyceride - Google Patents
Synthetic method of monoglyceride Download PDFInfo
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- CN109678703B CN109678703B CN201910085486.6A CN201910085486A CN109678703B CN 109678703 B CN109678703 B CN 109678703B CN 201910085486 A CN201910085486 A CN 201910085486A CN 109678703 B CN109678703 B CN 109678703B
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Abstract
The invention belongs to the field of glyceride synthesis, and provides a method for synthesizing monoglyceride, which comprises the following steps: mixing triglyceride, glycerol and amino acid base eutectic solvent, and performing ester exchange reaction to obtain monoglyceride; the amino acid-based eutectic solvent is prepared from amino acid and quaternary ammonium base. The invention provides a method for synthesizing monoglyceride, which takes an amino acid base eutectic solvent as a catalyst, effectively solves the problem of equipment corrosion caused by taking inorganic base as the catalyst, has better compatibility with a reaction substrate, and effectively improves the reaction yield and the product purity. The example result shows that the yield of the synthesis method of the monoglyceride provided by the invention is 37-64.84%, and the purity is 97.61-99.92%.
Description
Technical Field
The invention relates to the field of glyceride synthesis, in particular to a synthesis method of monoglyceride.
Background
Monoglyceride (MAG) is a structural lipid formed by replacing two fatty acids with hydroxyl in Triacylglycerol (TAG), the molecular structure of the monoglyceride contains lipophilic long-carbon chain alkyl and hydrophilic hydroxyl, the hydrophilic-lipophilic balance value is 3-4, the monoglyceride has good emulsification property, and the monoglyceride is often used as a nonionic surfactant and is widely applied to the industries of food, medicine, chemical engineering and the like.
At present, monoglyceride is prepared mainly by glycerolysis of fats and oils by enzymatic and chemical methods. Among them, lipase is mainly used for enzymatic glycerolysis, and most of them are commercially available immobilized lipases. The enzyme method production has the advantages of mild reaction conditions, strong catalytic specificity, easy obtainment of high-purity products and the like, but the lower reaction temperature can cause the reaction system to have higher viscosity, and the reaction system is easy to be divided into a hydrophobic oil phase, a hydrophilic glycerol phase and an immobilized enzyme phase, which can reduce the reaction efficiency. In addition, due to the problems of price and recycling of the enzyme, the production cost is high, and the industrial production of monoglyceride prepared by catalyzing the glycerolysis of the oil and fat through the enzyme is limited to a certain extent.
Compared with an enzyme method, the monoglyceride prepared by a chemical method is not limited by reaction temperature, the production cost is low, and the large-scale production is easy to realize. However, in the existing chemical method for preparing monoglyceride, inorganic base (KOH/NaOH) is usually used as a catalyst, the reaction is carried out at high temperature (220-260 ℃) under the protection of vacuum or inert gas, the yield of monoglyceride is 30%, and the catalyst in the chemical method is easy to cause equipment corrosion.
Disclosure of Invention
The invention provides a method for synthesizing monoglyceride, which takes an amino acid-based eutectic solvent as a catalyst, effectively solves the problem of equipment corrosion caused by taking inorganic base as the catalyst, and has higher yield and purity of the monoglyceride prepared by the synthesis method.
The invention provides a method for synthesizing monoglyceride, which comprises the following steps:
mixing triglyceride, glycerol and amino acid base eutectic solvent, and performing ester exchange reaction to obtain monoglyceride; the amino acid-based eutectic solvent is prepared from amino acid and quaternary ammonium base.
Preferably, the temperature of the ester exchange reaction is 80-120 ℃, and the time is 5-240 min.
Preferably, the mass ratio of the triglyceride to the glycerol is 1: 4.82-38.60.
Preferably, the mass ratio of the amino acid-based eutectic solvent to the triglyceride is 0.01-0.2: 1.
Preferably, the amino acid in the amino acid-based eutectic solvent comprises one or more of arginine, lysine, histidine, tryptophan and glutamic acid.
Preferably, the quaternary ammonium base in the amino acid eutectic solvent comprises one or more of choline hydroxide, tetramethylammonium hydroxide hydrate and tetrabutylammonium hydroxide hydrate.
Preferably, the amino acid based eutectic solvent comprises [ tetramethylammonium hydroxide pentahydrate ] [ arginine ], [ tetrabutylammonium hydroxide thirty hydrate ] [ arginine ], [ choline hydroxide ] [ arginine ].
Preferably, the preparation method of the amino acid based eutectic solvent includes the steps of:
(1) reacting aqueous solution of quaternary ammonium base and aqueous solution of amino acid in water, and removing water to obtain a product mixture;
(2) and mixing the product mixture with an organic solvent, precipitating impurity components, and then desolventizing the filtrate to obtain the amino acid-based eutectic solvent.
Preferably, in the step (1), the molar ratio of the quaternary ammonium hydroxide in the aqueous quaternary ammonium hydroxide solution to the amino acid in the aqueous amino acid solution is 1: 1-1.5.
Preferably, the organic solvent in step (2) includes one or more of acetonitrile, methanol, absolute ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, acetone, tetrahydrofuran, ethyl acetate, diethyl ether, dichloromethane, chloroform and n-hexane.
The invention provides a method for synthesizing monoglyceride, which comprises the following steps: mixing triglyceride, glycerol and amino acid base eutectic solvent, and performing ester exchange reaction to obtain monoglyceride; the amino acid-based eutectic solvent is prepared from amino acid and quaternary ammonium base. The invention provides a method for synthesizing monoglyceride, which takes an amino acid base eutectic solvent as a catalyst, effectively solves the problem of equipment corrosion caused by taking inorganic base as the catalyst, has better compatibility with a reaction substrate, and effectively improves the reaction yield and the product purity. The example result shows that the yield of the synthesis method of the monoglyceride provided by the invention is 37-64.84%, and the purity is 97.61-99.92%.
Drawings
FIG. 1 is a GC chromatogram of the product prepared in example 1 of the present invention.
Detailed Description
The invention provides a method for synthesizing monoglyceride, which comprises the following steps:
mixing triglyceride, glycerol and amino acid base eutectic solvent, and performing ester exchange reaction to obtain monoglyceride; the amino acid-based eutectic solvent consists of amino acid and quaternary ammonium base.
According to the invention, triglyceride, glycerol and an amino acid-based eutectic solvent are mixed and then subjected to ester exchange reaction to obtain monoglyceride.
In the present invention, the triglyceride preferably comprises a vegetable oil, and the vegetable oil further preferably comprises one or more of soybean oil, sunflower oil, palm oil, olive oil, corn oil, peanut oil and coconut oil. The present invention does not particularly require the source of triglyceride and glycerin, and commercially available products may be used. In the present invention, the mass ratio of the triglyceride to the glycerol is preferably 1:4.82 to 38.60, more preferably 1:9.64 to 28.92, and even more preferably 1: 19.28.
The present invention preferably mixes the triglyceride and glycerol first and then with the amino acid based eutectic solvent. In the invention, the temperature of the ester exchange reaction is preferably 80-120 ℃, more preferably 90-110 ℃, and the time is preferably 5-240 min, more preferably 10-200 min, more preferably 20-100 min, and most preferably 30-60 min.
In the reaction process, the triglyceride and the glycerol are subjected to transesterification reaction to prepare the monoglyceride, the transesterification reaction mode is shown as a formula I, wherein the triglyceride is represented by 'TAG', the glycerol is represented by 'G', the diglyceride is represented by 'DAG', and the monoglyceride is represented by 'MAG':
in the present invention, the triglyceride TAG undergoes glycerolysis to form the primary product diglyceride DAG, which is further glycerolysed to form the monoglyceride MAG.
The present invention preferably performs molecular distillation treatment on the transesterification reaction product to purify monoglyceride from the transesterification reaction product. The present invention does not require any particular embodiment of the molecular distillation treatment, and it is sufficient to employ a method for purifying monoglyceride from monoglyceride, diglyceride and triglyceride, which is well known to those skilled in the art. In a particular embodiment of the invention, the molecular distillation preferably comprises a primary distillation, a secondary distillation and a tertiary distillation carried out in sequence; the temperature of the primary distillation is preferably 150-172 ℃, the vacuum degree is preferably 51.2-54.5 Pa, and the light component obtained by the primary distillation is a monoglyceride crude product; performing secondary distillation on the crude monoglyceride, wherein the temperature of the secondary distillation is preferably 115-125 ℃, the vacuum degree is preferably 25.6-27.8 Pa, and the light component obtained by the secondary distillation is a monoglyceride purified product; and (3) carrying out three-stage distillation on the purified monoglyceride, wherein the temperature of the three-stage distillation is preferably 140-162 ℃, the vacuum degree is preferably 19.0-21.2 Pa, and the monoglyceride can be obtained after the three-stage distillation.
In the present invention, the transesterification reaction is carried out under the condition that an amino acid-based eutectic solvent is used as a catalyst; the amino acid-based eutectic solvent is prepared from amino acid and quaternary ammonium base; the amino acid preferably comprises one or more of arginine, lysine, histidine, tryptophan and glutamic acid; the quaternary ammonium base preferably comprises one or more of choline hydroxide, tetramethylammonium hydroxide hydrate, and tetrabutylammonium hydroxide hydrate; the amino acid-based eutectic solvent preferably includes [ tetramethylammonium hydroxide pentahydrate ] [ arginine ] (abbreviated as [ TMA ] [ Arg ]), [ tetrabutylammonium hydroxide triacontahydrate ] [ arginine ] (abbreviated as [ TBA ] [ Arg ]), and [ choline hydroxide ] [ arginine ] (abbreviated as [ CHOH ] [ Arg ]). In the present invention, the molar ratio of the quaternary ammonium hydroxide to the amino acid in the amino acid-based eutectic solvent is preferably 1:0.8 to 1.2, and more preferably 1:1. In the present invention, the mass ratio of the amino acid-based eutectic solvent to the triglyceride is preferably 0.01 to 0.2:1, more preferably 0.05 to 0.15:1, and still more preferably 0.1 to 0.15: 1.
In the present invention, the preparation method of the amino acid eutectic solvent preferably includes the steps of:
(1) reacting aqueous solution of quaternary ammonium base and aqueous solution of amino acid in water, and removing water to obtain a product mixture;
(2) and mixing the product mixture with an organic solvent, precipitating impurity components, and then desolventizing the filtrate to obtain the amino acid-based eutectic solvent.
In the invention, quaternary ammonium base aqueous solution and amino acid aqueous solution react in water, and then the water is removed to obtain a product mixture. The quaternary ammonium base aqueous solution is preferably added into the amino acid aqueous solution drop by drop, and the invention preferably adopts the mixing mode, thereby being beneficial to the full reaction of the quaternary ammonium base aqueous solution and the amino acid aqueous solution and obtaining higher yield and catalytic effect of the amino acid base eutectic solvent. In the invention, the reaction of the aqueous solution of the quaternary ammonium base and the aqueous solution of the amino acid is preferably room temperature, the reaction time is preferably 12-48 h, and in the reaction process, the amino acid and the quaternary ammonium base are subjected to acid-base neutralization reaction to generate the amino acid-base eutectic solvent. The invention preferably adopts a rotary evaporation mode to remove water, and the rotary evaporation temperature is preferably 70-90 ℃, and further preferably 80 ℃; the rotary evaporation is preferably carried out under vacuum conditions.
In the present invention, the product mixture preferably comprises a reaction product of a quaternary ammonium base and an amino acid and a mixture of excess amino acid.
According to the invention, the organic solvents of the product mixture are mixed, and the filtrate is desolventized after impurity components are separated out, so that the amino acid-based eutectic solvent is obtained. In the invention, the organic solvent preferably comprises one or more of acetonitrile, methanol, absolute ethyl alcohol, n-propanol, isopropanol, n-butanol, tert-butanol, acetone, tetrahydrofuran, ethyl acetate, diethyl ether, dichloromethane, chloroform and n-hexane, and more preferably is a mixed solvent of acetonitrile and methanol in a volume ratio of 7: 3; the volume ratio of the organic solvent to the amino acid-based eutectic solvent is preferably 1: 1-5, and more preferably 1: 2-4. According to the invention, the excessive amino acid which does not participate in the reaction in the mixed solution is precipitated in the form of impurity components by adding the organic solvent. The invention preferably separates the precipitated impurity components by a reduced pressure suction filtration mode, and collects the filtrate. The invention preferably adopts a rotary evaporation mode to desolventize the filtrate to obtain light yellow liquid; the rotary evaporation temperature is preferably 50-70 ℃, more preferably 60 ℃, and when the solvent can not be evaporated again by rotary evaporation, the rotary evaporation is stopped.
After the rotary evaporation is finished, the invention preferably carries out drying treatment on the light yellow liquid obtained by the rotary evaporation to obtain the amino acid-based eutectic solvent. In the invention, the temperature of the drying treatment is preferably 80-100 ℃, further preferably 90 ℃, and the time is preferably 0.5-2 h; the drying treatment is preferably performed under vacuum.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting the flask into a stirrer, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 80 ℃ for 5min at the rotating speed of 300rpm, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 10 percent of the mass of the soybean oil, starting the reaction, taking out the product after 1h of the reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 13.52g monoglyceride product. The yield of Monoglyceride (MAG) in the product was 54.08%, and the separated and purified monoglyceride was analyzed by GC and had a purity of 98.31%.
In all examples of the present invention, the yield was calculated as weight g of monoglyceride product/weight g of reactant triglyceride) x 100%.
The results of the GC analysis of example 1 are shown in FIG. 1, where MAG represents monoglyceride, TAG represents triglyceride and DAG represents diglyceride in FIG. 1.
Example 2
Adding 25g (0.0028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting a stirrer, opening a magnetic stirrer, stirring and preheating at 300rpm in an oil bath kettle at 100 ℃ for 5min, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:0.8) accounting for 10% of the mass of the soybean oil, starting the reaction, taking out the product after 0.5h, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 16.21g monoglyceride product. The yield of the monoglyceride in the product is 64.84%, and the purity of the monoglyceride obtained by separation and purification is 99.15% by GC analysis.
Example 3
A150 mL round bottom flask is added with 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol, a stirrer is placed, a magnetic stirrer is opened, the mixture is stirred and preheated for 5min at the rotating speed of 300rpm in an oil bath kettle at the temperature of 120 ℃, then [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1.2) accounting for 10 percent of the weight of the oil is added, the reaction is started, after 0.5h of reaction, the product is taken out and is subjected to molecular distillation treatment to obtain monoglyceride, and the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 15.94g monoglyceride product. The yield of the monoglyceride in the product is 63.76%, and the purity of the monoglyceride obtained by separation and purification is 99.28% by GC analysis.
Example 4
In a 150mL round bottom flask, 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 2.590g (0.028mol) of glycerol are added, a stirrer is placed, a magnetic stirrer is opened, the mixture is stirred and preheated for 5min at the rotating speed of 300rpm in an oil bath kettle at the temperature of 100 ℃, then [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 10 percent of the weight of the oil is added, the reaction is started, after 0.5h of reaction, the product is taken out and subjected to molecular distillation treatment to obtain monoglyceride, and the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 15.47g monoglyceride product. The yield of the monoglyceride in the product is 61.88 percent, and the purity of the monoglyceride obtained by separation and purification is 97.91 percent by GC analysis.
Example 5
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080(0.056mol) of glycerol into a 150mL round bottom flask, putting a stirrer into the flask, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 100 ℃ for 5min at the rotating speed of 300rpm, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 8 percent of the weight of the oil, starting reaction, taking out a product after 1h of reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 16.07g monoglyceride product. The yield of the monoglyceride in the product is 64.28%, and the purity of the monoglyceride obtained by separation and purification is 98.90% by GC analysis.
Example 6
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting a stirrer, opening a magnetic stirrer, stirring and preheating at the rotating speed of 300rpm in an oil bath kettle at the temperature of 110 ℃ for 5min, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 10% of the weight of the oil, starting the reaction, taking out the product after 0.5h of reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 15.89g monoglyceride product. The yield of the monoglyceride in the product is 63.56%, and the purity of the monoglyceride obtained by separation and purification is 99.52% by GC analysis.
Example 7
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting the flask into a stirrer, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 100 ℃ for 5min at the rotating speed of 300rpm, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 8 percent of the weight of the oil, starting the reaction, taking out the product after 0.5h of the reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 14.82g monoglyceride product. The yield of the monoglyceride in the product is 59.28%, and the purity of the monoglyceride obtained by separation and purification is 97.90% by GC analysis.
Example 8
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting a stirrer into the flask, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 100 ℃ for 5min at the rotating speed of 300rpm, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 10 percent of the weight of the oil, starting the reaction, taking out the product after 1h of the reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 15.68g monoglyceride product. The yield of the monoglyceride in the product is 62.72%, and the separated and purified monoglyceride has the purity of 97.61% by GC analysis.
Example 9
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting a stirrer, opening a magnetic stirrer, stirring and preheating at 300rpm in an oil bath kettle at the temperature of 100 ℃ for 5min, adding [ TMA ] [ Arg ] (the molar ratio of TMA to Arg is 1:1) accounting for 10% of the weight of the oil, starting the reaction, taking out the product after 0.5h of reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60Pa, third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 15.98g monoglyceride product. The yield of the monoglyceride in the product is 63.92 percent, and the purity of the monoglyceride obtained by separation and purification is 99.92 percent by GC analysis.
Example 10
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting the flask into a stirrer, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 80 ℃ for 5min at the rotating speed of 300rpm, adding [ TBA ] [ Arg ] (the molar ratio of TBA to Arg is 1:1) accounting for 10 percent of the mass of the soybean oil, starting the reaction, taking out the product after 1h of the reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 9.25g monoglyceride product. The yield of Monoglyceride (MAG) in the product was 37%, and the purity of monoglyceride obtained by separation and purification was 98.31% by GC analysis.
Example 11
Adding 25g (0.028mol) of soybean oil (average molecular weight 888.78) and 5.080g (0.056mol) of glycerol into a 150mL round bottom flask, putting the flask into a stirrer, opening a magnetic stirrer, stirring and preheating the flask in an oil bath kettle at the temperature of 100 ℃ for 5min at the rotating speed of 300rpm, adding [ CHOH ] [ Arg ] (the molar ratio of CHOH to Arg is 1:1) accounting for 10 percent of the mass of the soybean oil, starting the reaction, taking out the product after 4h of the reaction, and carrying out molecular distillation treatment on the product to obtain monoglyceride, wherein the experimental parameters of the molecular distillation treatment are as follows: the primary distillation temperature is 160 ℃, the vacuum degree is 53.2Pa, and the light component is a monoglyceride crude product; the crude monoglyceride product was further purified (second stage distillation temperature 120 deg.C, vacuum degree 26.60 Pa; third stage distillation temperature 150 deg.C, vacuum degree 20.0Pa) to obtain 11.65g monoglyceride product. The yield of the monoglyceride in the product is 46.6%, and the purity of the monoglyceride obtained by separation and purification is 99.15% by GC analysis.
In conclusion, the method provided by the invention has the advantages that the yield of the monoglyceride is 37-64.84%, the purity is 97.61-99.92%, and the reaction time is 0.5-1 h. In the preparation method provided by the invention, the yield is highest by taking [ TMA ] [ Arg ] as the catalyst, and the yield of monoglyceride prepared by taking [ TMA ] [ Arg ] as the catalyst is 54.08-64.84%. Therefore, the invention takes the amino acid-based eutectic solvent as the catalyst, the biocompatibility of the catalyst and a reaction substrate is good, the reaction is rapid, the product yield and the purity are higher, the emulsification and saponification phenomena are not found in the production process, and the product is clear.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A synthetic method of monoglyceride comprises the following steps:
mixing triglyceride, glycerol and amino acid base eutectic solvent, and performing ester exchange reaction to obtain monoglyceride; the amino acid-based eutectic solvent is prepared from amino acid and quaternary ammonium base;
the amino acid in the amino acid-based eutectic solvent comprises one or more of arginine, lysine, histidine, tryptophan and glutamic acid;
the quaternary ammonium base in the amino acid eutectic solvent comprises one or more of choline hydroxide, tetramethylammonium hydroxide hydrate and tetrabutylammonium hydroxide hydrate.
2. The synthesis method according to claim 1, wherein the temperature of the transesterification reaction is 80-120 ℃ and the time is 5-60 min.
3. The synthesis method according to claim 1 or 2, wherein the mass ratio of the triglyceride to the glycerol is 1: 4.82-38.60.
4. The synthesis method according to claim 1 or 2, wherein the mass ratio of the amino acid-based eutectic solvent to the triglyceride is 0.01 to 0.2: 1.
5. The method of synthesis according to claim 1, wherein the amino acid based eutectic solvent comprises [ tetramethylammonium hydroxide pentahydrate ] [ arginine ], [ tetrabutylammonium hydroxide triacontahydrate ] [ arginine ], [ choline hydroxide ] [ arginine ].
6. The synthesis method according to claim 1, wherein the preparation method of the amino acid based eutectic solvent comprises the steps of:
(1) reacting aqueous solution of quaternary ammonium base and aqueous solution of amino acid in water, and removing water to obtain a product mixture;
(2) and mixing the product mixture with an organic solvent, precipitating impurity components, and then desolventizing the filtrate to obtain the amino acid-based eutectic solvent.
7. The synthesis method according to claim 6, wherein the molar ratio of the quaternary ammonium hydroxide in the aqueous quaternary ammonium hydroxide solution to the amino acid in the aqueous amino acid solution in the step (1) is 1: 1-1.5.
8. The synthesis method according to claim 6, wherein the organic solvent in step (2) comprises one or more of acetonitrile, methanol, absolute ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, acetone, tetrahydrofuran, ethyl acetate, diethyl ether, dichloromethane, chloroform and n-hexane.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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