CN113214082A - Preparation method of lauric acid monoglyceride - Google Patents
Preparation method of lauric acid monoglyceride Download PDFInfo
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- CN113214082A CN113214082A CN202110489350.9A CN202110489350A CN113214082A CN 113214082 A CN113214082 A CN 113214082A CN 202110489350 A CN202110489350 A CN 202110489350A CN 113214082 A CN113214082 A CN 113214082A
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- lauric acid
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- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention provides a preparation method of lauric acid monoglyceride, belonging to the field of organic synthesis. According to the invention, lauric acid and glycerol are used as raw materials, the glycerol esterification reaction of long-chain fatty acid lauric acid is catalyzed by an acid catalyst, and the eutectic solvent is used as a solvent, so that the activation energy of the esterification reaction can be reduced, the esterification reaction can be carried out at a lower temperature, and the eutectic solvent is easy to separate and recover from a product. The results of the examples show that the lauric acid monoglyceride can be prepared by the method provided by the application at a low temperature of 120-160 ℃, the product selectivity is 87.1%, the yield is 76.4%, and the purity is 89.4%.
Description
Technical Field
The invention relates to the field of organic synthesis, and in particular relates to a preparation method of lauric acid monoglyceride.
Background
Lauric acid monoglyceride (GML) is a waxy solid which appears white to yellowish at ordinary temperature, and is a long-chain ester having 12 carbon atoms in one carboxylic acid moiety and 15 carbon atoms in total. The lauric acid monoglyceride has wide application in the fields of food, cosmetics, medicine, oil well drilling operation and the like. And, it is widely used as a nonionic surfactant, an emulsifier, an antibacterial agent, a thickener, etc. due to its structural characteristics of containing both a hydroxyl group and a long chain alkyl group. According to the national standard GB2760-2014, the lauric acid monoglyceride belongs to food flavor additives and has extremely high industrial added value.
The direct esterification synthesis of lauric acid and glycerol is one of the main methods for preparing lauric monoglyceride. The traditional esterification process takes sulfuric acid, hydrochloric acid or p-toluenesulfonic acid as a catalyst, and lauric acid and glycerol as raw materials, so that the raw materials are relatively low in cost and high in atom utilization rate, and the principle of sustainable development and economy is met. However, the esterification process in the method usually requires a high temperature of more than 200 ℃, the content of diester as a by-product in the prepared product is high, and the yield of the lauric acid monoglyceride is only 40-50%.
Disclosure of Invention
The preparation method of the monolaurin provided by the invention has the advantages of low reaction temperature, good selectivity, high yield of the product monolaurin and few byproducts.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of lauric acid monoglyceride, which comprises the following steps:
mixing lauric acid, glycerol, an acidic catalyst and a eutectic solvent, and then carrying out esterification reaction to obtain the lauric acid monoglyceride.
Preferably, the mass of the acidic catalyst is 0.03-0.2% of the total mass of lauric acid and glycerol.
Preferably, the eutectic solvent includes a quaternary ammonium salt and a boric acid compound.
Preferably, the quaternary ammonium salt has a structure shown in formula I or formula II;
wherein R in the formula I1And R in said formula II2Independently is C2～C5Alkyl radicalX in the formulae I and II-Independently chloride or bromide.
Preferably, R in said formula I1And R in said formula II2Independently ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or isopentyl.
Preferably, the boric acid based compound comprises one or more of boric acid and an organoboronic acid based compound.
Preferably, the ratio of the amounts of the substance of the quaternary ammonium salt and the boric acid compound is 1: (0.5-2).
Preferably, the eutectic solvent includes one or more of a choline chloride-boric acid eutectic solvent, a tetraethylammonium bromide-boric acid eutectic solvent, a tetrapropylammonium bromide-boric acid eutectic solvent, and a tetrabutylammonium bromide-boric acid eutectic solvent.
Preferably, the mass of the eutectic solvent is 5-40% of the total mass of lauric acid and glycerol;
preferably, the temperature of the esterification reaction is 120-160 ℃; the esterification reaction time is 3-12 h.
The invention provides a preparation method of lauric acid monoglyceride, which comprises the following steps: mixing lauric acid, glycerol, an acidic catalyst and a eutectic solvent, and then carrying out esterification reaction to obtain the lauric acid monoglyceride. According to the invention, lauric acid and glycerol are used as raw materials, the glycerol esterification reaction of long-chain fatty acid lauric acid is catalyzed by an acid catalyst, and the eutectic solvent is used as a solvent, so that the activation energy of the esterification reaction can be reduced, the esterification reaction can be carried out at a lower temperature, and the eutectic solvent is easy to separate and recover from a product. The results of the examples show that the lauric acid monoglyceride can be prepared by the method provided by the application at a low temperature of 120-160 ℃, the product selectivity is 87.1%, the yield is 76.4%, and the purity is 89.4%.
The preparation method of the lauric acid monoglyceride provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.
Drawings
FIG. 1 is a schematic diagram of the procedure for preparing monolaurin according to example 1 of the present invention.
Detailed Description
The invention provides a preparation method of lauric acid monoglyceride, which comprises the following steps:
mixing lauric acid, glycerol, an acidic catalyst and a eutectic solvent, and then carrying out esterification reaction to obtain the lauric acid monoglyceride.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the operation is carried out at room temperature unless otherwise specified.
According to the invention, lauric acid, glycerol, an acidic catalyst and a eutectic solvent are mixed and then subjected to esterification reaction to obtain the lauric acid monoglyceride. The operation of mixing the lauric acid, the glycerol, the acidic catalyst and the eutectic solvent is not particularly limited in the present invention, and a technical scheme for preparing a mixed solution, which is well known to those skilled in the art, may be adopted.
In the present invention, the ratio of the amount of the lauric acid and glycerin is preferably 1: (1 to 8), more preferably 1: (2-5), more preferably 1: 4. the invention controls the molar ratio of the lauric acid to the glycerol within the range, is favorable for promoting the relatively complete conversion of the lauric acid into the lauric acid monoglyceride, and improves the yield of the product.
In the present invention, the acidic catalyst is preferably hydrochloric acid or hydrobromic acid; the mass concentration of the hydrochloric acid is preferably 36%; the mass concentration of the hydrobromic acid is preferably 40%. In the invention, the acidic catalyst can catalyze the glycerin esterification reaction of the long-chain fatty acid lauric acid, and the reaction time is shortened.
In the present invention, the mass of the acidic catalyst is preferably 0.04 to 0.2%, more preferably 0.05 to 0.15%, and even more preferably 0.06 to 0.09% of the total mass of lauric acid and glycerin. The invention controls the quality of the acid catalyst in the range, is favorable for controlling the progress of esterification reaction of lauric acid and glycerol, shortens the reaction time and reduces the generation of byproducts.
In the present invention, the eutectic solvent preferably includes a quaternary ammonium salt and a boric acid compound. In the invention, the eutectic solvent is preferably in a liquid state at 77-196 ℃. In the invention, the eutectic solvent is a liquid formed by mixing hydrogen bond acceptor quaternary ammonium salt and hydrogen bond donor boric acid compound, the melting point of the eutectic solvent is far lower than the melting points of the two components under the action of intermolecular hydrogen bonds, therefore, the liquid state can be presented within 77-196 ℃ under a proper temperature operation window, and the liquid state has the characteristics of strong solvent property, low vapor pressure, strong stability and low toxicity, in the subsequent esterification reaction, the eutectic solvent is used as a solvent, so that the activation energy of the esterification reaction can be reduced, the esterification reaction can be carried out at a lower temperature, meanwhile, the method is easy to separate and recover from the product, on one hand, the hydroxyl on the glycerol structure can be protected, the directional and selective generation of the lauric acid monoglyceride in the esterification reaction is promoted, and the generation of the byproduct diester is inhibited, so that the selectivity, yield and purity of the product lauric acid monoglyceride are improved.
In the present invention, the preparation method of the eutectic solvent preferably includes: mixing the pretreated quaternary ammonium salt and boric acid compound, and stirring under heating condition to obtain the eutectic solvent.
In the present invention, the pretreatment is preferably vacuum drying. In the present invention, the temperature and time of the vacuum drying are not particularly limited, and the water in the quaternary ammonium salt can be removed. The operation of mixing the pretreated quaternary ammonium salt and the boric acid compound is not particularly limited, and the technical scheme for preparing the mixed solution, which is well known to those skilled in the art, can be adopted. In the invention, the heating temperature is preferably 50-90 ℃, and more preferably 70-85 ℃. In the invention, the stirring speed is preferably 300-1000 RPM, and more preferably 500-800 RPM. In the invention, the stirring time is preferably 10-50 min, and more preferably 20-40 min. The eutectic solvent prepared by the method is beneficial to promoting hydrogen bonds to be fully formed between the quaternary ammonium salt and the boric acid compound, so that the eutectic solvent with better performance is obtained, the separation and the recovery of the eutectic solvent and a product are easy, and the selectivity, the yield and the purity of the product lauric acid monoglyceride are improved.
In the invention, the quaternary ammonium salt preferably has a structure shown in a formula I or a formula II;
in the invention, R in the formula I1And R in said formula II2Preferably independently C2～C5Alkyl, further preferably independently ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or isopentyl. In the invention, X in the formulas I and II-Preferably independently chloride or bromide.
In an embodiment of the present invention, the quaternary ammonium salt may be embodied as one of tetrapropylammonium bromide, choline chloride, tetraethylammonium bromide, and tetrapropylammonium bromide.
In the present invention, the boric acid-based compound preferably comprises one or more of boric acid and an organoboronic acid-based compound. In the present invention, the organoboronic acid compound is preferably phenylboronic acid. In the invention, the boric acid compound can protect hydroxyl on a glycerol structure, promote the esterification reaction to directionally and selectively generate the lauric acid monoglyceride, and inhibit the generation of a byproduct diester, so that the selectivity, yield and purity of the product lauric acid monoglyceride are improved, and a eutectic solvent formed by the boric acid compound and quaternary ammonium salt has a lower melting point and is in a liquid state, thereby being beneficial to separation and recycling of the product.
In the invention, the molar ratio of the quaternary ammonium salt to the boric acid compound is 1: (0.5 to 2), more preferably 1: (0.8 to 1.2), and more preferably 1: 1. The invention controls the molar ratio of the quaternary ammonium salt and the boric acid compound in the range, which is favorable for obtaining the eutectic solvent with stable thermodynamic property, thereby being favorable for recovering the eutectic solvent and avoiding the excessive components from remaining in the ester phase.
In the present invention, the eutectic solvent preferably includes one or more of a choline chloride-boric acid eutectic solvent, a tetraethylammonium bromide-boric acid eutectic solvent, a tetrapropylammonium bromide-boric acid eutectic solvent, and a tetrabutylammonium bromide-boric acid eutectic solvent.
In the present invention, the mass of the eutectic solvent is preferably 5 to 40%, more preferably 10 to 35% of the total mass of lauric acid and glycerin. The invention controls the quality of the eutectic solvent in the range, is beneficial to realizing the reduction of activation energy and the improvement of product selectivity, saves raw materials and reduces cost.
In the invention, the temperature of the esterification reaction is 120-160 ℃, and more preferably 130-150 ℃; in the invention, the esterification reaction time is 3-12 h, and more preferably 5-10 h. The invention controls the temperature and time of the esterification reaction within the range, is favorable for promoting the lauric acid and the glycerol to have the esterification reaction completely, converts the lauric acid and the glycerol into the lauric acid monoglyceride and improves the yield of the product.
In the esterification reaction process, on one hand, the hydrogen bond acceptor quaternary ammonium salt of the eutectic solvent exerts a solvent effect to prevent lauric acid and glycerol from being in a liquid-liquid phase separation state, so that a homogeneous reaction environment with excessive glycerol is formed, and the activation energy of the esterification reaction is reduced, on the other hand, the hydrogen bond donor boric acid compound of the eutectic solvent reacts with hydroxyl on the glycerol to generate a boric acid glyceride intermediate, so that the selective generation of lauric acid monoglyceride is realized, and the generation of a byproduct diester is inhibited.
After the esterification reaction, the invention preferably carries out heat preservation and standing, liquid-liquid separation, water washing, rotary evaporation and purification on the product of the esterification reaction in sequence to obtain the lauric acid monoglyceride.
In the invention, the product of the esterification reaction is preferably kept warm and kept stand to obtain a layered solution. In the invention, the upper layer of the layered solution is an ester phase; the lower layer of the layering solution is a glycerin phase. In the present invention, the ester phase preferably includes a major amount of monoglycerol ester of lauric acid, a minor amount of lauric acid, glycerin, diglycerol ester of lauric acid, and a very small amount of eutectic solvent; the glycerol phase preferably comprises (unreacted glycerol and most of the eutectic solvent). In the invention, the temperature of the heat preservation and standing is preferably 65-90 ℃, more preferably 70-85 ℃, and further preferably 80 ℃. In the invention, the time for heat preservation and standing is preferably 0.5-4 h, and more preferably 1-3 h. The temperature and the time of the heat preservation and standing are controlled within the range, so that the lauric acid monoglyceride serving as a product is ensured to be liquid, the lauric acid monoglyceride is prevented from being condensed into solid, the fluidity of the lauric acid monoglyceride is kept, the liquid-liquid separation is conveniently carried out subsequently, and the glycerin phase and the ester phase are effectively separated.
After obtaining the layered solution, the present invention preferably performs liquid-liquid separation on the layered solution to obtain a glycerin phase and an ester phase, respectively. The liquid-liquid separation method is not particularly limited, and the glycerol phase and the ester phase can be effectively separated.
After obtaining the glycerin phase, the glycerin phase is preferably recycled and directly put into the reaction system of the esterification reaction.
After obtaining the ester phase, the present invention preferably washes the ester phase with water to obtain a washed ester phase. The present invention is not particularly limited in the manner of the water washing, and glycerin, a very small amount of ammonium salt and boric acid dissolved in the water-soluble substance in the ester phase may be removed. In the present invention, the number of washing with water is preferably 2 to 5, and more preferably 3. In the present invention, the water used for the water washing is preferably deionized water; the volume of the deionized water is preferably 1-3 times of that of an ester phase system.
After obtaining the ester phase after water washing, the invention preferably performs rotary evaporation on the ester phase after water washing to obtain the ester phase after rotary evaporation. In the present invention, the spin-evaporation method is not particularly limited, and water in the ester phase after water washing may be removed. In the invention, the rotary evaporation temperature is preferably 70-90 ℃, and more preferably 80 ℃. In the invention, the degree of vacuum of the rotary evaporation is preferably 2-4 KPa, and more preferably 3 KPa. In the invention, the time of the rotary evaporation is preferably 2-10 h, more preferably 3-8 h, and further preferably 6 h.
After obtaining the rotary evaporated ester phase, the application preferably separates and purifies the rotary evaporated ester phase to obtain the lauric acid monoglyceride. The method for separation and purification is not particularly limited in the present application, and a method well known in the art may be used.
According to the preparation method provided by the invention, lauric acid and glycerol are used as raw materials, the glycerol esterification reaction of long-chain fatty acid lauric acid is catalyzed by an acid catalyst, and the eutectic solvent is used as a solvent, so that the activation energy of the esterification reaction can be reduced, the esterification reaction can be carried out at a lower temperature, and the esterification reaction and a product can be easily separated and recovered.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The process for preparing lauric acid monoglyceride in example 1 of the present invention is shown in fig. 1, and comprises the steps of adding lauric acid, glycerol, an acidic catalyst and a eutectic solvent into a reaction kettle to perform an esterification reaction, sequentially performing heat preservation and standing, liquid-liquid separation, water washing and rotary evaporation to obtain a rotary evaporated ester phase, and performing product detection.
1. Preparation method of eutectic solvent
Mixing 0.46kg of tetrapropylammonium bromide subjected to vacuum drying pretreatment and 0.11kg of boric acid, placing the mixture in a reaction kettle, and heating the mixture for 30min at 80 ℃ and at the stirring speed of 600rpm to obtain 0.57kg of colorless homogeneous liquid tetrapropylammonium bromide-boric acid eutectic solvent;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1.
2. Preparation method of lauric acid monoglyceride
Adding 1.00kg of lauric acid, 1.84kg of glycerol, 0.02kg of hydrobromic acid aqueous solution with the acid catalyst mass fraction of 40% and the tetrapropylammonium bromide-boric acid eutectic solvent prepared by the preparation method into a reaction kettle, heating to 150 ℃ to perform esterification reaction for 8h, preserving heat at 80 ℃ after the reaction is finished, standing for 2h for layering, separating an upper ester phase from liquid-liquid, washing with deionized water for three times, and performing rotary evaporation for 6h under the conditions of 80 ℃ and the vacuum degree of 3Kpa to remove water to obtain a rotary evaporated ester phase;
wherein the molar ratio of lauric acid to glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol;
product detection component analysis is carried out on the rotary evaporated ester phase by using high performance liquid chromatography, and the product is found to only contain lauric acid monoglyceride and lauric acid diglyceride and not to contain lauric acid triglyceride, wherein the selectivity of the prepared lauric acid monoglyceride can reach 85.7%, the yield can reach 76.4%, and the purity can reach 89.1%.
Example 2
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1:1, the molar ratio of the lauric acid to the glycerol is 1:4, the mass of the acidic catalyst is 0.7% of the total mass of the lauric acid and the glycerol, the mass of the eutectic solvent is 20% of the total mass of the lauric acid and the glycerol, and the temperature of the esterification reaction is 140 ℃.
Example 3
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1:1, the molar ratio of the lauric acid to the glycerol is 1:4, the mass of the acidic catalyst is 0.7% of the total mass of the lauric acid and the glycerol, the mass of the eutectic solvent is 30% of the total mass of the lauric acid and the glycerol, and the temperature of the esterification reaction is 160 ℃.
Example 4
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.23kg of vacuum-dried pretreated tetrapropylammonium bromide and 0.055kg of boric acid;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 10% of the total mass of lauric acid and glycerol.
Example 5
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.69kg of vacuum-dried pretreated tetrapropylammonium bromide and 0.165kg of boric acid;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 30% of the total mass of lauric acid and glycerol;
example 6
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.39kg of vacuum-dried pretreated tetrapropylammonium bromide, 0.09kg of boric acid, 1.38kg of glycerin, 0.017kg of an acidic catalyst, 40% aqueous hydrobromic acid solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 3; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol;
example 7
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.54kg of vacuum-dried pretreated tetrapropylammonium bromide, 0.12kg of boric acid, 2.31kg of glycerin, 0.023kg of acidic catalyst 40% hydrobromic acid aqueous solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 5; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol;
example 8
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.01kg of an acidic catalyst 40% aqueous hydrobromic acid solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.35 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol;
example 9
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.03kg of an acidic catalyst 40% aqueous hydrobromic acid solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 1.06 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol;
example 10
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.19kg of vacuum-dried pretreated tetrapropylammonium bromide, 0.05kg of boric acid, 1.38kg of glycerin, 0.01kg of an acidic catalyst, 40% aqueous hydrobromic acid solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 3; the mass of the acidic catalyst is 0.42 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 10% of the total mass of lauric acid and glycerin, and the temperature of the esterification reaction is 140 ℃.
Example 11
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.82kg of vacuum-dried pretreated tetrapropylammonium bromide, 0.19kg of boric acid, 2.38kg of glycerin, 0.03kg of an acidic catalyst, 40% aqueous hydrobromic acid solution;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 5; the mass of the acidic catalyst is 0.89% of the total mass of lauric acid and glycerol; the mass of the eutectic solvent is 30% of the total mass of lauric acid and glycerin, and the temperature of the esterification reaction is 160 ℃.
Example 12
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.39kg of choline chloride pretreated by vacuum drying, 0.18kg of boric acid;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol.
Example 13
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.44kg of tetraethylammonium bromide pretreated by vacuum drying;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol.
Example 14
Lauric acid monoglyceride was prepared according to the method of example 1, and the selectivity, yield, and purity thereof were tested by the same method, and the specific results are shown in table 1;
the raw materials are changed into: 0.48kg of tetrabutylammonium bromide pretreated by vacuum drying, 0.09kg of boric acid;
wherein the molar ratio of the tetrapropylammonium bromide to the boric acid is 1: 1; the molar ratio of the lauric acid to the glycerol is 1: 4; the mass of the acidic catalyst is 0.7 percent of the total mass of the lauric acid and the glycerol; the mass of the eutectic solvent is 20% of the total mass of lauric acid and glycerol.
TABLE 1 lauric acid monoglyceride prepared in examples 1 to 14, yield and purity
The example and the table 1 show that the lauric acid monoglyceride can be prepared by the method provided by the application at the low temperature of 140-160 ℃, the product selectivity is 87.1%, the yield is 76.4%, and the purity is 89.4%. In addition, the preparation method provided by the invention takes lauric acid and glycerol as raw materials, the glycerol esterification reaction of long-chain fatty acid lauric acid is catalyzed by an acid catalyst, and the eutectic solvent is used as a solvent on one hand, so that the activation energy of the esterification reaction can be reduced, the esterification reaction can be carried out at a lower temperature, and the esterification reaction is easy to separate and recover from a product.
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 (10)
1. A preparation method of lauric acid monoglyceride comprises the following steps: mixing lauric acid, glycerol, an acidic catalyst and a eutectic solvent, and then carrying out esterification reaction to obtain the lauric acid monoglyceride.
2. The production method according to claim 1, wherein the mass of the acidic catalyst is 0.03 to 0.2% of the total mass of lauric acid and glycerin.
3. The method according to claim 1, wherein the eutectic solvent includes a quaternary ammonium salt and a boric acid compound.
4. The method according to claim 2, wherein the quaternary ammonium salt has a structure represented by formula I or formula II;
wherein R in the formula I1And R in said formula II2Independently is C2～C5Alkyl, X in the formulae I and II-Independently chloride or bromide.
5. The process according to claim 4, wherein R in the formula I1And R in said formula II2Independently is ethyl, n-propyl, isoPropyl, n-butyl, isobutyl, n-pentyl or isopentyl.
6. The method according to claim 3, wherein the boric acid compound comprises one or more of boric acid and an organoboronic acid compound.
7. The production method according to claim 1, wherein the ratio of the amounts of the substance of the quaternary ammonium salt and the boric acid compound is 1: (0.5-2).
8. The production method according to claim 1 or 3, characterized in that the eutectic solvent includes one or more of a choline chloride-boric acid eutectic solvent, a tetraethylammonium bromide-boric acid eutectic solvent, a tetrapropylammonium bromide-boric acid eutectic solvent, and a tetrabutylammonium bromide-boric acid eutectic solvent.
9. The method according to claim 1 or 3, wherein the mass of the eutectic solvent is 5 to 40% of the total mass of lauric acid and glycerin.
10. The preparation method according to claim 1, wherein the temperature of the esterification reaction is 120 to 160 ℃; the esterification reaction time is 3-12 h.
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