CN112759507B - Preparation method of ethylhexyl glycerol - Google Patents
Preparation method of ethylhexyl glycerol Download PDFInfo
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- CN112759507B CN112759507B CN202011517370.4A CN202011517370A CN112759507B CN 112759507 B CN112759507 B CN 112759507B CN 202011517370 A CN202011517370 A CN 202011517370A CN 112759507 B CN112759507 B CN 112759507B
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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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method of ethylhexyl glycerin, which takes isooctanol, 3-chloro-1, 2-propanediol and common inorganic base as raw materials, a phase transfer catalyst is not added, a target product is prepared through one-step reaction, and then a high-purity ethylhexyl glycerin product is obtained through the process steps of separating an organic phase, distilling and the like. The preparation method has the characteristics of simple process, mild reaction conditions, high selectivity, low energy consumption, green synthetic route, high product purity and the like, and is favorable for popularization and application of ethylhexyl glycerol in daily chemicals, cosmetics and other industries.
Description
Technical Field
The invention belongs to the technical field of preparation processes of fine chemical products, and relates to a preparation method of ethylhexyl glycerol.
Background
Ethylhexyl glycerol (ethylhexyl glycerol) is an important "no-additive" preservative representative, and is a multifunctional cosmetic additive that is currently accepted worldwide, and is widely used in various bath products, cleaning products, deodorants, eye cosmetics, foundations, hair care products, and sunscreen products. The ethylhexyl glycerin can improve the moisturizing effect of the emollient and the humectant formula and increase the smooth skin feel, and can improve the absorption efficiency of skin to cream and overcome the defects of sticky and whitewashing skin feel and the like when being added into a cream system. The ethylhexyl glycerin and the substance with antiseptic effect have the synergistic effect of mixing, wherein the ethylhexyl glycerin and the substance with antiseptic effect are used together with the traditional antiseptic, and more are matched with the polyalcohol to form an additive-free antiseptic system, so that the skin feel of the cosmetics can be obviously improved, and the diffusion capability of the fragrance is improved.
As a multifunctional auxiliary agent developed in recent years, the related synthesis process of ethylhexyl glycerin is reported to be less. Chinese patent publication No. CN108191614a discloses a process for preparing ethylhexyl glycerol comprising: (1) Under the stirring condition, the isooctanol and the glycidyl esters react under stirring at room temperature by taking boron trifluoride diethyl ether solution as a catalyst to generate an intermediate; (2) Adding acid as a catalyst into the intermediate obtained in the step (1), adding water or alcohol, and reacting under normal pressure or reduced pressure to hydrolyze or alcoholyze the intermediate obtained in the step (1); (3) And (3) washing the product obtained in the step (2) with water to obtain a liquid, and distilling to obtain the ethylhexyl glycerol. The process needs boron trifluoride diethyl etherate solution and acid as catalysts, and has the defects of multiple reaction steps, complex process, difficult separation and environmental pollution. Chinese patent publication No. CN104817436A also discloses a method for preparing high-purity ethylhexyl glycerin, which comprises the steps of generating an intermediate 4-alkoxymethyl-1, 3-dioxoalkane by using 2-ethylhexyl glycidyl ester and acetone under the catalysis of boron trifluoride diethyl ether, adding a terminating agent in time, hydrolyzing, neutralizing an oil phase substance after liquid separation by using sodium bicarbonate, washing, adding a stabilizing agent, and finally obtaining the ethylhexyl glycerin by short-path distillation. The process needs to use 2-ethylhexyl glycidyl ester with higher cost as an initial raw material, so that the cost of a final product is too high, and the process has the defects of multiple processes, complex operation and the like in the synthesis process. The defects limit the popularization and the application of the ethylhexyl glycerol as a novel multifunctional additive in the cosmetic and daily chemical industries to a great extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing the target product ethylhexyl glycerol through one-step reaction by adopting isooctanol, inorganic base and 3-chloro-1, 2-propanediol which are easy to obtain in the market as raw materials without adding a phase transfer catalyst.
The technical means adopted for achieving the above object are as follows.
The preparation method of the ethylhexyl glycerol comprises the following synthesis steps: adding isooctanol and 3-chloro-1, 2-propanediol into a reactor according to the molar ratio of 1:1.0-2.0, controlling the temperature of materials in the reactor to 20-80 ℃ under stirring, dropwise adding inorganic alkali solution with the concentration of 10-50% into the reactor, keeping the molar ratio of the added inorganic alkali solution to isooctanol to 1.0-1.5:1, reacting for 2-8 h, regulating the pH value to be neutral (pH=7) by using a hydrochloric acid solution, cooling to 20 ℃, separating oil from water by using a separating funnel, washing the organic phase twice by using a water separating funnel after the water phase is released, separating out the organic phase, distilling the organic phase component under the vacuum degree of 40-50 Pa by using a molecular distillation device, and collecting fraction with the temperature of 138+/-3 ℃ as a product to obtain ethylhexyl glycerol with the purity of more than or equal to 99%.
The further technical solution of the invention also comprises: the preferred molar ratio of isooctanol to 3-chloro-1, 2-propanediol added to the reactor is 1:1.1-1.5.
The further technical solution of the invention also comprises: the inorganic alkali solution is aqueous solution of sodium hydroxide or potassium hydroxide, the preferable concentration value of the inorganic alkali solution is 20% -30%, and the preferable molar ratio of the addition amount of the inorganic alkali solution to isooctyl alcohol is 1.1-1.3:1.
The further technical solution of the invention also comprises: the preferable reaction temperature of the materials in the reactor is 40-60 ℃, and the preferable reaction time of heat preservation is 3-5 h.
The further technical solution of the invention also comprises: the reactor is a three-mouth bottle provided with a spherical condenser and a thermometer.
Compared with the existing ethylhexyl glycerin preparation technology in the field, the invention has the beneficial effects that: the method takes isooctanol, 3-chloro-1, 2-propanediol and common inorganic alkali as raw materials, does not add a phase transfer catalyst, prepares the target product ethylhexyl glycerol through one-step reaction, has simple process, high synthesis yield and product purity, avoids the defects of more wastes, larger environmental pollution, complex process and the like in the prior art, and is suitable for industrialized mass production. The method for preparing the ethylhexyl glycerol can obtain higher yield, the highest product yield can reach more than 86%, the purity can reach more than 99.0%, the appearance of the product is colorless and transparent, and the product is odorless and superior to the similar products in the current market.
Drawings
FIG. 1 is an IR chart of ethylhexyl glycerin prepared according to one example (example 3) of this invention.
FIG. 2 is ethylhexyl glycerol prepared according to this example (example 3) 1 HNMR diagram.
Fig. 3 is a GC diagram of ethylhexyl glycerin prepared according to this example (example 3).
Detailed Description
The present invention will be further described with reference to examples.
Example 1
65g (0.5 mol) of isooctanol and 60.8g (0.5 mol) of 3-chloro-1, 2-propanediol are added into a 250ml three-port bottle provided with a spherical condenser and a thermometer, the mixture is stirred and kept at 20 ℃, 112g (0.5 mol) of 25% potassium hydroxide aqueous solution is added dropwise after 30min, the reaction is stopped after 2h of heat preservation, the pH value is regulated to be neutral (pH value=7) by hydrochloric acid solution, the product is subjected to oil-water separation by a separating funnel at 20 ℃, after the water phase is discharged, the organic phase is washed twice by 100ml of water, the organic phase is separated, a fraction of 138+/-3 ℃ is collected by a molecular distillation device under the vacuum degree of 40 Pa, 58g of colorless transparent liquid ethylhexyl glycerol is obtained, and the purity of the ethylhexyl glycerol is 99.0% and the yield is 56.9% by gas chromatography analysis.
Example 2
65g (0.5 mol) of isooctanol and 60.8g (0.5 mol) of 3-chloro-1, 2-propanediol are added into a 250ml three-port bottle provided with a spherical condenser and a thermometer, the mixture is stirred and heated to 40 ℃, 110g (0.55 mol) of 20% sodium hydroxide aqueous solution is added dropwise after 30min, the reaction is stopped after heat preservation for 3h, the pH value is regulated to be neutral by hydrochloric acid solution, the temperature is reduced to 20 ℃, oil-water separation is carried out on the product by a separating funnel, after the water phase is discharged, the organic phase is washed twice by 100ml of water, the organic phase is separated, the fraction is collected by a molecular distillation device at the vacuum degree of 40-50 Pa, 138+/-3 ℃ to obtain 77.9g colorless transparent liquid ethylhexyl glycerol, the purity of the ethylhexyl glycerol is 99.1% and the yield is 76.4% by gas chromatography analysis.
Example 3
65g (0.5 mol) of isooctanol and 71.8g (0.65 mol) of 3-chloro-1, 2-propanediol are added into a 250ml three-port bottle provided with a spherical condenser and a thermometer, the mixture is stirred, heated and warmed to 50 ℃, 120g (0.6 mol) of 20% sodium hydroxide aqueous solution is added dropwise after 30min, the reaction is stopped after heat preservation for 4h, the pH value is regulated to be neutral by hydrochloric acid solution, the temperature is reduced to 20 ℃, oil-water separation is carried out on the product by a separating funnel, after the water phase is discharged, the organic phase is washed twice by 100ml of water, the organic phase is separated, the fraction is collected by a molecular distillation device at the vacuum degree of 40-50 Pa, 138+/-3 ℃ to obtain 88g colorless transparent liquid ethylhexyl glycerol, and the purity of the ethylhexyl glycerol is 99.5% and the yield is 86.3% by gas chromatography analysis.
Example 4
65g (0.5 mol) of isooctanol and 99.45g (0.9 mol) of 3-chloro-1, 2-propanediol are added into a 250ml three-port bottle provided with a spherical condenser and a thermometer, the mixture is stirred and heated to 80 ℃, 105g (0.75 mol) of 40% potassium hydroxide aqueous solution is added dropwise after 30min, the reaction is stopped after heat preservation for 8h, the pH value is regulated to be neutral by hydrochloric acid solution, the temperature is reduced to 20 ℃, oil-water separation is carried out on the product by a separating funnel, after the water phase is discharged, the organic phase is washed twice by 100ml of water, the organic phase is separated, the fraction is collected by a molecular distillation device at the vacuum degree of 40-50 Pa, 138+/-3 ℃ to obtain 71.7g colorless transparent liquid ethylhexyl glycerol, the purity of the ethylhexyl glycerol is 99.2% and the yield is 70.3% by gas chromatography analysis.
Claims (3)
1. A preparation method of ethylhexyl glycerol is characterized by comprising the following steps: adding 65g of isooctanol and 60.8g of 3-chloro-1, 2-propanediol into a 250ml three-port bottle with a spherical condenser and a thermometer, stirring, heating to 40 ℃, dropwise adding 110g of 20% sodium hydroxide aqueous solution for 30min, preserving heat for 3h, stopping the reaction, regulating the pH value to be neutral, reducing the temperature to 20 ℃, separating oil and water of the product by using a separating funnel, washing an organic phase twice by using 100ml of water after the water phase is discharged, separating the organic phase, collecting a fraction of 138+/-3 ℃ at the vacuum degree of 40-50 Pa by using a molecular distillation device, and obtaining 77.9g of colorless transparent liquid ethylhexyl glycerol with the purity of 99.1%.
2. A preparation method of ethylhexyl glycerol is characterized by comprising the following steps: adding 65g of isooctanol and 71.8g of 3-chloro-1, 2-propanediol into a 250ml three-port bottle with a spherical condenser and a thermometer, stirring, heating to 50 ℃, dropwise adding 120g of 20% sodium hydroxide aqueous solution for 30min, preserving heat for 4h, stopping the reaction, regulating the pH value to be neutral, reducing the temperature to 20 ℃, separating oil and water of the product by using a separating funnel, washing an organic phase twice by using 100ml of water after the water phase is discharged, separating the organic phase, collecting a fraction of 138+/-3 ℃ at the vacuum degree of 40-50 Pa by using a molecular distillation device, and obtaining 88g of colorless transparent liquid ethylhexyl glycerol with the purity of 99.5%.
3. A preparation method of ethylhexyl glycerol is characterized by comprising the following steps: adding 65g of isooctanol and 99.45g of 3-chloro-1, 2-propanediol into a 250ml three-port bottle with a spherical condenser and a thermometer, stirring, heating to 80 ℃, dropwise adding 105g of 40% potassium hydroxide aqueous solution after 30min, preserving heat for 8h, stopping the reaction, regulating the pH value to be neutral by using a hydrochloric acid solution, reducing the temperature to 20 ℃, separating oil from water by using a separating funnel, washing an organic phase twice by using 100ml of water after the water phase is discharged, separating the organic phase, collecting a fraction of 138+/-3 ℃ at the vacuum degree of 40-50 Pa by using a molecular distillation device, and obtaining 71.7g of colorless transparent liquid ethylhexyl glycerol with the purity of 99.2%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445436A (en) * | 2008-12-22 | 2009-06-03 | 天津市若围药物研究所 | Method for preparing medical compound chlorphenesin |
| CN109280038A (en) * | 2018-09-17 | 2019-01-29 | 大丰跃龙化学有限公司 | A kind of synthetic method of Sensiva SC50 ether |
| CN110770271A (en) * | 2017-05-19 | 2020-02-07 | 埃特纳科技有限公司 | Method for preparing functionalized fluorinated monomers, fluorinated monomers and compositions for preparing same |
| CN111056928A (en) * | 2019-12-30 | 2020-04-24 | 陕西省石油化工研究设计院 | Method for synthesizing chlorphenesin |
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- 2020-12-21 CN CN202011517370.4A patent/CN112759507B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445436A (en) * | 2008-12-22 | 2009-06-03 | 天津市若围药物研究所 | Method for preparing medical compound chlorphenesin |
| CN110770271A (en) * | 2017-05-19 | 2020-02-07 | 埃特纳科技有限公司 | Method for preparing functionalized fluorinated monomers, fluorinated monomers and compositions for preparing same |
| CN109280038A (en) * | 2018-09-17 | 2019-01-29 | 大丰跃龙化学有限公司 | A kind of synthetic method of Sensiva SC50 ether |
| CN111056928A (en) * | 2019-12-30 | 2020-04-24 | 陕西省石油化工研究设计院 | Method for synthesizing chlorphenesin |
Non-Patent Citations (2)
| Title |
|---|
| Curing Behavior and Properties of Sustainable Furan-Based Epoxy/Anhydride Resins;Angela Marotta 等;《Biomacromolecules》;20191231;第20卷;全文 * |
| 二茂铁四唑和二茂铁甲醛缩3-取代丙二醇衍生物的合成;张慧卿 等;《有机化学》;20081231;第28卷(第4期);第744页2.8化合物14的制备 * |
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