CN113797968B - Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst and preparation method of polyglycerol fatty acid ester - Google Patents
Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst and preparation method of polyglycerol fatty acid ester Download PDFInfo
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- CN113797968B CN113797968B CN202110954761.0A CN202110954761A CN113797968B CN 113797968 B CN113797968 B CN 113797968B CN 202110954761 A CN202110954761 A CN 202110954761A CN 113797968 B CN113797968 B CN 113797968B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- 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
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Abstract
The invention provides a preparation method of polyglycerol fatty acid ester. The preparation method of the polyglycerol fatty acid ester comprises the following steps: 1) preparing a novel solid acid catalyst 2-chloroisonicotinic acid-phosphomolybdic acid; 2) preparation of polyglyceryl fatty acid ester under solid acid catalysis 3) purification of polyglyceryl fatty acid ester. The solid acid catalyst prepared by the method has high esterification rate and high yield for the synthesis of the polyglycerol fatty acid ester, the obtained polyglycerol fatty acid ester has a specific polymerization degree (3-10), the separation condition of the reaction process is simple, the method has industrial amplification potential, and the prepared polyglycerol fatty acid ester has high purity (more than 97.5%), light color and good product applicability.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing polyglycerol fatty acid ester by using novel solid acid catalysis.
Background
In the fields of food, medicine and cosmetics, polyglycerol fatty acid esters have been widely used as a safe and efficient surfactant. The polyglycerol ester has strong stability, is not easy to decompose even in acid-base environment, has good antibacterial property and emulsifying property, has excellent biodegradability, and is a natural green surfactant.
In the aspect of synthesis of polyglycerol fatty acid ester, in the process of preparing the polyglycerol fatty acid ester by adopting an acid method, high-temperature and high-pressure reaction conditions are often needed, strong-corrosivity acid catalysts such as sulfuric acid or phosphoric acid are used, the catalytic efficiency is low, the fatty acid esterification rate is low, the color and luster are deep, and the content of cyclic polyglycerol as a byproduct is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing polyglycerol fatty acid ester by using a novel solid acid catalyst 2-chloroisonicotinic acid-phosphomolybdic acid.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, comprising:
1) respectively dissolving a certain amount of phosphomolybdic acid and 2-chloroisonicotinic acid in an alcohol solvent, and stirring for a certain period of time at a certain temperature.
2) Slowly mixing the 2-chloroisonicotinic acid solution and the phosphomolybdic acid solution, continuing stirring for a period of time after mixing, then carrying out suction filtration to remove insoluble substances, and drying the solid obtained by suction filtration under reduced pressure for a period of time to obtain the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst.
In the preparation method of the catalyst, the mass ratio of the 2-chloroisonicotinic acid to the phosphomolybdic acid in the step 1) is 1: 9-13, preferably 1: 10-12;
the alcohol solvent is one or more of methanol, ethanol and isopropanol, preferably ethanol;
the stirring temperature is 30-50 ℃, and preferably 35-40 ℃; the stirring time is 0.5-4 h, preferably 1-2 h;
in the preparation method of the catalyst, in the step 2), the stirring time is 1-4 hours, preferably 1.5-3 hours;
the reduced pressure drying temperature is 45-80 ℃, and preferably 50-70 ℃; the drying time is 2-10 h, preferably 3-7 h.
In a second aspect of the present invention, a method for synthesizing a polyglycerin fatty acid ester is provided, which comprises the following steps:
(1) weighing a certain amount of polyglycerol, fatty acid and 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, respectively adding the polyglycerol, fatty acid and 2-chloroisonicotinic acid-phosphomolybdic acid catalyst into a reactor, adding a certain amount of alcohol solvent, introducing nitrogen, heating and refluxing for a period of time, adding a certain amount of inorganic salt, continuously reacting for a period of time, cooling to room temperature after the reaction is finished, carrying out suction filtration to remove insoluble substances, and finally carrying out reduced pressure distillation on the reaction liquid to obtain crude polyglycerol fatty acid ester.
(2) Dissolving crude polyglycerol fatty acid ester in an organic solvent, heating to 45-60 ℃, washing for multiple times by using a saturated ammonium chloride aqueous solution, extracting and separating liquid to obtain a polyglycerol ester solution, and finally distilling under reduced pressure to remove the solvent to obtain oily polyglycerol fatty acid ester.
In the method for synthesizing the polyglycerol fatty acid ester, the polymerization degree of the polyglycerol in the step (1) is 3-10, preferably 7-10;
the fatty acid is selected from one or more of caprylic acid, capric acid, palmitic acid, stearic acid, oleic acid and lauric acid;
the mass ratio of the fatty acid to the polyglycerol is 1: 1-10, preferably 1: 3-8;
the mass ratio of the fatty acid to the 2-chloroisonicotinic acid catalyst is 1: 0.02-0.2, preferably 1: 0.08-0.15;
the alcohol solvent is one or more selected from methanol, ethanol and n-butanol;
the heating reflux temperature is 80-130 ℃, and preferably 90-120 ℃; the time is 1-5 h, preferably 2-4 h;
the inorganic salt is one or more of anhydrous sodium sulfate, magnesium sulfate and calcium sulfate, and preferably anhydrous sodium sulfate;
the mass ratio of the fatty acid to the inorganic salt is 1: 0.2-0.5, preferably 1: 0.3-0.4; the continuous reaction time is 0.5-3 h, preferably 1-2 h;
in the synthesis method of the polyglycerol fatty acid ester, the organic solvent in the step (2) is one or more of ethyl acetate, dichloromethane and propyl acetate, and ethyl acetate is preferred;
the mass ratio of the crude polyglycerol fatty acid ester to the organic solvent is 1: 2-5, preferably 1: 2.5-4;
the number of washing times with a saturated ammonium chloride aqueous solution is 2 to 5, preferably 3 to 4.
By adopting the technical scheme, the invention has the following advantages:
1) the reaction process for synthesizing the polyglycerol fatty acid ester under the catalysis of the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst is mild, the use of high-temperature and high-pressure reaction conditions is avoided, the traditional liquid acid catalyst is replaced, and the catalyst has extremely high catalytic efficiency and high esterification rate;
2) the polyglycerol fatty acid ester prepared by the method has a specific polymerization degree (3-10);
3) the reaction process has simple separation conditions and industrial amplification potential;
4) the prepared polyglycerol fatty acid ester has high purity (more than 97.5 percent), light color and good product applicability.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but is not limited thereto.
Example 1
Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst:
weighing 10g of phosphomolybdic acid and 1g of 2-chloroisonicotinic acid, respectively dissolving in 20ml of absolute ethanol, stirring for 1h at 35 ℃, then slowly dropwise adding the 2-chloroisonicotinic acid ethanol solution into the phosphomolybdic acid solution, continuously stirring for 1h after dropwise adding, then removing insoluble substances by suction filtration, and vacuum drying the solid obtained by suction filtration for 5h at 50 ℃ to obtain the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, wherein the yield is 82%.
Preparation of polyglycerol oleate:
respectively weighing 50g of polyglycerol with the polymerization degree of 7, 5g of oleic acid and 0.5g of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, respectively adding the polyglycerol into a three-neck flask, adding 200ml of methanol, introducing nitrogen, heating and refluxing for 2h at 95 ℃, then adding 2g of anhydrous sodium sulfate, continuing to react for 1h, cooling to room temperature after the reaction is finished, then carrying out suction filtration to remove insoluble substances, and finally carrying out reduced pressure distillation on the reaction solution to obtain crude polyglycerol oleate. Dissolving crude polyglycerol oleate in 200g of ethyl acetate, heating to 50 ℃, washing for 3 times by using saturated ammonium chloride aqueous solution, then extracting and separating liquid to obtain the ethyl acetate solution of polyglycerol oleate, and finally removing the solvent by reduced pressure distillation to obtain 48g of oily polyglycerol oleate with the purity of 97.8 percent and light color.
Example 2
Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst:
weighing 12g of phosphomolybdic acid and 1g of 2-chloroisonicotinic acid, respectively dissolving in 20ml of anhydrous methanol, stirring for 1.5h at 40 ℃, then slowly dropwise adding the 2-chloroisonicotinic acid solution into the phosphomolybdic acid solution, continuously stirring for 2h after dropwise adding, then carrying out suction filtration to remove insoluble substances, and carrying out vacuum drying on the solid obtained by suction filtration for 3h at 60 ℃ to obtain the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, wherein the yield is 85%.
Preparation of polyglycerol palmitate:
respectively weighing 50g of polyglycerol with the polymerization degree of 10, 10g of palmitic acid and 1.2g of 2-chloroisonicotinic acid-phosphomolybdic acid, respectively adding the polyglycerol into a three-neck flask, adding 200ml of ethanol, introducing nitrogen, heating and refluxing for 3h at 100 ℃, then adding 3g of anhydrous sodium sulfate, continuing to react for 1h, cooling to room temperature after the reaction is finished, then carrying out suction filtration to remove insoluble substances, and finally carrying out reduced pressure distillation on the reaction solution to obtain crude polyglycerol palmitate. Dissolving crude polyglycerol palmitate in 230g of dichloromethane, heating to 60 ℃, washing for 3 times by using saturated ammonium chloride aqueous solution, extracting and separating liquid to obtain a dichloromethane solution of polyglycerol palmitate, and finally removing the solvent by reduced pressure distillation to obtain 48g of oily polyglycerol palmitate with the purity of 98.1% and light color.
Example 3
Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst:
weighing 9g of phosphomolybdic acid and 1g of 2-chloroisonicotinic acid, respectively dissolving in 20ml of absolute ethanol, stirring for 2h at 45 ℃, then slowly dropwise adding the 2-chloroisonicotinic acid ethanol solution into the phosphomolybdic acid solution, continuously stirring for 2h after dropwise adding, then carrying out suction filtration to remove insoluble substances, and carrying out vacuum drying on the solid obtained by suction filtration for 3h at 50 ℃ to obtain the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst, wherein the yield is 79%.
Preparation of polyglycerol decanoate:
respectively weighing 50g of polyglycerol with the polymerization degree of 8, 17g of capric acid and 1.4g of 2-chloroisonicotinic acid-phosphomolybdic acid, respectively adding the polyglycerol into a three-neck flask, adding 200ml of ethanol, introducing nitrogen, heating and refluxing for 2h at 80 ℃, then adding 5.7g of anhydrous sodium sulfate, continuing to react for 2h, cooling to room temperature after the reaction is finished, then carrying out suction filtration to remove insoluble substances, and finally carrying out reduced pressure distillation on the reaction solution to obtain crude polyglycerol decanoate. The crude polyglycerol decanoate was dissolved in 250g of ethyl acetate, heated to 60 ℃, washed 2 times with a saturated aqueous ammonium chloride solution, then subjected to extraction and liquid separation to obtain an ethyl acetate solution of polyglycerol decanoate, and finally the solvent was removed by distillation under reduced pressure to obtain 52g of polyglycerol decanoate in oil form, having a purity of 98.3% and light color.
Comparative example 1
Respectively weighing 50g of polyglycerol with the polymerization degree of 8, 17g of capric acid and 1.4g of phosphoric acid, respectively adding the polyglycerol with the polymerization degree of 8, adding 200ml of ethanol, introducing nitrogen, heating and refluxing for 2h at 80 ℃, then adding 5.7g of anhydrous sodium sulfate, continuing to react for 2h, cooling to room temperature after the reaction is finished, then carrying out suction filtration to remove insoluble substances, and finally carrying out reduced pressure distillation on the reaction liquid to obtain crude polyglycerol decanoate. Dissolving crude polyglycerol decanoate in 250g of ethyl acetate, heating to 60 ℃, washing for 2 times by using saturated ammonium chloride aqueous solution, then extracting and separating liquid to obtain the ethyl acetate solution of polyglycerol decanoate, and finally removing the solvent by reduced pressure distillation to obtain 10g of oily polyglycerol decanoate with the purity of 80.1%, yellow brown color and dark color.
Claims (14)
1. A preparation method of a 2-chloroisonicotinic acid-phosphomolybdic acid catalyst comprises the following steps:
1) respectively dissolving a certain amount of phosphomolybdic acid and 2-chloroisonicotinic acid in an alcohol solvent, and stirring for a period of time at a certain temperature;
2) and (3) slowly mixing the 2-chloroisonicotinic acid solution and the phosphomolybdic acid solution, continuously stirring for a period of time after mixing is finished, removing insoluble substances, and drying the obtained solid to obtain the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst.
2. The method according to claim 1, wherein the mass ratio of 2-chloroisonicotinic acid to phosphomolybdic acid is 1: 9-13.
3. The method according to claim 1 or 2, wherein in the step 1), the stirring temperature is 30-50 ℃ and the stirring time is 0.5-4 h.
4. The method according to any one of claims 1 to 2, wherein in step 2), the stirring time is 1 to 4 hours; the drying temperature is 45-80 ℃, and the drying time is 2-10 h.
5. A method for preparing polyglycerol fatty acid ester, which comprises the following steps:
(1) weighing a certain amount of polyglycerol, fatty acid and the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst prepared by the method of any one of claims 1 to 4, respectively adding the polyglycerol, the fatty acid and the 2-chloroisonicotinic acid-phosphomolybdic acid catalyst into a reactor, adding an alcohol solvent, heating and refluxing, adding a certain amount of inorganic salt for continuous reaction, cooling to room temperature after the reaction is finished, removing insoluble substances, and distilling the reaction liquid under reduced pressure to obtain crude polyglycerol fatty acid ester;
(2) dissolving crude polyglycerol fatty acid ester in an organic solvent, heating to 45-60 ℃, washing, extracting and separating liquid to obtain a polyglycerol ester solution, and finally removing the solvent to obtain the polyglycerol fatty acid ester.
6. The method according to claim 5, wherein the degree of polymerization of the polyglycerol in the step (1) is 3 to 10;
the fatty acid is selected from one or more of caprylic acid, capric acid, palmitic acid, stearic acid, oleic acid and lauric acid.
7. The method according to claim 6, wherein the degree of polymerization of the polyglycerol in the step (1) is 7 to 10.
8. The method according to claim 6, wherein the mass ratio of the fatty acid to the polyglycerol is 1:1 to 10, and the mass ratio of the fatty acid to the catalyst is 1:0.02 to 0.2.
9. The method according to claim 5, wherein in the step (1), the alcohol solvent is selected from one or more of methanol, ethanol and n-butanol;
the heating reflux temperature is 80-130 ℃, and the time is 1-5 h.
10. The method according to any one of claims 5 to 9, wherein in step (1), the inorganic salt is one or more of anhydrous sodium sulfate, magnesium sulfate, and calcium sulfate.
11. The method according to claim 10, wherein the mass ratio of the fatty acid to the inorganic salt is 1: 0.2-0.5.
12. The method according to claim 5, wherein the organic solvent in step (2) is one or more of ethyl acetate, dichloromethane and propyl acetate.
13. The method according to claim 12, wherein the mass ratio of the crude polyglycerin fatty acid ester to the organic solvent is 1:2 to 5.
14. The method according to claim 5, wherein the washing in step (2) is performed with 2 to 5 times of saturated aqueous ammonium chloride solution.
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| US4592866A (en) * | 1982-09-30 | 1986-06-03 | A. H. Robins Company, Inc. | Fused aromatic oxazepinones, thiazepinones, diazepinones and sulfur analogs thereof |
| WO1999033807A2 (en) * | 1997-12-24 | 1999-07-08 | Pdi-Research Laboratories, Inc. | Synthesis of pharmaceutically useful pyridine derivatives (intermediates) employing free radical substitution reactions to functionalize the 2-position of the pyridine |
| CN101381304A (en) * | 2008-10-22 | 2009-03-11 | 上海化工研究院 | Synthetic method of tricaprylin-carboxyl-<13>C3 |
| CN101429119A (en) * | 2008-12-10 | 2009-05-13 | 江南大学 | Process for producing polyglycerol fatty acid monoester |
| CN102618255A (en) * | 2012-03-19 | 2012-08-01 | 上海施科特光电材料有限公司 | Method for preparing photoluminescent phosphomolybdate isonicotinic acid crystal |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4592866A (en) * | 1982-09-30 | 1986-06-03 | A. H. Robins Company, Inc. | Fused aromatic oxazepinones, thiazepinones, diazepinones and sulfur analogs thereof |
| WO1999033807A2 (en) * | 1997-12-24 | 1999-07-08 | Pdi-Research Laboratories, Inc. | Synthesis of pharmaceutically useful pyridine derivatives (intermediates) employing free radical substitution reactions to functionalize the 2-position of the pyridine |
| CN101381304A (en) * | 2008-10-22 | 2009-03-11 | 上海化工研究院 | Synthetic method of tricaprylin-carboxyl-<13>C3 |
| CN101429119A (en) * | 2008-12-10 | 2009-05-13 | 江南大学 | Process for producing polyglycerol fatty acid monoester |
| CN102618255A (en) * | 2012-03-19 | 2012-08-01 | 上海施科特光电材料有限公司 | Method for preparing photoluminescent phosphomolybdate isonicotinic acid crystal |
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