CN113861024A - Preparation method of fatty acid polyglycol ester - Google Patents
Preparation method of fatty acid polyglycol ester Download PDFInfo
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- CN113861024A CN113861024A CN202111169820.XA CN202111169820A CN113861024A CN 113861024 A CN113861024 A CN 113861024A CN 202111169820 A CN202111169820 A CN 202111169820A CN 113861024 A CN113861024 A CN 113861024A
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 61
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 61
- 239000000194 fatty acid Substances 0.000 title claims abstract description 61
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 61
- 229920001522 polyglycol ester Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 37
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 230000032050 esterification Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- -1 hypophosphorous acid compound Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 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
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 128
- 229910052757 nitrogen Inorganic materials 0.000 description 63
- 238000003756 stirring Methods 0.000 description 36
- 238000001816 cooling Methods 0.000 description 31
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 29
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 28
- 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
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 13
- 210000000476 body water Anatomy 0.000 description 12
- 238000007599 discharging Methods 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
- 229940049964 oleate Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 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
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229940095098 glycol oleate Drugs 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 150000007513 acids 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 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
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration 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 polyglycol ester, which mainly solves the problem of high chroma of products obtained by the existing preparation method of fatty acid polyglycol ester, and the preparation method of fatty acid polyglycol ester comprises the following steps: a first esterification reaction: the method comprises the steps of carrying out first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acidic 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 technical scheme that the second esterification raw material mixture comprises the first esterification product mixture and the second part of raw material fatty acid enables the second esterification raw material mixture to undergo a second esterification reaction to obtain a fatty acid polyglycol ester product, well solves the technical problem, and can be used for production of fatty acid polyglycol ester.
Description
Technical Field
The invention relates to a preparation method of fatty acid polyglycol ester.
Background
The fatty acid polyglycol ester is a nonionic surfactant and has wide application in various spinning oil, chemical auxiliary, daily chemical and other fields.
The fatty acid polyglycol ester can be obtained by an esterification reaction between a fatty acid and polyethylene glycol in the presence of an acid catalyst, for example, a synthesis study of a polyethylene glycol oleate catalyst (dawn, heavy waves, anyongfang, a synthesis study of a polyethylene glycol oleate catalyst [ J ]. 50-52, published by university of science and technology of shanxi, 2008, 26 (2)) conducted by dawn, etc., but the product of the fatty acid polyglycol ester obtained in this way has a darker color, and is limited in market popularization in a field where the product has a higher requirement for low color.
Disclosure of Invention
The invention mainly solves the technical problem of high product chromaticity of the existing preparation method of the fatty acid polyglycol ester, and provides a novel preparation method of the fatty acid polyglycol ester, which has the advantage of reducing the product chromaticity of the fatty acid polyglycol ester.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the fatty acid polyglycol ester comprises the following steps:
a first esterification reaction: the method comprises the steps of carrying out first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acidic 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 subjecting a second esterification raw material mixture to a second esterification reaction 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 the one-stage esterification reaction process adopting the esterification reaction of all the polyethylene glycol and all the raw material fatty acid under the same ratio condition, the product chroma value obtained by the two-stage esterification process adopting the two-stage esterification reaction of the all the polyethylene glycol and the first part of the raw material fatty acid for the first esterification reaction and then adding the rest raw material fatty acid for the second esterification reaction is lower.
In the above technical solution, preferably, the molar ratio of the first part of raw material fatty acid to the polyethylene glycol is 0.05 to 0.8. For example, but not limited to, the molar ratio of the first portion of feedstock fatty acids 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, and the like. More preferably, the molar ratio of the first part of raw material fatty acid to the polyethylene glycol is 0.1-0.5.
In the above technical solution, preferably, the reaction auxiliary 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 esterification process color inhibitor includes at least one selected from a hypophosphorous acid compound and a fatty acid stannous.
In the above technical solution, preferably, the acidic catalyst includes at least one selected from the group consisting of an aromatic sulfonic acid, a sulfuric acid, and an acid sulfate.
In the technical scheme, preferably, the feeding amount of the catalyst accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, catalyst loading 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%, etc., by weight of the polyethylene glycol.
In the above technical solution, preferably, the aromatic sulfonic acid corresponds to the following formula 1:
wherein R is1And R2Is independently selected from H or alkyl of C1-C3. Examples but not limited to, of said arylsulfonic acids are benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid, and the like.
In the above technical solution, preferably, the hypophosphite compound comprises hypophosphorous acid and/or hypophosphite. The hypophosphite is preferably an alkali metal hypophosphite, and more preferably the alkali metal is potassium or sodium.
In the above technical solution, preferably, the fatty acid stannous is in accordance with the following structural formula 2:
wherein R is3And R4Independently selected from C9-C20 hydrocarbyl groups (such as but not limited to R)3And R4Independently selected from C10 hydrocarbyl, C11 hydrocarbyl, C12 hydrocarbyl, C13 hydrocarbyl, C14 hydrocarbyl, C15 hydrocarbyl, C16 hydrocarbyl, C17 hydrocarbyl, C18 hydrocarbyl, C19 hydrocarbyl).
In the above technical scheme, R3And R4Independently, linear hydrocarbon groups are preferred.
In the above technical scheme, R3And R4Independently, primary hydrocarbyl groups are preferred.
In the above technical scheme, R3And R4Independently, alkenyl or alkyl groups are preferred.
In the above technical scheme, preferably, the feeding amount of the color inhibitor accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, the amount of the color inhibitor 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 the polyethylene glycol.
The presence of the color inhibitor reduces the color of the product during the esterification reaction.
In the technical scheme, the reaction temperature of the first esterification reaction and the reaction temperature of the second esterification reaction are preferably 110-160 ℃ independently. For example, but not limited to, the reaction temperature of the first esterification reaction and the second esterification reaction is 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ and the like, independently.
In the technical scheme, the reaction time of the first esterification reaction and the second esterification reaction is preferably 1-5 hours independently. For example, but not limited to, the reaction times for the first esterification reaction and the second esterification reaction are 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 solution, preferably, the molar ratio of (the first part of raw material fatty acids + the second part of raw material fatty acids) to the polyethylene glycol is 0.9 to 2.2. For example, but not limited to, a molar ratio of (first portion of feedstock fatty acids + second portion of feedstock fatty acids) 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, and the like.
In the above technical solution, the raw material fatty acid is preferably a C8-C20 monobasic acid. For example, 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 straight chain fatty acids; optionally saturated or unsaturated fatty acids. For comparison, oleic acid is used in the specific embodiments.
In the technical scheme, the number average molecular weight of the polyethylene glycol is preferably 200-1000. For example, but not limited to, the 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 (abbreviated as PEG400) is used in the examples and comparative examples.
In the above technical scheme, those skilled in the art know that, in order to reduce the color 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, the continuous introduction of nitrogen is preferred. The nitrogen atmosphere is favorable for reducing the chroma of the product, and the continuous introduction of nitrogen is also favorable for taking the water generated by the esterification reaction out of the reaction system by using nitrogen, so that the esterification reaction is favorable for increasing the esterification degree. The space velocity of the nitrogen gas is preferably 0.2-0.5 ml of nitrogen gas per gram of polyethylene glycol per minute relative to the weight of polyethylene glycol.
In the above technical solution, preferably, the color inhibitor includes a hypophosphorous acid compound and fatty acid stannous. The hypophosphorous acid compound and the fatty acid stannous have mutual promotion effect on the aspect of reducing the chromaticity of the product.
In the above technical solution, the weight ratio of the fatty acid stannous to the hypophosphorous acid compound is preferably greater than 0 and less than 0.5, and further non-limiting specific examples are: the weight ratio of fatty acid stannous 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 chromaticity of the fatty acid polyglycol ester product is measured according to a standard method (GB/T605-2006 chemical reagent chromaticity determination general method).
The acid value of the fatty acid polyglycol ester product is measured by a standard method (GB/T6365-2006 surfactant free alkalinity or free acidity determination titration method).
Detailed Description
Example 1
Adding 400 g of polyethylene glycol 400, 70 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling 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 nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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.
Comparative example 1
Adding 400 g of polyethylene glycol 400, 560 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 5 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 2
Adding 400 g of polyethylene glycol 400, 280 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 280 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the reaction kettle to 150 ℃, reacting 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 3
Adding 400 g of polyethylene glycol 400, 140 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and 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, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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
Adding 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 into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling 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 nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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.
Comparative example 2
Adding 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 into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen, increasing the temperature of the kettle to 150 ℃ for reaction for 5 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain a fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 5
Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of stannous linoleate into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the reaction kettle to 150 ℃, reacting for 2 hours, and cooling 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 nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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.
Comparative example 3
Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of stannous oleate into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen, increasing the temperature of the kettle to 150 ℃ for reaction for 5 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain a fatty acid polyethylene glycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 6
Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid into a 2L 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 of an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling 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 nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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.
Comparative example 4
Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in 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 ℃, reacting for 5 hours, cooling to 60 ℃, stopping stirring and introducing nitrogen, and discharging to obtain the fatty acid polyglycol ester product.
For comparison, the main process parameters and the product test results are listed in table 1.
Example 7
Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid into a 2L 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 of an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling 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 nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting 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.
Comparative example 5
Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid into a 2L 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 passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in 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 ℃, reacting for 5 hours, cooling to 60 ℃, stopping stirring and introducing nitrogen, and discharging to obtain the fatty acid polyglycol ester product.
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 reaction temperature, T is reaction time, T is1Is the first esterification reaction temperature, t1For the first esterification reaction time, T2Is the second esterification reaction temperature, t2For a second esterification reaction time; a represents stannous oleate, B represents stannous oleate and hypophosphorous acid, and the value in () behind B is the weight ratio of stannous oleate to hypophosphorous acid; d is the molar ratio of the first part of raw material fatty acid to the polyethylene glycol.
Claims (10)
1. The preparation method of the fatty acid polyglycol ester comprises the following steps:
a first esterification reaction: the method comprises the steps of carrying out first esterification reaction on a first esterification raw material mixture in the presence of a reaction auxiliary agent containing an acidic 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 subjecting a second esterification raw material mixture to a second esterification reaction 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.
2. The process according to claim 1, wherein the molar ratio of the first portion of raw fatty acids to the polyethylene glycol is 0.05 to 0.8, preferably 0.05 to 0.5.
3. The method according to claim 1, wherein the reaction auxiliary is an acidic catalyst; or the reaction auxiliary agent is an acid catalyst and an esterification process color inhibitor.
4. The method according to claim 3, wherein the esterification-process color inhibitor comprises at least one selected from the group consisting of a hypophosphorous acid compound and a stannous fatty acid.
5. The method according to claim 1, wherein the acidic catalyst comprises at least one member selected from the group consisting of an arylsulfonic acid, a sulfuric acid and an acid sulfate. And/or preferably, the feeding amount of the catalyst accounts for 0.2-1% of the weight of the polyethylene glycol. And/or preferably the aromatic sulfonic acid corresponds to the following formula 1:
wherein R is1And R2Is independently selected from H or alkyl of C1-C3.
6. The method according to claim 4, wherein the hypophosphite compound comprises hypophosphorous acid and/or hypophosphite.
7. The method according to claim 4, wherein the fatty acid stannous is represented by the following formula 2:
wherein R is3And R4Independently selected from C9-C20 hydrocarbyl, and/or R3And R4Independently preferably a linear hydrocarbon group, and/or R3And R4Independently preferably a primary hydrocarbyl group, and/or R3And R4Independently, alkenyl or alkyl groups are preferred.
8. The preparation method according to claim 3, wherein the amount of the color inhibitor is 0.2-1% by weight of the polyethylene glycol.
9. The method according to claim 1, wherein the reaction temperature of the first esterification reaction and the second esterification reaction is preferably 110 to 160 ℃.
10. The method according to claim 1, wherein the first esterification reaction and the second esterification reaction are preferably carried out independently for 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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