CN113416135B - Preparation method of isooctanol polyoxyethylene ether isooctoate - Google Patents
Preparation method of isooctanol polyoxyethylene ether isooctoate Download PDFInfo
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- CN113416135B CN113416135B CN202110864465.1A CN202110864465A CN113416135B CN 113416135 B CN113416135 B CN 113416135B CN 202110864465 A CN202110864465 A CN 202110864465A CN 113416135 B CN113416135 B CN 113416135B
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- polyoxyethylene ether
- isooctanol
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- isooctoate
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
Abstract
The invention provides a preparation method of isooctanol polyoxyethylene ether isooctoate, which comprises the following steps: s1, carrying out a polymerization reaction by using isooctyl alcohol and ethylene oxide as raw materials under the action of a polymerization catalyst, and carrying out bubbling degassing for 1-3 hours by using nitrogen after the reaction is finished to obtain isooctyl alcohol polyoxyethylene ether; s2, adding reaction amount of isooctanol polyoxyethylene ether and isooctanoic acid into a flask, adding an esterification catalyst while stirring, and slowly heating; and S3, timely separating out water under the condition of nitrogen flow, and filtering to obtain a colorless to yellowish transparent product. The invention adopts the solid alkaline catalyst to carry out polymerization reaction, and carries out esterification reaction under the action of the solid alkaline catalyst, so that the process is simple, side reactions are few, and the cost can be effectively reduced; the content of dioxane in the prepared isooctanol polyoxyethylene ether isooctoate is less than or equal to 10ppm, and the isooctanol polyoxyethylene ether isooctoate has excellent spreadability, absorbability and no irritation.
Description
Technical Field
The invention belongs to the technical field of preparation of ester compounds in organic chemistry, and particularly relates to a preparation method of isooctanol polyoxyethylene ether isooctoate.
Background
Isooctanol polyoxyethylene ether isooctanoate is a cosmetic additive, which is a derivative of polyethoxy introduced into ester bond of isooctanol isooctanoate, and the introduction of water-based group makes the polarity of the product after film forming be very small, the spreadability is better, and the detergency, wetting power and emulsifying power of the cosmetic are correspondingly improved. In addition, isooctanol polyoxyethylene ether isooctanoate is widely applied in the industries of textile printing and dyeing, leather, papermaking, paint, metal processing and the like.
At present, the synthesis method of isooctanol polyoxyethylene ether isooctanoate is not reported. In general, organic acid is directly used as a catalyst for esterification reaction, such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the reaction effect is good, but the catalysts also have the defects of many byproducts, easy corrosion of equipment and the like, and the byproducts include dioxane. Dioxane is irritant to ear, nose and throat, and the content of dioxane in cosmetics and personal care products is required to be not more than 10ppm after 12 months and 31 years 2022.
The factors influencing the content of dioxane in isooctanol polyoxyethylene ether isooctanoate are two: firstly, free ethylene oxide in isooctanol polyoxyethylene ether can cause generation of dioxane in downstream esterification products, and the free ethylene oxide residue in common processes in the isooctanol polyoxyethylene ether is more and even up to 300ppm; secondly, esterification is carried out under the action of acid catalysis, EO chain is split to form a by-product dioxane, and the content of the product dioxane after esterification reaches thousands of ppm.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing isooctanol polyoxyethylene ether isooctoate, which solves the problem of higher content of a byproduct dioxane in the preparation process, and enables the product to be suitable for being added into cosmetics and skin care products.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of isooctanol polyoxyethylene ether isooctoate comprises the following steps:
s1, carrying out a polymerization reaction by using isooctyl alcohol and ethylene oxide as raw materials under the action of a polymerization catalyst, and carrying out bubbling degassing for 1-3 hours by using nitrogen after the reaction is finished to obtain isooctyl alcohol polyoxyethylene ether;
s2, adding reaction amount of isooctanol polyoxyethylene ether and isooctanoic acid into a flask, adding a certain amount of esterification catalyst under stirring, and slowly heating;
and S3, timely separating out water under the condition of nitrogen flow, and filtering to obtain a colorless to yellowish transparent product.
In the S1, the molar ratio of isooctyl alcohol to ethylene oxide is 1:3-10. The nitrogen bubbling flow rate is 5-10ml/min.
In the S1, the polymerization catalyst is a solid basic catalyst, such as potassium hydroxide or sodium hydroxide. The addition amount of the polymerization catalyst is 0.01-0.5% of the total weight of isooctyl alcohol and ethylene oxide.
In the S2, the molar ratio of isooctanol polyoxyethylene ether to isooctanoic acid is 1.
The esterification catalyst is a solid basic catalyst, such as solid potassium hydroxide or sodium hydroxide. The addition amount of the esterification catalyst is 0.1-0.3% of the total weight of isooctanol polyoxyethylene ether and isooctanoic acid.
In the step S3, water is discharged in time under the condition of nitrogen flow, and the method further includes: keeping the temperature for 5 hours under the reaction condition of 160-170 ℃, cooling to 70 ℃, and filtering to obtain a colorless to yellowish transparent product.
The polymerization reaction equation in S1 is:
wherein n is 3 to 10.
The dehydration esterification reaction equation in the S2 is as follows:
wherein n is 3 to 10.
The invention relates to a preparation method of isooctanol polyoxyethylene ether isooctoate, which comprises the steps of polymerizing isooctanol and ethylene oxide to obtain isooctanol polyoxyethylene ether, and then carrying out dehydration esterification reaction with isooctanol under the action of a solid base catalyst to obtain the isooctanol polyoxyethylene ether isooctoate.
The esterification reaction adopts a solid catalyst, so that the problem that the product has too dark color due to too strong alkalinity of an aqueous solution is solved.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the solid alkaline catalyst to carry out polymerization reaction, and carries out esterification reaction under the action of the solid alkaline catalyst, so that the process is simple, the side reaction is less, and the cost can be effectively reduced;
2. degassing under nitrogen bubbling to make residual free ethylene oxide less than or equal to 10ppm;
3. the invention has mild reaction conditions and simple adopted equipment, thereby saving equipment investment and energy consumption;
4. the content of dioxane in isooctanol polyoxyethylene ether isooctoate prepared by the method is less than or equal to 10ppm, and the isooctanol polyoxyethylene ether isooctoate has excellent spreadability, absorbability, nonirritant and the like;
5. the preparation process of the invention hardly pollutes the environment, meets the current environmental protection requirement and is worthy of popularization.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Isooctanol, ethylene oxide, isooctanoic acid and catalyst bases (sodium hydroxide and potassium hydroxide) are commercially available for use in the following examples and comparative examples.
The formula of the dehydration condensation reaction in the preparation method of the invention is as follows:
the formula of the dehydration esterification reaction in the preparation method is as follows:
wherein n is 3 to 10.
In the following examples and comparative examples, the residual free ethylene oxide content was measured by headspace gas GC-HS; the dioxane content was determined by gas chromatography-mass spectrometry (GC-MS).
Example 1
Adding 130g of isooctanol and 0.13g of KOH solid into a high-pressure reaction kettle, heating to 80 ℃, carrying out vacuum dehydration for 1 hour, slowly dropwise adding 132g of ethylene oxide, reacting for 3 hours at 150-160 ℃, carrying out basically complete reaction, cooling to 100 ℃, carrying out bubbling degassing for 2 hours, controlling the nitrogen flow to be 5ml/min, controlling the vacuum to be below-0.090 MPa, cooling to below 80 ℃, discharging to obtain isooctanol polyoxyethylene ether, and measuring the content of free ethylene oxide to be 1.0ppm;
adding 200 g of isooctanol polyoxyethylene ether and 110 g of isooctanol into a flask, adding 0.93 g of solid catalyst KOH under stirring, slowly heating, separating water in time under the condition of nitrogen flow, keeping the temperature for 5 hours under the reaction condition of 160-170 ℃, cooling to below 80 ℃ to obtain the product isooctanol polyoxyethylene ether isooctanol ester, and measuring the content of the dioxane to be 8.2ppm.
Comparative example 1
As with the other conditions of example 1, no nitrogen sparge was used, except for vacuum degassing. The content of free ethylene oxide in isooctanol polyoxyethylene ether is 56ppm, and the content of dioxane in the isooctanol polyoxyethylene ether isooctoate is 160ppm.
Example 2
Adding 130g of isooctanol and 0.35g of KOH solid into a high-pressure reaction kettle, heating to 80 ℃, carrying out vacuum dehydration for 1 hour, slowly dropwise adding 220g of ethylene oxide, carrying out reaction for 3 hours at 150-160 ℃, carrying out basically complete reaction, cooling to 100 ℃, carrying out bubbling degassing for 1 hour, controlling the nitrogen flow to be 6ml/min, controlling the vacuum to be below-0.090 MPa, cooling to below 80 ℃, discharging to obtain isooctanol polyoxyethylene ether, and measuring the content of free ethylene oxide to be 0.8ppm;
adding 200 g of isooctanol polyoxyethylene ether and 82.28 g of isooctanol into a flask, adding 0.85 g of a solid catalyst KOH under stirring, slowly heating, discharging water under the condition of nitrogen flow, keeping the temperature for 5 hours under the reaction condition of 160-170 ℃, cooling to below 80 ℃ to obtain the isooctanol polyoxyethylene ether isooctoate, and measuring the content of the dioxane to be 7.6ppm.
Comparative example 2
The same other conditions as in example 2 were followed except that p-toluenesulfonic acid was used as the esterification catalyst. The dioxane content of the isooctyl alcohol polyoxyethylene ether isooctanoate is 700ppm.
Example 3
Adding 130g of isooctyl alcohol and 1.45g of KOH solid into a high-pressure reaction kettle, heating to 80 ℃, carrying out vacuum dehydration for 1 hour, slowly dropwise adding 352g of ethylene oxide, carrying out reaction for 3 hours at 150-160 ℃, carrying out complete reaction basically, cooling to 100 ℃, carrying out bubbling degassing for 1 hour, controlling the nitrogen flow to be 8ml/min, controlling the vacuum to be below-0.090 MPa, cooling to below 80 ℃, and discharging to obtain isooctyl alcohol polyoxyethylene ether with the free ethylene oxide content of 0.5ppm;
adding 200 g of isooctanol polyoxyethylene ether and 56.76 g of isooctanol into a flask, adding 0.51 g of catalyst KOH under stirring, slowly heating, discharging water in time under the condition of nitrogen flow, keeping the temperature for 5 hours under the reaction condition of 160-170 ℃, cooling to below 80 ℃ to obtain the product isooctanol polyoxyethylene ether isooctoate, and measuring the content of dioxane to be 6.2ppm.
Comparative example 3
As with the other conditions of example 3, no nitrogen bubbling was used and only vacuum degassing was used. The content of free ethylene oxide in isooctanol polyoxyethylene ether is 22ppm, and the content of dioxane in the isooctanol polyoxyethylene ether isooctoate is 80ppm.
Example 4
Adding 130g of isooctanol and 2.85g of KOH solid into a high-pressure reaction kettle, heating to 80 ℃, carrying out vacuum dehydration for 1 hour, slowly dropwise adding 440g of ethylene oxide, reacting for 3 hours at 150-160 ℃, carrying out basically complete reaction, cooling to 100 ℃, carrying out bubbling degassing for 1 hour, carrying out nitrogen flow of 10ml/min, controlling the vacuum to be below-0.090 MPa, cooling to below 80 ℃, discharging to obtain isooctanol polyoxyethylene ether, and measuring the content of free ethylene oxide to be 0.45ppm;
adding 200 g of isooctanol polyoxyethylene ether and 45.47 g of isooctanol into a flask, adding 0.25 g of catalyst KOH under stirring, slowly heating, separating water under the condition of nitrogen flow, keeping the temperature for 5 hours under the reaction condition of 160-170 ℃, cooling to below 80 ℃ to obtain the product isooctanol polyoxyethylene ether isooctanol isooctoate, and measuring the content of the dioxane to be 6.0ppm.
Comparative example 4
As with the other conditions of example 3, without nitrogen bubbling, only vacuum degassing was used, and the esterification catalyst was p-toluenesulfonic acid, an acidic catalyst. The content of free ethylene oxide in isooctanol polyoxyethylene ether is 35ppm, and the content of dioxane in the isooctanol polyoxyethylene ether isooctoate is 1621ppm.
In conclusion, the invention adopts alkali as the catalyst to carry out polymerization reaction, and carries out esterification reaction under the action of the solid alkali catalyst, thereby having simple process, less side reaction and effectively reduced cost. Degassing under nitrogen bubbling to obtain residual free ethylene oxide content less than or equal to 5ppm.
The invention has mild reaction condition and simple adopted equipment, thereby saving equipment investment and energy consumption. The isooctanol polyoxyethylene ether isooctoate prepared by the method has the dioxane content of less than or equal to 10ppm, and has excellent spreadability, absorbability, nonirritant and the like.
The preparation process of the invention hardly pollutes the environment, meets the current environmental protection requirement and is worth popularizing.
The above-mentioned embodiments are only used for explaining the inventive concept of the present invention, and do not limit the protection of the claims of the present invention, and any insubstantial modifications of the present invention using this concept shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of isooctanol polyoxyethylene ether isooctoate is characterized by comprising the following steps:
s1, carrying out a polymerization reaction by using isooctyl alcohol and ethylene oxide as raw materials under the action of a polymerization catalyst, and carrying out bubbling degassing for 1-3 hours by using nitrogen after the reaction is finished to obtain isooctyl alcohol polyoxyethylene ether;
s2, adding reaction amount of isooctanol polyoxyethylene ether and isooctanoic acid into a flask, adding an esterification catalyst while stirring, and slowly heating;
s3, timely separating out water under the condition of nitrogen flow, and filtering to obtain a colorless to yellowish transparent product;
the polymerization catalyst is a solid basic catalyst; the esterification catalyst is a solid basic catalyst.
2. The method according to claim 1, wherein the polymerization equation in S1 is:
wherein n is 3 to 10.
3. The method according to claim 1, wherein the dehydration esterification reaction equation in S2 is:
wherein n is 3 to 10.
4. The production method according to claim 1, wherein in the S1, the molar ratio of isooctanol to ethylene oxide is 1:3-10.
5. The production method according to claim 1 or 4, wherein the nitrogen bubbling flow rate in S1 is 5 to 10ml/min.
6. The production method according to claim 1, wherein the polymerization catalyst is added in an amount of 0.01 to 0.5% by weight based on the total weight of the isooctyl alcohol and ethylene oxide.
7. The process according to claim 1, wherein in said S2, the molar ratio of isooctanol polyoxyethylene ether to isooctanoic acid is 1.
8. The method according to claim 7, wherein the esterification catalyst is added in an amount of 0.1 to 0.3% by weight based on the total weight of isooctanol polyoxyethylene ether and isooctanoic acid.
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| KR20110081921A (en) * | 2010-01-09 | 2011-07-15 | 김도균 | Polyolester bonded phosphorus |
| WO2012024610A1 (en) * | 2010-08-20 | 2012-02-23 | Elementis Specialties, Inc. | Viscosity regulating composition |
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| CN102477154B (en) * | 2012-02-28 | 2012-10-24 | 三江化工有限公司 | Preparation method of fatty alcohol polyoxyethylene ether |
| CN106554492B (en) * | 2015-09-28 | 2018-11-27 | 上海东大化学有限公司 | A kind of isomery alcohol alkoxy polyether and preparation method thereof |
| CN108586234B (en) * | 2017-12-29 | 2021-01-26 | 浙江皇马科技股份有限公司 | Preparation method of isooctanol polyoxypropylene ether fatty acid ester |
| CN111574555A (en) * | 2020-05-15 | 2020-08-25 | 江苏九洲环保技术有限公司 | Method for synthesizing fatty alcohol-polyoxyethylene ether phosphating product |
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| KR20110081921A (en) * | 2010-01-09 | 2011-07-15 | 김도균 | Polyolester bonded phosphorus |
| WO2012024610A1 (en) * | 2010-08-20 | 2012-02-23 | Elementis Specialties, Inc. | Viscosity regulating composition |
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