CN104817436A - Method for preparing high-purity ethylhexylglycerin - Google Patents
Method for preparing high-purity ethylhexylglycerin Download PDFInfo
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- CN104817436A CN104817436A CN201510239933.0A CN201510239933A CN104817436A CN 104817436 A CN104817436 A CN 104817436A CN 201510239933 A CN201510239933 A CN 201510239933A CN 104817436 A CN104817436 A CN 104817436A
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- sensiva
- glycidyl ether
- high purity
- ethylhexyl glycidyl
- molecular formula
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing high-purity ethylhexylglycerin. According to the method, an intermediate 4-alkoxymethyl-1,3-dioxoane is generated from 2-ethylhexylglycidyl ether and acetone under the action of boron trifluoride diethyl etherate, a terminator is added in good time before hydrolysis, and after liquid separation, an oil-phase substance is neutralized by use of sodium hydrogen carbonate and then washed, next, a stabilizer is added, and finally, the high-purity ethylhexylglycerin is obtained by use of short-path distillation. The method is suitable for cosmetic additives and suitable for large-scale industrial production, and has the advantages of simple process, small energy consumption, product yield of greater than 88%, purity of 99.3%, no color and no taste, and the like.
Description
Technical field
The invention belongs to sanitas field, relate to a kind of method preparing high purity Sensiva SC50.
Background technology
Sensiva SC50 be a kind of newly there is the multifunctional cosmetics additive that preservative efficacy takes into account moisturizing deodouring effect, toxicological security due to various traditional preservatives is subject to more and more query, non-stimulated as green, the appearance with the Sensiva SC50 of preservative efficacy brings hope, particularly utilize the synergism of itself and other traditional preservatives for daily chemical products system, greatly can reduce the add-on of traditional preservatives, the toxic of remarkable reduction protective system is its maximum bright spot, there is preservative efficacy, not skin irritation characteristic, gentle humidity-holding effect, energy synergy traditional preservatives ability, Sensiva SC50 will be played a significant role in the green protective system in future.
Sensiva SC50 boiling point reaches about 300 DEG C, easy oxidation stain, easily be polymerized during synthesis, separating-purifying difficulty, in addition, the Sensiva SC50 color and luster that foreign matter content is high is dark, there is peculiar smell, some impurity can affect toxicity safety, can not as daily use chemicals additive, Sensiva SC50 can be produced at present by etherification technology, a kind of is that the epoxy group(ing) opening hexyl glycidyl ether by catalysis carries out Carbonyl addition, then be hydrolyzed, another kind method is exactly that alcohol and glycidyl ether prepare Sensiva SC50 under acid or base catalysis, long reaction time, impurity is many, the third method is with basic hydrolysis after acid anhydrides and glycidyl ether addition reaction, but very easily generate the autohemagglutination by product of glycidyl ether, and the important deficiency of these methods existing is that side reaction is many, scent of, purity is low, there is color and luster, follow-up polishing purification is by traditional rectificating method and activated carbon decolorizing, equipment investment is large, cost is high, purity is low, can not use as makeup and household product additive.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of method preparing high purity Sensiva SC50, by improving the synthetic method of Sensiva SC50, obtain high purity, high yield, the Sensiva SC50 of colorless and odorless, is applicable to the multifunction additive of makeup and household product.
To achieve these goals, technical scheme of the present invention is:
One prepares the method for the high purity Sensiva SC50 with molecular formula (I),
Comprise the following steps:
1) in acetone soln, 2-ethylhexyl glycidyl ether and catalyzer is added, be that 5 ~ 35 ° of C reaction generates 4-alkoxy methyls-1 in 2 ~ 3 hours in temperature, 3-dioxo alkane solution, wherein catalyzer and 2-ethylhexyl glycidyl ether molar mass are than being 1:20 ~ 50, and 2-ethylhexyl glycidyl ether is 1:3 ~ 10 with the molar mass ratio of acetone;
2) to step 1 4-alkoxy methyl-1,3-dioxo alkane solution in add terminator, keeps 10 ~ 20 minutes, decompression steams excessive propanone, and wherein terminator and 2-ethylhexyl glycidyl ether molar mass are than being 1:5 ~ 10;
3) in the solution of step 2, add formic acid, be hydrolyzed reaction, and temperature of reaction is 40 ~ 60 ° of C, 3 ~ 4 hours time;
4) oil phase thing sodium bicarbonate after hydrolysate separatory neutralized and add stablizer after washing;
5) product step 4 obtained, by short-path distillation equipment distillation oil phase, distillation temperature 135 ~ 145 DEG C, vacuum tightness 40 ~ 50Pa, finally obtains the high purity Sensiva SC50 with molecular formula (I).
In described step 1, catalyzer is boron trifluoride diethyl etherate, and catalyzer and 2-ethylhexyl glycidyl ether molar mass are than preferred 1:20 ~ 30.
In described step 1,2-ethylhexyl glycidyl ether and the molar mass of acetone are than preferred 1:3 ~ 5.
Adding terminator in described step 2 is methylamine or ammonium hydroxide aqueous solution.Terminator and 2-ethylhexyl glycidyl ether molar mass are than preferred 1:5 ~ 6.
Described step 4 washs preferably 2 washings.
The excessive propanone of described step 2 Distillation recovery can replace acetone secondary response again in step 1.
The invention has the beneficial effects as follows:
1) high purity: Sensiva SC50 purity can reach more than 99.0%, colourless, tasteless.
2) high yield: the yield for 2-ethylhexyl glycidyl ether reaches more than 88%.
3) effectively lower-boiling impurity is controlled: short-path distillation can make lower-boiling impurity (as glycidyl ether, ethylhexanol, the raw material impurities such as organochlorine compound) drop to less than 0.5%, particularly lower distillation temperature can effectively suppress product variable color and impurity to decompose the smell brought.
4) the adding of a small amount of terminator, make reaction terminating rapidly, and prevention produces side reaction in the ketone still-process of surplus, this is also very important for control color and luster, and the terminator after effect is finally easy to removing in the mode of crystallization, does not affect product purity.
5) highly selective: lower-boiling impurity nearly all in product derives from raw material, and high-boiling-point impurity derives from reaction process, in selected technique the finished product, high-boiling-point impurity is less than 0.2%.
6) reaction process is simpler: except crossing short distance still-process, respond is carried out in a reactor.
7) select formic acid to do hydrolytic accelerating agent, the residual contamination product of minimizing organohalogen compound of trying one's best or strong inorganic acid are to the corrosion of equipment.
8) excess material is recyclable applies mechanically: lower ketones is as sterically hindered little in acetone, and reactive behavior is high, and its lower boiling can facilitate recovery simultaneously, reduces energy consumption and raw materials cost.
9) sodium bicarbonate is as neutralizing agent, and product can be avoided to aggregate into superpolymer under strongly alkaline conditions, and these superpolymer definitely abstain to occur in the product.
10) gentle reaction conditions, in the relatively short reaction times, the preparation technology that stable repeatability is good, is easy to large-scale production.
Embodiment
By the following examples the present invention is described further;
Embodiment 1
Mechanical stirrer is being housed, thermometer, in 2000 milliliters of four-hole boiling flasks of dropping funnel, add the 2-ethylhexyl glycidyl ether of 330 grams, flask is placed in water-bath, stir lower control temperature 10 ~ 20 DEG C, drip acetone and the catalyzer 10 grams of 175 grams simultaneously, time for adding is 40 minutes, keeping adding aqueous methylamine solution 15 grams after 120 minutes keeps underpressure distillation after 10 minutes to go out remaining acetone, to adding 40 grams, formic acid in residual reactant, distilled water 50 grams, heated water bath was 50 ~ 55 DEG C of reactions 180 minutes, leave standstill separatory, oil phase sodium bicarbonate is neutralized to neutrality, stablizer is added after washing twice, carry out short-path distillation again, vacuum degree control is at 40 ~ 50Pa, collect the cut of distillation temperature 135 ~ 145 DEG C of scopes, obtain high purity Sensiva SC50 of the present invention, through gas chromatographic analysis, purity 99.3%, yield 89.1%, colorless and odorless.
Embodiment 2
Replace the aqueous methylamine solution in example 1 with 20 grams of ammoniacal liquor, itself and step, with embodiment 1, obtain high purity Sensiva SC50 of the present invention, through gas chromatographic analysis, and purity 99.5 %, yield 89.0%, colorless and odorless.
Embodiment 3
Contrast with embodiment 1, do not add terminator.
In 2000 milliliters of four-hole boiling flasks that mechanical stirrer, thermometer, dropping funnel are housed, add the 2-ethylhexyl glycidyl ether of 330 grams, flask is placed in water-bath.Stir lower control temperature 10 ~ 20 DEG C, drip acetone and the boron trifluoride diethyl etherate catalyzer 15 grams of 175 grams simultaneously, time for adding is 40 minutes reaction solutions is brown, step is with embodiment 1 afterwards, the product obtained through gas chromatographic analysis, purity 48.3%, yield 56%, color and luster is light brown, and smell is large, can not be used as the additive of daily chemical products.
Embodiment 4
Mechanical stirrer is being housed, thermometer, in 2000 milliliters of four-hole boiling flasks of dropping funnel, add the 2-ethylhexyl glycidyl ether of 330 grams, flask is placed in water-bath, stir lower control temperature 20 ~ 30 DEG C, drip acetone and the catalyzer 13 grams of 360 grams simultaneously, time for adding is 40 minutes, keep adding 20 grams of ammoniacal liquor after 120 minutes, underpressure distillation after 15 minutes is kept to go out remaining acetone, to adding 40 grams, formic acid in residual reactant, distilled water 50 grams, heated water bath was 60 ~ 65 DEG C of reactions 240 minutes, step is with embodiment 1 afterwards, obtain high purity Sensiva SC50 of the present invention, through gas chromatographic analysis, purity 99.4%, yield 88.7%, colorless and odorless.
Embodiment 5
Contrast with embodiment 4, with the process of conventional vacuum rectification method.
Mechanical stirrer is being housed, thermometer, in 2000 milliliters of four-hole boiling flasks of dropping funnel, add the 2-ethylhexyl glycidyl ether of 330 grams, flask is placed in water-bath, stir lower control temperature 20 ~ 30 DEG C, drip acetone and the catalyzer 13 grams of 360 grams simultaneously, time for adding is 40 minutes, keeping adding aqueous methylamine solution 15 grams after 120 minutes keeps underpressure distillation after 15 minutes to go out remaining acetone, to adding 40 grams, formic acid in residual reactant, distilled water 50 grams, heated water bath was 60 ~ 65 DEG C of reactions 240 minutes, leave standstill separatory, oil phase sodium bicarbonate is neutralized to neutrality, stablizer is added after washing twice, carry out conventional vacuum rectifying again, vacuum degree control is at 500 ~ 600Pa, collect the cut of distillation temperature 160 ~ 170 DEG C of scopes, obtain Sensiva SC50, through gas chromatographic analysis, purity 79.3%, yield 58.1%, light yellow, there is peculiar smell, with the nearly unavailable fruit of activated carbon decolorizing, the additive of daily chemical products can not be used as.
Embodiment 6
Operation steps, with embodiment 4, just replaces an acetone, the product colorless and odorless obtained, yield 88.0%, purity 99.1% with the secondary acetone of aforementioned each example Distillation recovery.
Claims (6)
1. prepare a method for the high purity Sensiva SC50 with molecular formula (I),
It is characterized in that, comprise the following steps:
1) in acetone soln, 2-ethylhexyl glycidyl ether and catalyzer is added, be that 5 ~ 35 ° of C reaction generates 4-alkoxy methyls-1 in 2 ~ 3 hours in temperature, 3-dioxo alkane solution, wherein catalyzer and 2-ethylhexyl glycidyl ether molar mass are than being 1:20 ~ 50, and 2-ethylhexyl glycidyl ether is 1:3 ~ 10 with the molar mass ratio of acetone;
2) to step 1 4-alkoxy methyl-1,3-dioxo alkane solution in add terminator, keeps 10 ~ 20 minutes, decompression steams excessive propanone, and wherein terminator and 2-ethylhexyl glycidyl ether molar mass are than being 1:5 ~ 10;
3) in the solution of step 2, add formic acid, be hydrolyzed reaction, and temperature of reaction is 40 ~ 60 ° of C, 3 ~ 4 hours time;
4) oil phase thing sodium bicarbonate after hydrolysate separatory neutralized and add stablizer after washing;
5) product step 4 obtained, by short-path distillation equipment distillation oil phase, distillation temperature 135 ~ 145 DEG C, vacuum tightness 40 ~ 50Pa, finally obtains the high purity Sensiva SC50 with molecular formula (I).
2. one according to claim 1 prepares the method for the high purity Sensiva SC50 with molecular formula (I), it is characterized in that, in described step 1, catalyzer is boron trifluoride diethyl etherate, and catalyzer and 2-ethylhexyl glycidyl ether molar mass are than preferred 1:20 ~ 30.
3. one according to claim 1 prepares the method for the high purity Sensiva SC50 with molecular formula (I), it is characterized in that, in described step 1,2-ethylhexyl glycidyl ether and the molar mass of acetone are than preferred 1:3 ~ 5.
4. one according to claim 1 prepares the method for the high purity Sensiva SC50 with molecular formula (I), it is characterized in that, adding terminator in described step 2 is methylamine or ammonium hydroxide aqueous solution, and terminator and 2-ethylhexyl glycidyl ether molar mass are than preferred 1:5 ~ 6.
5. one according to claim 1 prepares the method for the high purity Sensiva SC50 with molecular formula (I), it is characterized in that, described step 4 washs preferably 2 washings.
6. one according to claim 1 prepares the method for the high purity Sensiva SC50 with molecular formula (I), it is characterized in that, the excessive propanone of described step 2 Distillation recovery can replace acetone secondary response again in step 1.
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| CN201510239933.0A CN104817436B (en) | 2015-05-13 | 2015-05-13 | Method for preparing high-purity ethylhexylglycerin |
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| CN201510239933.0A CN104817436B (en) | 2015-05-13 | 2015-05-13 | Method for preparing high-purity ethylhexylglycerin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191614A (en) * | 2017-12-29 | 2018-06-22 | 广州星业科技股份有限公司 | A kind of method for preparing Sensiva SC50 |
| CN110078596A (en) * | 2018-12-23 | 2019-08-02 | 陕西省石油化工研究设计院 | A kind of recycling method of acetone in Sensiva SC50 preparation |
| CN116253702A (en) * | 2022-12-29 | 2023-06-13 | 苏州元素集化学工业有限公司 | Synthesis method of alkyl glycidyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030216283A1 (en) * | 2002-02-22 | 2003-11-20 | Takasago International Corporation | Fragrance composition |
| JP2007332036A (en) * | 2006-06-12 | 2007-12-27 | Kao Corp | Method for purifying glyceryl ether |
| CN101948371A (en) * | 2009-07-08 | 2011-01-19 | 乔治洛德方法研究和开发液化空气有限公司 | The method for preparing the 1-alkyl glycerylether |
| CN104402682A (en) * | 2014-11-10 | 2015-03-11 | 平湖优康药物研发有限公司 | Synthesis technology of novel cosmetic antibacterial agent (ethylhexylglycerin) |
-
2015
- 2015-05-13 CN CN201510239933.0A patent/CN104817436B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030216283A1 (en) * | 2002-02-22 | 2003-11-20 | Takasago International Corporation | Fragrance composition |
| JP2007332036A (en) * | 2006-06-12 | 2007-12-27 | Kao Corp | Method for purifying glyceryl ether |
| CN101948371A (en) * | 2009-07-08 | 2011-01-19 | 乔治洛德方法研究和开发液化空气有限公司 | The method for preparing the 1-alkyl glycerylether |
| CN104402682A (en) * | 2014-11-10 | 2015-03-11 | 平湖优康药物研发有限公司 | Synthesis technology of novel cosmetic antibacterial agent (ethylhexylglycerin) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191614A (en) * | 2017-12-29 | 2018-06-22 | 广州星业科技股份有限公司 | A kind of method for preparing Sensiva SC50 |
| CN110078596A (en) * | 2018-12-23 | 2019-08-02 | 陕西省石油化工研究设计院 | A kind of recycling method of acetone in Sensiva SC50 preparation |
| CN110078596B (en) * | 2018-12-23 | 2022-04-29 | 陕西省石油化工研究设计院 | Recycling method of acetone in preparation of ethylhexyl glycerol |
| CN116253702A (en) * | 2022-12-29 | 2023-06-13 | 苏州元素集化学工业有限公司 | Synthesis method of alkyl glycidyl ether |
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| CN104817436B (en) | 2017-01-11 |
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Address after: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |