CN110760386B - Method for inhibiting acyl transfer of di-monoglyceride - Google Patents

Method for inhibiting acyl transfer of di-monoglyceride Download PDF

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CN110760386B
CN110760386B CN201910948895.4A CN201910948895A CN110760386B CN 110760386 B CN110760386 B CN 110760386B CN 201910948895 A CN201910948895 A CN 201910948895A CN 110760386 B CN110760386 B CN 110760386B
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water activity
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CN110760386A (en
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王小三
高亮
王笑寒
赵彧
王兴国
金青哲
黄健花
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0092—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0028—Carboxylic acids; Their derivates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0042—Preserving by using additives, e.g. anti-oxidants containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0071—Preserving by using additives, e.g. anti-oxidants containing halogens, sulfur or phosphorus

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for inhibiting acyl transfer of di-monoglyceride relates to the technical field of grease. The method is characterized in that 2-monoglyceride and a polar solvent are mixed, the water activity in a mixed system is kept to be 0-0.50, the storage temperature is-30-70 ℃, and the method effectively inhibits the acyl transfer of 2-MAG in the storage process, is simple and practical, and can be applied to industrial production.

Description

Method for inhibiting acyl transfer of di-monoglyceride
Technical Field
The invention relates to the technical field of grease, in particular to a method for inhibiting acyl transfer of dibasic monoglyceride.
Background
Starting in the twentieth of the nineteenth century, scientists discovered that fatty acids located on the MAG glycerol backbone could be spontaneously transacylated. Acyl transfer refers to the intramolecular transfer of one acyl group to an adjacent unoccupied hydroxyl group on the glycerol backbone. The acyl transfer of 2-MAG is a bimolecular nucleophilic substitution reaction.
The rate of acyl transfer is influenced by factors that alter the charge dispersion of the transition state of the nucleophilic substitution reaction. In the presence of protons, the electrophilic character of the carbonyl increases, and the adjacent hydroxyl group acts as a nucleophile to attack the carbonyl carbon, forming a five-membered ring transition state intermediate, i.e., the orthoester. The hydroxyl oxygen attacks the carbon atom again, opening the five-membered ring and forming 1-MAG. When the reaction conditions favor charge dispersion in the transition state of the reaction, the transition state energy is low, the activation energy is reduced, and the acyl transfer rate of the 2-MAG is increased.
However, the literature reports that the reaction process is a research on acyl transfer, and during the storage process, the acyl transfer of 2-MAG can also occur spontaneously without the catalysis of enzyme, namely the transfer of 2-MAG to 1-MAG. Therefore, there is a need to develop a method for inhibiting acyl transfer of 2-MAG during storage.
Disclosure of Invention
Aiming at the problem of acyl transfer during the storage of 2-MAG, the invention aims to provide a method for inhibiting the acyl transfer of 2-MAG, which comprises the steps of mixing 2-MAG, water and a polar solvent, adjusting the water activity in a mixed system to be 0-0.50 and storing at the temperature of-30-70 ℃.
The water activity represents a parameter of the energy state of water in the system, namely the ratio of the vapor pressure of water in the system to the vapor pressure of pure water at the same temperature. When the water activity in the system can reach 1 to the maximum, the state of the water is close to free water, and the water activity of the system cannot be improved by increasing the water content of the system. The detection method and the calculation method of the water activity are obtained by adopting the international standard ISO 417-.
In one embodiment, the 2-MAG is an unsaturated fatty acid 2-MAG, including monounsaturated fatty acid 2-MAG, polyunsaturated fatty acid 2-MAG.
In one embodiment, the method of regulating water activity comprises: drying or adding saturated salt solution into the mixed system.
In one embodiment, the saturated salt solution comprises a LiCl saturated salt solution, Mg (NO)3)2Saturated salt solutions or K2SO4Saturated salt solution.
In one embodiment, the polar solvent is a solvent having a solvent hydrophobic interaction parameter log P value of less than 1.5.
Generally, in the chemical reaction involving an organic solvent as a reaction medium, the strength of the organic solvent can be represented by a polar coefficient log P, where P refers to the partition coefficient of the solvent in both phases of n-octane and water. The larger the polarity coefficient, the smaller the polarity is; conversely, the smaller the polarity coefficient, the stronger the polarity.
In one embodiment, the polar solvent comprises one or more of acetonitrile, acetone, ethanol, tert-butanol, methanol, acetic acid, propanol, propionic acid, butanone, tetrahydrofuran, butanol, pentanone, ethyl acetate, diethyl ether, ethyl chloride, methylbutylamine, pentanol.
In one embodiment, the water activity in the mixed system is 0 to 0.25.
In one embodiment, the ratio of 2-MAG to polar solvent is 1: 1 to 30 m/v.
In one embodiment, the ratio of 2-MAG to polar solvent is 1: 2 to 20 m/v.
Advantageous effects
The method for inhibiting 2-MAG acyl transfer provided by the invention mixes 2-MAG, water and a polar solvent, and effectively inhibits the 2-MAG from generating acyl transfer in the water activity range of 0-0.5 and under the storage condition of the temperature of minus 30-70 ℃.
In chemical reactions, organic solvents are used as a reaction medium and generally do not participate in the reaction, and in addition, the organic solvents are divided into hydrophobic solvents and hydrophilic solvents, which affect the acyl transfer of glycerides. Depending on the effect of the organic solvent on the acyl transfer in the chemical reaction, the addition of the organic solvent and the inhibition of the acyl transfer at a certain water activity during storage is an effective method.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The detection method and the calculation method of the water activity of the following experiments are obtained by adopting the international standard ISO 417-.
Example 1:
2-docosahexaenoic acid-MAG was reacted with t-butanol at a ratio of 1: 4(m/v), adding water to make the water activity of the system 0.31, storing at 25 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 2:
2-oleic acid-MAG was reacted with ethanol in a 1: 5(m/v), adding water to make the water activity of the system 0.12, storing at-10 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, calculating the change of the content of 2-MAG, and the results are shown in Table 1.
Example 3:
2-linoleic acid-MAG was reacted with acetone in a 1: 7(m/v), adding water to make the water activity of the system 0.87, storing at 50 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, the results are shown in Table 1.
Example 4:
2-eicosapentaenoic acid-MAG was reacted with methanol at a ratio of 1: 5(m/v), adding water to make the water activity of the system 0.24, storing at-25 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, calculating the change of the content of 2-MAG, and the results are shown in Table 1.
Example 5:
2-palmitoleic acid-MAG was reacted with acetonitrile at a ratio of 1: 10(m/v), adding water to make the water activity of the system 0.13, storing at 35 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, the results are shown in Table 1.
Example 6:
2-linolenic acid-MAG was mixed with tert-butanol at a ratio of 1: 10(m/v), adding water to make the water activity of the system 0.64, storing at 65 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 7:
2-docosahexaenoic acid-MAG was reacted with diethyl ether at a ratio of 1: 5(m/v), adding water to make the water activity of the system 0.51, storing at 25 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 8:
2-linoleic acid-MAG was reacted with formic acid in a 1: 3(m/v), adding water to make the water activity of the system 0.29, storing at 0 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 9:
2-tetradecenoic acid-MAG was reacted with butanone in a ratio of 1: 15(m/v), adding water to make the water activity of the system 0.48, storing at 15 ℃ for 30 days, measuring the 2-MAG content before mixing and the 2-MAG content after storing for 30 days, and calculating the change of the 2-MAG content therein, the results are shown in Table 1.
Example 10:
2-docosapentaenoic acid-MAG was reacted with tetrahydrofuran in a 1: 20(m/v) was mixed, the water activity of the water system was 0.37, the mixture was stored at-4 ℃ for 30 days, the content of 2-MAG before mixing and the content of 2-MAG after 30 days of storage were measured, and the change in the content of 2-MAG was calculated, and the results are shown in Table 1.
Example 11:
2-eicosenoic acid-MAG was reacted with ethyl acetate at a ratio of 1: 8(m/v), adding water to make the water activity of the system 0.69, storing at 40 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 12:
2-oleic acid-MAG with propionic acid in a 1: 2(m/v), adding water to make the water activity of the system 0.38, storing at 50 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, the results are shown in Table 1.
Example 13:
2-docosahexaenoic acid-MAG was reacted with ethyl chloride in a 1: 4(m/v), adding water to make the water activity of the system 0.12, storing at 25 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Example 14:
2-tetracosenoic acid-MAG was reacted with diethyl ether at a ratio of 1: 25(m/v), adding water to make the water activity of the system 0.36, storing at 15 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, the results are shown in Table 1.
Example 15:
2-eicosatetraenoic acid-MAG was reacted with propanol at a ratio of 1: 3(m/v), adding water to make the water activity of the system 0.23, storing at 25 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
Comparative example 1:
2-docosahexaenoic acid-MAG was stored at 25 ℃ for 30 days, water was added to make the water activity of the system 0.89, the content of 2-MAG before mixing and the content of 2-MAG after storage for 30 days were measured, and the change in the content of 2-MAG was calculated, and the results are shown in Table 1.
Comparative example 2:
2-linoleic acid-MAG was reacted with n-hexane in a 1: 10(m/v) Water was mixed to give a water activity of 0.96, and the mixture was stored at 55 ℃ for 30 days, and the content of 2-MAG before mixing and the content of 2-MAG after 30 days of storage were measured to calculate the change in the content of 2-MAG, and the results are shown in Table 1.
Comparative example 3:
2-oleic acid-MAG was stored at-20 ℃ for 30 days, water was added to make the water activity of the system 0.47, the content of 2-MAG before mixing and the content of 2-MAG after storage for 30 days were measured, and the change in the content of 2-MAG was calculated, and the results are shown in Table 1.
Comparative example 4:
2-Docosahopentaenoic acid-MAG was stored at 80 ℃ for 30 days, water was added to make the water activity of the system 0.85, the content of 2-MAG before mixing and the content of 2-MAG after 30 days of storage were measured, and the change in the content of 2-MAG was calculated, and the results are shown in Table 1.
Comparative example 5:
2-linolenic acid-MAG was reacted with cyclohexane at a molar ratio of 1: 5(m/v), adding water to make the water activity of the system 0.37, storing at 0 ℃ for 30 days, measuring the content of 2-MAG before mixing and the content of 2-MAG after storing for 30 days, and calculating the change of the content of 2-MAG, wherein the results are shown in Table 1.
TABLE 1
Figure GDA0002463101290000051
Note:
Figure GDA0002463101290000052
therefore, the method for inhibiting the 2-MAG acyl transfer is simple and practical in the whole operation process, compared with the method for storing 2-MAG in a solvent-free system, the method obviously improves the acyl transfer of the 2-MAG, and can effectively inhibit the 2-MAG acyl transfer when a polar solvent with a log P value less than 1.5 and water activity are stored in a range of 0-0.50, particularly when the polar solvent with the log P value less than 1.5 and the water activity are stored in a range of 0-0.25.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (6)

1. A method of inhibiting the acyl transfer of a di-monoglycerides 2-MAG, wherein the acyl transfer of a di-monoglycerides,
the method comprises the steps of mixing 2-oleic acid-MAG, water and ethanol, wherein the ratio of the 2-oleic acid-MAG to the ethanol is 1: 5m/v, adjusting the water activity in the mixed system to be 0.12, and storing at the temperature of minus 10 ℃;
or the method is to mix 2-eicosapentaenoic acid-MAG, water and methanol, wherein the ratio of the 2-eicosapentaenoic acid-MAG to the methanol is 1: 5m/v, adjusting the water activity in the mixed system to be 0.24, and storing at the temperature of-25 ℃.
2. The method of claim 1, wherein the step of adjusting the water activity comprises: drying or regulating water activity of the mixed system with saturated salt solution.
3. The method of claim 2, wherein the saturated salt solution comprises LiCl saturated salt solution, Mg (NO)3)2Saturated salt solutions or K2SO4Saturated salt solution.
4. A method for inhibiting acyl transfer of di-monoglycerides, wherein the di-monoglycerides are 2-MAG, the method comprises mixing 2-linoleic acid-MAG, water and formic acid, and the ratio of 2-linoleic acid-MAG to formic acid is 1: 3 m/v, adjusting the water activity in the mixed system to be 0.29 and the storage temperature to be 0 ℃.
5. The method of claim 4, wherein the step of adjusting the water activity comprises: drying or regulating water activity of the mixed system with saturated salt solution.
6. The method of claim 5, wherein the saturated salt solution comprises LiCl saturated salt solution, Mg (NO)3)2Saturated salt solutions or K2SO4Saturated salt solution.
CN201910948895.4A 2019-10-08 2019-10-08 Method for inhibiting acyl transfer of di-monoglyceride Active CN110760386B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105483170A (en) * 2016-01-08 2016-04-13 江南大学 Method for synthesizing Sn-2-monoglyceride through enzymic method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105483170A (en) * 2016-01-08 2016-04-13 江南大学 Method for synthesizing Sn-2-monoglyceride through enzymic method

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