CN112812001A - Preparation method of 9, 10-dihydroxystearic acid - Google Patents
Preparation method of 9, 10-dihydroxystearic acid Download PDFInfo
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- CN112812001A CN112812001A CN202011604062.5A CN202011604062A CN112812001A CN 112812001 A CN112812001 A CN 112812001A CN 202011604062 A CN202011604062 A CN 202011604062A CN 112812001 A CN112812001 A CN 112812001A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
Abstract
The invention discloses a preparation method of 9, 10-dihydroxystearic acid, which comprises the following steps: evenly mixing oleic acid and a catalyst, then dropwise adding a hydrogen peroxide solution, and reacting for 0.5-24 hours at 20-80 ℃; after the reaction is finished, removing a water layer, washing and drying an oil layer to obtain a target product 9, 10-dihydroxystearic acid; wherein the catalyst is one or a mixture of two of phosphotungstic acid and supported phosphotungstic acid. According to the preparation method of the 9, 10-dihydroxystearic acid, strong acid such as formic acid and sulfuric acid is not added, alkali is not required to be added for neutralization after the reaction is finished, and the preparation method has the advantages of small corrosion to equipment, small environmental pollution, good selectivity, high activity and the like, meets the requirements of environmental protection, and has an industrial application prospect.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, and particularly relates to a preparation method of 9, 10-dihydroxystearic acid.
Background
9, 10-dihydroxystearic acid is a very important chemical intermediate, and has important application in the fields of medicines, cosmetics, feed additives, surfactants and the like. The product is white waxy or powdery solid, insoluble in water and petroleum ether, slightly soluble in ethyl acetate, and easily soluble in organic solvents such as methanol, ethanol, acetone, etc., and is a hydroxy fatty acid containing two hydroxy groups and one carboxy group. However, polyhydroxy fatty acids are rarely found in nature, and thus synthesis of 9, 10-dihydroxystearic acid is required through some chemical reactions. The structure is as follows:
the 9, 10-dihydroxystearic acid is prepared by adding hydrogen peroxide into oleic acid as a raw material and reacting under the action of formic acid or sulfuric acid to generate the 9, 10-dihydroxystearic acid. The 9, 10-dihydroxystearic acid is prepared from oleic acid under the catalysis of formic acid by Eimetijiang Sawuti et al; methyl epoxy oleate and oleic acid are used as raw materials, sulfuric acid is used as a catalyst, and 9, 10-dihydroxystearate are prepared respectively by using xylonite and the like. However, strong acids such as formic acid, sulfuric acid and the like exist in the reaction process, equipment is easy to corrode, alkali needs to be added for neutralization after the reaction is finished, and the problems of large wastewater amount, serious pollution and the like exist.
Michael A.Oakley et al obtained 9, 10-dihydroxyoctadecanoic acid with 60 wt% hydrogen peroxide in the presence of tungstic acid as catalyst, but at a low yield. Vincenzo Benessere et al studied the synthesis of azelaic acid in a two-step process, first oxidation of oleic acid to 9, 10-dihydroxyoctadecanoic acid with 60 wt% hydrogen peroxide followed by oxidative cleavage with sodium hypochlorite, and proposed techniques for isolation and purification of azelaic acid, but with yields of only 40% -50%.
Selection of hydrophobic ionic liquid BMIMPF by Xinjiang physicochemical institute Ayixiamu and other people in Chinese academy of sciences6As solvent, using 50 wt% hydrogen peroxide and tungstic acid as catalyst to obtain 9, 10-dihydroxy octadecanoic acid, the yield can reach 85% at most. However, the high concentration of hydrogen peroxide not only increases the risk factor of the experiment, but also is expensive, which is not favorable for further industrialization.
Sunpongqiang et al use tungstic acid as a catalyst and oleic acid and acetic acid as reactants to obtain 9, 10-dihydroxyoctadecanoic acid under the oxidation of 30% hydrogen peroxide. Although the acidity of acetic acid is weak compared with strong acids such as formic acid and sulfuric acid, the acetic acid still corrodes equipment, alkali needs to be added for neutralization after reaction, and the generated wastewater is much and pollutes the environment; in addition, peroxyacetic acid generated by the reaction of acetic acid and hydrogen peroxide is extremely unstable, is easy to explode, affects the safety of preparation, and is not beneficial to industrial production.
Recently, KMnO has also been reported4Oxidation process, OsO4Oxidation method, etc. to prepare 9, 10-dihydroxystearic acid. Wherein OsO4High toxicity, high price, and is not suitable for industrial production, in KMnO4A large amount of strong base and strong oxidant are needed in the oxidation method, equipment can be corroded, the environment is polluted, the green chemical concept advocated by the nation is not met, and the large-scale industrial production is not suitable.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of 9, 10-dihydroxystearic acid, which does not add strong acid such as formic acid, sulfuric acid and the like, does not need to add alkali for neutralization after the reaction is finished, has the advantages of small corrosion to equipment, small environmental pollution, good selectivity, high activity and the like, meets the requirements of environmental protection, and has industrial application prospect.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of 9, 10-dihydroxystearic acid, which comprises the following steps:
evenly mixing oleic acid and a catalyst, then dropwise adding a hydrogen peroxide solution, and reacting for 0.5-24 hours at 20-80 ℃; after the reaction is finished, removing a water layer, washing and drying an oil layer to obtain a target product 9, 10-dihydroxystearic acid;
wherein the catalyst is one or a mixture of two of phosphotungstic acid and supported phosphotungstic acid.
Compared with the prior art in which tungstic acid is used as a catalyst, the catalyst of the invention is phosphotungstic acid or supported phosphotungstic acid, which has high catalytic activity, and does not need to add strong acids such as formic acid, acetic acid, sulfuric acid and the like, thereby reducing the corrosion to equipment and also not needing to add alkali for neutralization.
Further, the carrier of the supported phosphotungstic acid is one or a mixture of more of silicon dioxide, molecular sieve, resin, calcium carbonate, magnesium oxide and titanium dioxide.
Further, the supported phosphotungstic acid is obtained by stirring phosphotungstic acid and a carrier in a solvent for 0.5-50 hours, filtering and drying; the solvent is one or a mixture of methanol, ethanol, isopropanol, acetone, ethyl acetate and methyl acetate.
Furthermore, the dosage of the catalyst is 0.01-30% of the mass of the oleic acid.
Further, the mass concentration of the hydrogen peroxide solution is 30%, and the using amount of the hydrogen peroxide solution is 0.8-400% of the mass of the oleic acid.
Further, the purity of the oleic acid is 65-95%.
Further, the dropping temperature of the hydrogen peroxide solution is 20-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the 9, 10-dihydroxystearic acid does not add strong acid such as formic acid, sulfuric acid and the like, does not need to add alkali for neutralization after the reaction is finished, has the advantages of small corrosion to equipment, small environmental pollution, good selectivity, high activity and the like, meets the requirements of environmental protection, and has industrial application prospect.
2. The raw materials adopted by the invention are common industrial products, the cost is low, the conversion rate of the reaction is high, and the full utilization of the raw materials is realized; and the yield of the target product is as high as 92%.
Drawings
FIG. 1 is a nuclear magnetic spectrum of 9, 10-dihydroxystearic acid;
FIG. 2 is a mass spectrum of 9, 10-dihydroxystearic acid.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1
5.0g of oleic acid (85%) and 0.2g of phosphotungstic acid are mixed and stirred uniformly, 5g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 30 ℃, and after dripping is finished, the reaction is carried out for about 4 hours at the temperature of 80 ℃. After the reaction is finished, standing and layering the reaction solution, removing a water layer, washing an oil layer with water, and drying to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 95%, and the yield of the target product is 90%.
Example 2
5.0g of oleic acid (85%) and 0.5g of phosphotungstic acid are mixed and stirred uniformly, 6g of 30% hydrogen peroxide solution is slowly dripped at 40 ℃, and after dripping is finished, the reaction lasts for about 3 hours at 70 ℃. After the reaction is finished, standing and layering the reaction solution, removing a water layer, washing an oil layer with water, and drying to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 90%, and the yield of the target product is 88%.
Example 3
Mixing and stirring 100g of molecular sieve, 15g of phosphotungstic acid and 5-500 mL of absolute ethyl alcohol for 1-50 hours, filtering and drying to obtain the molecular sieve supported phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1g of molecular sieve-loaded phosphotungstic acid are uniformly mixed, 6g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 60 ℃, and the mixture reacts for about 6 hours at the temperature of 80 ℃ after the dripping is finished. And filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 96 percent, and the yield of the target product is 92 percent.
Example 4
Mixing and stirring 100g of activated carbon, 20g of phosphotungstic acid and 5-500 mL of methanol for 1-50 hours, filtering and drying to obtain the activated carbon supported phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1.2g of activated carbon-loaded phosphotungstic acid are uniformly mixed, 8g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 30 ℃, and the mixture reacts for about 5 hours at the temperature of 60 ℃ after the dripping is finished. Filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 90 percent, and the yield of the target product is 85 percent.
Example 5
Mixing and stirring 100g of macroporous resin, 12g of phosphotungstic acid and 5-500 mL of isopropanol for 1-50 hours, filtering and drying to obtain the resin-loaded phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1g of resin-loaded phosphotungstic acid are uniformly mixed, 7g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 30 ℃, and the mixture reacts for about 5 hours at the temperature of 60 ℃ after the dripping is finished. And filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 91 percent, and the yield of the target product is 86 percent.
Example 6
Mixing and stirring 100g of hydrophilic fumed silica, 10g of phosphotungstic acid and 5-500 mL of isopropanol for 1-50 hours, filtering and drying to obtain the hydrophilic silica supported phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1.2g of hydrophilic silicon dioxide supported phosphotungstic acid are uniformly mixed, 7g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 60 ℃, and the mixture reacts for about 4 hours at the temperature of 70 ℃ after the dripping is finished. And filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 82 percent, and the yield of the target product is 75 percent.
Example 7
Mixing and stirring 100g of silica gel, 15g of phosphotungstic acid and 5-500 mL of methanol for 1-50 hours, filtering and drying to obtain the silica gel supported phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1g of silica gel-supported phosphotungstic acid are mixed uniformly, 7g of 30% hydrogen peroxide solution is slowly dripped at 60 ℃, and after dripping is finished, the reaction lasts for about 5 hours at 80 ℃. Filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 90 percent, and the yield of the target product is 86 percent.
Example 8
Mixing and stirring 100g of hydrophobic silica, 15g of phosphotungstic acid and 5-500 mL of ethyl acetate for 1-50 hours, filtering and drying to obtain the hydrophobic silica supported phosphotungstic acid catalyst. 5.0g of oleic acid (65%) and 1.2g of hydrophobic silica-supported phosphotungstic acid are uniformly mixed, 6g of 30% hydrogen peroxide solution is slowly dripped at the temperature of 60 ℃, and the mixture reacts for about 6 hours at the temperature of 80 ℃ after the dripping is finished. And filtering after the reaction is finished, standing and layering the filtrate, removing a water layer, and collecting an oil layer to obtain the target product 9, 10-dihydroxystearic acid, wherein the conversion rate is 95 percent, and the yield of the target product is 91 percent.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. A method for preparing 9, 10-dihydroxystearic acid is characterized by comprising the following steps:
evenly mixing oleic acid and a catalyst, then dropwise adding a hydrogen peroxide solution, and reacting for 0.5-24 hours at 20-80 ℃; after the reaction is finished, removing a water layer, washing and drying an oil layer to obtain a target product 9, 10-dihydroxystearic acid;
wherein the catalyst is one or a mixture of two of phosphotungstic acid and supported phosphotungstic acid.
2. The method of claim 1, wherein the carrier of the supported phosphotungstic acid is one or more of silica, molecular sieve, resin, calcium carbonate, magnesium oxide and titanium dioxide.
3. The method for preparing 9, 10-dihydroxystearic acid according to claim 2, wherein the supported phosphotungstic acid is obtained by stirring phosphotungstic acid and a carrier in a solvent for 0.5 to 50 hours, filtering and drying; the solvent is one or a mixture of methanol, ethanol, isopropanol, acetone, ethyl acetate and methyl acetate.
4. The method of claim 1, wherein the amount of the catalyst is 0.01-30% by weight of the oleic acid.
5. The method of claim 1, wherein the hydrogen peroxide solution is used in an amount of 0.8-400% by mass based on the mass of the oleic acid, and the hydrogen peroxide solution has a mass concentration of 30%.
6. The method of claim 1, wherein the oleic acid is 65-95% pure.
7. The method of claim 1, wherein the hydrogen peroxide solution is added dropwise at a temperature of 20-80 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113843048A (en) * | 2021-09-15 | 2021-12-28 | 武汉工程大学 | Polyhydroxy fatty acid sodium soap and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044704A1 (en) * | 1999-01-28 | 2000-08-03 | Novance | Method for expoxidizing or dihydroxilating unsaturated fatty acids |
| WO2003062179A1 (en) * | 2002-01-24 | 2003-07-31 | Japan Science And Technology Agency | Novel process for producing 1,2-diol |
| CN1680253A (en) * | 2005-02-03 | 2005-10-12 | 中国科学院新疆理化技术研究所 | Preparation of azelaic acid by catalytic oxidizing system |
| US20050240041A1 (en) * | 2004-04-21 | 2005-10-27 | Salmiah Ahmad | Palm-based hydroxy fatty acid |
| CN101679181A (en) * | 2007-05-10 | 2010-03-24 | 诺瓦蒙特股份公司 | Process for the catalytic cleavage of vegetable oils |
| WO2017203191A1 (en) * | 2016-05-27 | 2017-11-30 | Institut National Polytechnique De Toulouse | Process for oxidation of an unsaturated fatty acid and reaction system for carrying out such a process |
| CN109942407A (en) * | 2019-04-16 | 2019-06-28 | 中国日用化学研究院有限公司 | A kind of 9,10- of synthesis dihydroxy, the 18 stearic method of carbon |
| CN111943839A (en) * | 2020-08-26 | 2020-11-17 | 德州市晟昊生物科技有限公司 | Two-step oxidation method for preparing dibasic acid by oxidative cracking of unsaturated fatty acid |
-
2020
- 2020-12-29 CN CN202011604062.5A patent/CN112812001A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044704A1 (en) * | 1999-01-28 | 2000-08-03 | Novance | Method for expoxidizing or dihydroxilating unsaturated fatty acids |
| WO2003062179A1 (en) * | 2002-01-24 | 2003-07-31 | Japan Science And Technology Agency | Novel process for producing 1,2-diol |
| US20050240041A1 (en) * | 2004-04-21 | 2005-10-27 | Salmiah Ahmad | Palm-based hydroxy fatty acid |
| CN1680253A (en) * | 2005-02-03 | 2005-10-12 | 中国科学院新疆理化技术研究所 | Preparation of azelaic acid by catalytic oxidizing system |
| CN101679181A (en) * | 2007-05-10 | 2010-03-24 | 诺瓦蒙特股份公司 | Process for the catalytic cleavage of vegetable oils |
| WO2017203191A1 (en) * | 2016-05-27 | 2017-11-30 | Institut National Polytechnique De Toulouse | Process for oxidation of an unsaturated fatty acid and reaction system for carrying out such a process |
| CN109942407A (en) * | 2019-04-16 | 2019-06-28 | 中国日用化学研究院有限公司 | A kind of 9,10- of synthesis dihydroxy, the 18 stearic method of carbon |
| CN111943839A (en) * | 2020-08-26 | 2020-11-17 | 德州市晟昊生物科技有限公司 | Two-step oxidation method for preparing dibasic acid by oxidative cracking of unsaturated fatty acid |
Non-Patent Citations (3)
| Title |
|---|
| HIDESHIHATTORI，YOSHIOONO著: "《固体酸催化》", 31 May 2016, 复旦大学出版社 * |
| NAHLA ARAJI ET AL.: "Selective dihydroxylation of methyl oleate to methyl-9,10-dihydroxystearate in the presence of a recyclable tungsten based catalyst and hydrogen peroxide", 《NEW J. CHEM》 * |
| 胡惟孝，杨忠愚 编著: "《有机化合物制备手册》", 31 March 1995, 天津科技翻译出版公司 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113843048A (en) * | 2021-09-15 | 2021-12-28 | 武汉工程大学 | Polyhydroxy fatty acid sodium soap and preparation method and application thereof |
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Application publication date: 20210518 |