CN113861024B - Preparation method of fatty acid polyethylene glycol ester - Google Patents
Preparation method of fatty acid polyethylene glycol ester Download PDFInfo
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- CN113861024B CN113861024B CN202111169820.XA CN202111169820A CN113861024B CN 113861024 B CN113861024 B CN 113861024B CN 202111169820 A CN202111169820 A CN 202111169820A CN 113861024 B CN113861024 B CN 113861024B
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- polyethylene glycol
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 63
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 63
- 239000000194 fatty acid Substances 0.000 title claims abstract description 63
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 63
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 54
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 54
- 150000002148 esters Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 230000032050 esterification Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- -1 hypophosphorous acid compound Chemical class 0.000 claims description 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 150
- 229910052757 nitrogen Inorganic materials 0.000 description 74
- 238000003756 stirring Methods 0.000 description 36
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 28
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 20
- 239000005642 Oleic acid Substances 0.000 description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 13
- 210000000476 body water Anatomy 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 9
- 229940049964 oleate Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 3
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229940095098 glycol oleate Drugs 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001522 polyglycol ester Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of fatty acid polyethylene glycol ester, which mainly solves the problem of high chromaticity of products obtained by the existing preparation method of the fatty acid polyethylene glycol ester, and comprises the following steps: first esterification reaction: comprises the steps of carrying out a first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acid catalyst to obtain a first esterification product mixture, wherein the first esterification raw material mixture comprises polyethylene glycol and a first part of raw material fatty acid; second esterification reaction: the second esterification raw material mixture is subjected to a second esterification reaction to obtain a fatty acid polyethylene glycol ester product, and the second esterification raw material mixture comprises the first esterification product mixture and a second part of raw material fatty acid.
Description
Technical Field
The invention relates to a preparation method of fatty acid polyethylene glycol ester.
Background
The fatty acid polyethylene glycol ester is a nonionic surfactant and has wide application in the fields of various spinning oil solutions, chemical additives, daily chemicals and the like.
Fatty acid polyethylene glycol esters can be obtained by an esterification reaction method between fatty acid and polyethylene glycol in the presence of an acidic catalyst, for example, polyethylene glycol oleate catalyst synthesis research (Luo Xiaomin, jiang Taotao, ren Longfang. Polyethylene glycol oleate catalytic synthesis research [ J ]. University of technology of Shaanxi, 2008, 26 (2): 50-52) is carried out by Luo Xiaomin, etc., but the obtained fatty acid polyethylene glycol esters have darker products, and the market popularization of the products is limited in the occasion with higher requirements on low chromaticity of the products.
Disclosure of Invention
The invention mainly solves the technical problem of high product chromaticity of the existing preparation method of the fatty acid polyethylene glycol ester, and provides a novel preparation method of the fatty acid polyethylene glycol ester, which has the advantage of reducing the product chromaticity of the fatty acid polyethylene glycol ester.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the fatty acid polyethylene glycol ester comprises the following steps:
first esterification reaction: comprises the steps of carrying out a first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acid catalyst to obtain a first esterification product mixture, wherein the first esterification raw material mixture comprises polyethylene glycol and a first part of raw material fatty acid;
second esterification reaction: and performing a second esterification reaction on a second esterification raw material mixture to obtain a fatty acid polyethylene glycol ester product, wherein the second esterification raw material mixture comprises the first esterification product mixture and a second part of raw material fatty acid.
Compared with a one-stage esterification process adopting all polyethylene glycol and all raw material fatty acid to perform esterification reaction under the same ratio, the product chromaticity value obtained by adopting the two-stage esterification process adopting all polyethylene glycol and a first part of raw material fatty acid to perform first esterification reaction and then adding the rest of raw material fatty acid to perform second esterification reaction is lower.
In the above technical scheme, preferably, the molar ratio of the first part of raw material fatty acid to polyethylene glycol is 0.05-0.8. For example, but not limited to, the molar ratio of the first portion of the starting fatty acid to polyethylene glycol is 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, etc. More preferably, the molar ratio of the first portion of the raw material fatty acid to the polyethylene glycol is 0.1 to 0.5.
In the above technical solution, preferably, the reaction auxiliary agent is an acid catalyst; or the reaction auxiliary agent is an acid catalyst and an esterification process color inhibitor.
In the above technical solution, preferably, the color inhibitor for the esterification process includes at least one selected from hypophosphorous acid compounds and stannous fatty acids.
In the above technical solution, preferably, the acidic catalyst includes at least one selected from the group consisting of arylsulfonic acid, sulfuric acid, and acid sulfate.
In the above technical scheme, preferably, the catalyst dosage accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, catalyst loading is 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95% by weight of polyethylene glycol, and the like.
In the above technical solution, preferably, the arylsulfonic acid corresponds to the following formula 1:
wherein R is 1 And R is 2 Independently selected from H or C1-C3 alkyl. Such as but not limited to, benzenesulfonic acid, p-toluenesulfonic acid, cumene sulfonic acid, xylenesulfonic acid and the like.
In the above technical solution, preferably, the hypophosphorous acid compound includes hypophosphorous acid and/or hypophosphite. The hypophosphite is preferably an alkali metal hypophosphite salt, and more preferably the alkali metal is potassium or sodium.
In the above technical solution, preferably, the stannous fatty acid meets the following structural formula 2:
wherein R is 3 And R is 4 Independently selected from C9-C20 hydrocarbyl groups (e.g., without limitation, R 3 And R is 4 Independently selected from the group consisting of C10 hydrocarbyl, C11 hydrocarbyl, C12 hydrocarbyl, C13 hydrocarbyl, C14 hydrocarbyl, C15 hydrocarbyl, C16 hydrocarbyl, C17 hydrocarbyl, C18 hydrocarbyl, C19 hydrocarbyl).
In the technical scheme, R 3 And R is 4 Straight-chain hydrocarbon groups are independently preferred.
In the technical scheme, R 3 And R is 4 Primary hydrocarbyl groups are independently preferred.
In the technical scheme, R 3 And R is 4 Alkenyl or alkyl groups are independently preferred.
In the above technical scheme, preferably, the dosage of the color inhibitor accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, the color inhibitor may be added in an amount of 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95% by weight of the polyethylene glycol, etc.
During the esterification reaction, the presence of the color inhibitor reduces the chromaticity of the product.
In the above technical scheme, the reaction temperature of the first esterification reaction and the second esterification reaction is independently preferably 110-160 ℃. Such as, but not limited to, the reaction temperatures of the first esterification reaction and the second esterification reaction are independently 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, and the like.
In the above technical scheme, the reaction time of the first esterification reaction and the second esterification reaction is independently preferably 1 to 5 hours. For example, but not limited to, the reaction time of the first esterification reaction and the second esterification reaction is independently preferably 1.5, 2.0, 2.5, 3.0, 3.5 hours, 4 hours, 4.5 hours, and the like.
In the above technical scheme, preferably, the molar ratio of (the first part of raw material fatty acid+the second part of raw material fatty acid) to polyethylene glycol is 0.9-2.2. Such as, but not limited to, a molar ratio of (first portion of raw fatty acid + second portion of raw fatty acid) to polyethylene glycol of 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.95, 2, 2.05, 2.1, 2.15, etc.
In the above technical scheme, preferably, the raw material fatty acid is a C8-C20 monoacid. Such as, but not limited to, the starting fatty acid is a C9 monoacid, a C10 monoacid, a C11 monoacid, a C12 monoacid, a C13 monoacid, a C14 monoacid, a C15 monoacid, a C16 monoacid, a C17 monoacid, a C18 monoacid, and the like. More preferably a linear fatty acid; optionally saturated or unsaturated fatty acids. For comparison, oleic acid is used in the specific embodiments.
In the above technical scheme, preferably, the polyethylene glycol has a number average molecular weight of 200 to 1000. Such as, but not limited to, polyethylene glycol, has a number average molecular weight of 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, and the like. For comparison, polyethylene glycol 400 (PEG 400) is used in the examples and comparative examples.
In the above technical solution, it is known to those skilled in the art that, in order to reduce the chromaticity of the product, the atmosphere of the first esterification reaction and the atmosphere of the second esterification reaction are independently nitrogen atmosphere, and more independently, preferably, nitrogen is continuously introduced. The nitrogen atmosphere is favorable for reducing the chromaticity of the product, and the continuous introduction of nitrogen is also favorable for bringing water generated by the esterification reaction into a reaction system by using the nitrogen so as to be favorable for the esterification reaction to be carried out in the direction of increasing the esterification degree. The space velocity of the nitrogen gas relative to the weight of the polyethylene glycol is preferably 0.2 to 0.5 ml of nitrogen gas per gram of polyethylene glycol per minute.
In the above technical solution, preferably, the color inhibitor includes a hypophosphorous acid compound and stannous fatty acid. The hypophosphorous acid compound has an interaction with stannous fatty acid in reducing the color of the product.
In the above technical solution, preferably, the weight ratio of stannous fatty acid to hypophosphorous acid compound is greater than 0 and less than 0.5, and further non-limiting specific examples are: the weight ratio of stannous fatty acid to hypophosphorous acid compound is 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, etc. Most preferably 0.10 to 0.45.
The measurement of the chromaticity of the fatty acid polyglycol ester product of the invention is carried out according to standard methods (GB/T605-2006 general method for measuring chromaticity of chemical reagents).
The acid value of the fatty acid polyglycol ester product of the invention is measured by standard method (GB/T6365-2006 method for determining the free alkalinity or the free acidity of the surfactant).
Detailed Description
Example 1
400 g of polyethylene glycol 400, 70 g of oleic acid and 2.0 g of p-toluenesulfonic acid are put into a 2 liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, the space in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the temperature of the kettle is raised to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Comparative example 1
400 g of polyethylene glycol 400, 560 g of oleic acid and 2.0 g of p-toluenesulfonic acid are put into a 2 liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condenser pipe), stirring is started and maintained, air in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for reaction for 5 hours, the temperature is reduced to 60 ℃, stirring is stopped, the introduction of the nitrogen is stopped, and the fatty acid polyethylene glycol ester product is obtained.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 2
400 g of polyethylene glycol 400, 280 g of oleic acid and 2.0 g of p-toluenesulfonic acid are put into a 2 liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, the space in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the temperature of the kettle is raised to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; stopping continuously introducing nitrogen, adding 280 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 3
400 g of polyethylene glycol 400, 140 g of oleic acid and 2.0 g of p-toluenesulfonic acid are put into a 2 liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, the space in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the temperature of the kettle is raised to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; stopping continuously introducing nitrogen, adding 420 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 4
400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of hypophosphorous acid are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condenser pipe), stirring is started and maintained, the space in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Comparative example 2
400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of hypophosphorous acid are put into a 2 liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condenser pipe), stirring is started and maintained, air in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 5 hours, the temperature is reduced to 60 ℃, stirring is stopped, the introduction of the nitrogen is stopped, and the fatty acid polyethylene glycol ester product is obtained after discharging.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 5
400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of paratoluenesulfonic acid and 2.0 g of stannous linoleate are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, nitrogen replaces the space in the reaction kettle for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Comparative example 3
400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of paratoluenesulfonic acid and 2.0 g of stannous oleate are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, air in the reaction kettle is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 5 hours, the temperature is reduced to 60 ℃, stirring is stopped, the introduction of the nitrogen is stopped, and the fatty acid polyethylene glycol ester product is obtained after discharging.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 6
400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of paratoluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, nitrogen is used for replacing the space in the reaction kettle for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Comparative example 4
400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of paratoluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, nitrogen is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 5 hours, the temperature is reduced to 60 ℃, stirring is stopped, the introduction of the nitrogen is stopped, and the fatty acid polyethylene glycol ester product is obtained.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 7
400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of paratoluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, nitrogen is used for replacing the space in the reaction kettle for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 2 hours, and the temperature is reduced to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with the nitrogen for three times, continuously introducing the nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing the nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Comparative example 5
400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of paratoluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid are put into a 2-liter reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port through an air reflux condensing pipe), stirring is started and maintained, nitrogen is replaced by nitrogen for three times, then nitrogen is continuously introduced, the flow rate of the nitrogen is 100 ml/min, the kettle is heated to 150 ℃ for 5 hours, the temperature is reduced to 60 ℃, stirring is stopped, the introduction of the nitrogen is stopped, and the fatty acid polyethylene glycol ester product is obtained.
For comparison, the main process parameters and the product test results are listed in table 1.
TABLE 1
In the table: tsOH is p-toluenesulfonic acid, T is the reaction temperature, T is the reaction time, T 1 Is the first esterification reaction temperature, t 1 For the first esterification reaction time, T 2 Is the second esterification reaction temperature, t 2 Is the second esterification reaction time; a represents stannous oleate, B represents stannous oleate and hypophosphorous acid, and the values in the () behind B are the weight ratio of stannous oleate to hypophosphorous acid; d is the mole ratio of the first part of raw material fatty acid to polyethylene glycol.
Claims (14)
1. The preparation method of the fatty acid polyethylene glycol ester comprises the following steps:
first esterification reaction: comprises the steps of carrying out a first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acid catalyst to obtain a first esterification product mixture, wherein the first esterification raw material mixture comprises polyethylene glycol and a first part of raw material fatty acid;
second esterification reaction: performing a second esterification reaction on a second esterification raw material mixture to obtain a fatty acid polyethylene glycol ester product, wherein the second esterification raw material mixture comprises a first esterification product mixture and a second part of raw material fatty acid;
the reaction auxiliary agent is an acid catalyst and an esterification process color inhibitor; the color inhibitor in the esterification process is hypophosphorous acid compound and fatty acid stannous; the weight ratio of the stannous fatty acid to the hypophosphorous acid compound is 0.01-0.5; the mole ratio of the first part of raw material fatty acid to polyethylene glycol is 0.05-0.8.
2. The method according to claim 1, wherein the weight ratio of stannous fatty acid to hypophosphorous acid compound is 0.10 to 0.45.
3. The method according to claim 1, wherein the molar ratio of the first portion of the raw material fatty acid to the polyethylene glycol is 0.05 to 0.5.
4. The method according to claim 1, wherein the acidic catalyst comprises at least one selected from the group consisting of arylsulfonic acid, sulfuric acid, and acid sulfate.
5. The preparation method of claim 1, wherein the acid catalyst is added in an amount of 0.2-1% by weight of the polyethylene glycol.
6. The process according to claim 4, wherein the arylsulfonic acid corresponds to the following formula 1:
a formula 1;
wherein R is 1 And R is 2 Independently selected from H or C1-C3 alkyl.
7. The method of claim 1, wherein the hypophosphorous acid compound comprises hypophosphorous acid and/or hypophosphite.
8. The preparation method according to claim 1, wherein the stannous fatty acid corresponds to the following structural formula 2:
formula 2;
wherein R is 3 And R is 4 Independently selected from C9-C20 alkyl.
9. The process according to claim 8, wherein R 3 And R is 4 Independently a straight hydrocarbon group.
10. The process according to claim 8, wherein R 3 And R is 4 Independently a primary hydrocarbyl group.
11. The process according to claim 8, wherein R 3 And R is 4 Independently an alkenyl or alkyl group.
12. The preparation method of claim 1, wherein the color inhibitor is added in an amount of 0.2-1% by weight of the polyethylene glycol.
13. The preparation method according to claim 1, wherein the reaction temperature of the first esterification reaction and the second esterification reaction is independently 110 to 160 ℃.
14. The production method according to claim 1, wherein the reaction time of the first esterification reaction and the second esterification reaction is independently 1 to 5 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB979673A (en) * | 1961-11-28 | 1965-01-06 | Ici Ltd | Preparation of ester of polyoxyalkylene compounds |
| CN111269410A (en) * | 2018-12-05 | 2020-06-12 | 上海多纶化工有限公司 | Decoloring agent and production method of secondary alcohol polyoxyethylene ether using decoloring agent |
| KR20200117870A (en) * | 2019-04-05 | 2020-10-14 | 효성티앤씨 주식회사 | Homopolyester polymerization catalyst and method for preparing polyester using the same |
| CN112552977A (en) * | 2020-12-30 | 2021-03-26 | 南京威尔药业集团股份有限公司 | Method for preparing synthetic ester base oil through step-by-step reaction |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB979673A (en) * | 1961-11-28 | 1965-01-06 | Ici Ltd | Preparation of ester of polyoxyalkylene compounds |
| CN111269410A (en) * | 2018-12-05 | 2020-06-12 | 上海多纶化工有限公司 | Decoloring agent and production method of secondary alcohol polyoxyethylene ether using decoloring agent |
| KR20200117870A (en) * | 2019-04-05 | 2020-10-14 | 효성티앤씨 주식회사 | Homopolyester polymerization catalyst and method for preparing polyester using the same |
| CN112552977A (en) * | 2020-12-30 | 2021-03-26 | 南京威尔药业集团股份有限公司 | Method for preparing synthetic ester base oil through step-by-step reaction |
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