CN115872860A - Method for accelerating synthesis reaction rate of long-chain fatty acid isobornyl ester - Google Patents
Method for accelerating synthesis reaction rate of long-chain fatty acid isobornyl ester Download PDFInfo
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Abstract
The invention discloses a method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester, belonging to the technical field of deep processing of forestry products. Because the long-chain fatty acid has larger molecular weight and low reaction rate with camphene, the energy consumption and the power cost are increased, the invention preferentially obtains the composite catalyst consisting of sulfate, alpha-hydroxycarboxylic acid and boric acid, and the application of the composite catalyst in the synthesis reaction step can effectively improve the synthesis reaction rate of the long-chain fatty acid isobornyl ester and greatly reduce the energy consumption cost.
Description
Technical Field
The invention relates to the technical field of deep processing of forest products, in particular to a method for accelerating reaction rate when long-chain fatty acid isobornyl ester synthesized by camphene reacts.
Background
The long-chain fatty acid isobornyl ester can be used as a green solvent, a surfactant, a plasticizer and the like, and has important application in the fields of medicine and high-end material manufacturing. The reaction for preparing long-chain fatty acid isobornyl ester by camphene esterification can be divided into homogeneous catalysis and heterogeneous catalysis according to a reaction system. The homogeneous catalysis takes liquid inorganic acid such as sulfuric acid and the like as a catalyst, and the catalytic reaction has the problems of poor selectivity, a plurality of byproducts, difficult subsequent separation, easy corrosion of equipment, generation of a large amount of acid-containing wastewater and the like. Heterogeneous catalysis takes ion exchange resin, zeolite, molecular sieve and the like as catalysts, but the problems of rapid deactivation, difficult regeneration and the like of the catalysts generally exist in industry.
In order to solve the problems existing in the prior art, technicians continuously search for new catalysts to improve the selectivity of camphene esterification reaction and increase the reusability and environmental protection of the catalysts. For example, guyun is a bright paper which uses sulfuric acid as a catalyst in the "influencing factor of esterification reaction of lower fatty acid and camphene and the preparation of C1-C5 isobornyl carboxylate" to discuss the influencing factor of esterification reaction of camphene and lower fatty acid and prepare C1-C5 short-chain isobornyl carboxylate (perfume and essence cosmetics, 2013, supplement). Chinese patent application CN201711290727.8 discloses a functionalized polyacid ionic liquid agent and a method for catalytically synthesizing isobornyl acetate by using the same, wherein camphene and acetic acid are used as raw materials, and the functionalized polyacid ionic liquid is used as a catalyst to prepare the isobornyl acetate through an esterification reaction. Cui Juntao, et al, in the published article "study on synthesis of isobornyl acetate by lewis acid-catalyzed isomeric esterification of camphene", disclose that ferric trichloride is used as a catalyst to catalyze esterification of camphene and glacial acetic acid to prepare isobornyl acetate, but ferric trichloride has strong irritant corrosivity (forest chemical and industrial, 2018, 38 (1)).
Because the long-chain fatty acid has large molecular weight and low reactivity, and usually needs longer time when reacting with camphene, on one hand, the energy consumption and the power cost are increased, and on the other hand, the side reactions are increased and the product color is deepened. Therefore, screening of suitable catalysts has become a new direction of research.
Disclosure of Invention
The invention provides a method for accelerating the reaction rate of long-chain fatty acid isobornyl ester in order to overcome the problem of low reaction rate in the synthesis of long-chain fatty acid isobornyl ester.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester comprises the following steps: the method comprises the following steps of synthetic reaction, filtration, washing, product purification, solvent recovery and product refining, wherein the synthetic reaction step comprises the following steps:
adding camphene and long-chain fatty acid into a reaction kettle according to the mol ratio of 1.2-1.6, the mass ratio of the composite catalyst to camphene of 0.05-0.3, starting stirring, controlling the reaction temperature to be 80-90 ℃ and the reaction time to be 15-24 h; the composite catalyst consists of anhydrous sulfate, alpha-hydroxy acid and boric acid according to a mass ratio of 1.
Preferably, the anhydrous sulfate comprises one or more of ferric sulfate, zirconium sulfate and titanium sulfate.
Preferably, the alpha-hydroxycarboxylic acid includes one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid and glycolic acid.
Preferably, the boric acid is dehydrated boric acid after being heated for 1 hour at the temperature of 105-110 ℃.
Preferably, the filtration step is as follows: and standing the liquid product after the reaction is finished, filtering the liquid product, transferring the liquid product into a washing tank, adding an organic solvent into the reaction kettle, washing the solid catalyst at the bottom of the kettle, filtering the washing liquid, and transferring the washing liquid into the washing tank.
Preferably, the water washing step is as follows: adding a certain mass of water, and washing by controlling the water temperature to obtain a mixture of long-chain fatty acid and long-chain fatty acid isobornyl ester.
Preferably, the product purification steps are as follows: adding an organic solvent into the mixture obtained by water washing for dissolving, then dripping an alkali solution, filtering out generated soap, and finally adding water for washing to obtain the layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium aqueous solution.
Preferably, the alkali solution comprises one of a potassium hydroxide solution and a sodium hydroxide solution.
Preferably, the solvent recovery step is as follows: decompressing and distilling to recover the solvent to obtain the crude product of the long-chain fatty acid isobornyl ester.
Preferably, the product refining steps are as follows: and (3) carrying out reduced pressure fractionation on the crude product of the long-chain fatty acid isobornyl ester obtained in the solvent recovery step to remove light components of camphene and terpinene, thus obtaining a fine product of the long-chain fatty acid isobornyl ester.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the composite catalyst used in the invention has the advantages of easily obtained and simple preparation raw materials, good repeatability, no toxicity, low corrosivity, easy realization of industrial production and the like, and the catalytic activity is improved by more than 1 time compared with that of a single component.
2. The composite catalyst used in the invention can greatly save energy consumption, but can accelerate the reaction rate, and the reaction can be completed within 24 hours under the condition of not increasing the dosage of the catalyst and the reaction temperature is only 80-90 ℃.
3. The selectivity of the target product of the composite catalyst used in the invention is more than or equal to 90%. The camphene does not generate side reactions such as isomerization and polymerization, and is beneficial to preparing high-quality long-chain fatty acid isobornyl ester products. The product color is black by using concentrated sulfuric acid as a catalyst, while the product color is light yellow by using the composite catalyst of the invention, the quality is high, the decoloring step can be omitted, and the cost is reduced.
4. The composite catalyst of the method can be recycled and reused after the reaction is finished.
5. The purity of the refined long-chain fatty acid isobornyl ester prepared by the method can reach more than 99 percent, and the refined long-chain fatty acid isobornyl ester can be used as a green solvent, a surfactant and a plasticizer, and has high popularization and application values.
6. Because the long-chain fatty acid has larger molecular weight and low reaction rate with camphene, the energy consumption and the power cost are increased, the composite catalyst consisting of sulfate, alpha-hydroxycarboxylic acid and boric acid is preferably obtained, and the composite catalyst is applied to the synthesis reaction of the long-chain fatty acid isobornyl ester, so that the synthesis reaction rate can be effectively increased, and the energy consumption cost is greatly reduced.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Sample analysis test method of examples or comparative examples
An analytical instrument: an agent 7890A gas chromatograph, agilent, usa; a chromatographic column: AT-35, quartz capillary column (60 m.times.0.25 mm.times.0.25 μm). GC analysis conditions were as follows: carrier gas, high-purity nitrogen; temperature programming: raising the temperature to 150 deg.C at 50 deg.C/min at 70 deg.C (2 min), standing for 3min, raising the temperature to 230 deg.C at 30 deg.C/min, and standing for 40min; sample inlet temperature: at 250 ℃, the total flow rate is 130.5ml/min, the split ratio is 50; FID detection, detection mouth temperature: at 250 ℃, the hydrogen flow is 40ml/min, the air flow is 450ml/min, and the nitrogen flow is 25ml/min. The sample amount was 0.2ul.
An area normalization method is adopted. The amount of camphene conversion is approximated by subtracting the GC content of camphene in the product from the GC content of camphene in the feed.
Camphene conversion = (GC content of camphene in feedstock-GC content of camphene in product)/GC content of camphene in feedstock.
Example 1
A method for accelerating the synthesis reaction rate of isobornyl laurate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.6, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 80 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous zirconium sulfate, tartaric acid and boric acid in a mass ratio of 1;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the lauric acid feed is excessive, the reaction is measured by camphene conversion. The camphene used in the experiment was industrial camphene, the GC content of camphene was 86%, and the GC content of tricyclene was 13% (the same shall apply to the following examples). After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 88 percent; the product was refined to give isobornyl laurate 93.5% GC, fenchyl laurate 3.9% and terpinyl laurate 2.6%.
Example 2
A method for accelerating the synthesis reaction rate of isobornyl laurate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 80 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous ferric sulfate, tartaric acid and boric acid according to a mass ratio of 1;
(2) And (3) filtering: standing after the reaction in the step (1), filtering the liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering the washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is methyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the lauric acid feed is excessive, the reaction is measured by camphene conversion. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene is 90%; the product was refined to give isobornyl laurate with a GC content of 96.5%, fenchyl laurate with a GC content of 1.8% and terpinyl laurate of 2.7%.
Example 3
A method for accelerating the synthesis reaction rate of isobornyl laurate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene with long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.25:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 80 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous titanium sulfate, tartaric acid and boric acid in a mass ratio of 1;
(2) And (3) filtering: standing after the reaction in the step (1), filtering the liquid product, transferring the liquid product into a water washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering the washing liquid, and transferring the washing liquid into the water washing tank, wherein the organic solvent a is ethyl acetate and hexane, and the mass ratio of the organic solvent a to the hexane is 1:1;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: vacuum distilling to recover solvent to obtain long chain fatty acid isobornyl ester crude product;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the lauric acid feed is excessive, the reaction is measured by camphene conversion. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene is 90%; the product was refined to give isobornyl laurate 97.5% GC, fenchyl laurate 1.5% GC and terpinyl laurate 1.0%.
Example 4
A method for accelerating the synthesis reaction rate of isobornyl laurate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.25:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 80 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, tartaric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is hexane;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is absolute ethyl alcohol;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the lauric acid feed is in excess, the extent of reaction progress is measured as camphene conversion. After the reaction is finished, analyzing the product to obtain the conversion rate of camphene of 90%; the product was refined to give isobornyl laurate with a GC content of 98.5%, fenchyl laurate with a GC content of 0.8% and terpinyl laurate with a GC content of 0.7%.
Example 5
A method for accelerating the synthesis reaction rate of isobornyl myristate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, tartaric acid and boric acid in a mass ratio of 1;
(2) And (3) filtering: standing after the reaction in the step (1), filtering the liquid product, transferring the liquid product into a water washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering the washing liquid, and transferring the washing liquid into the water washing tank, wherein the organic solvent a is ethyl acetate and petroleum ether, and the mass ratio of the organic solvent a to the petroleum ether is 1:1;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is absolute ethyl alcohol;
(5) Solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene turnover is a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain 80 percent of camphene conversion rate; after the product was purified, the GC content of isobornyl myristate was 97.5%, fenchyl myristate was 1.6%, and terpinyl myristate was 0.9%.
Example 6
A method for accelerating the synthesis reaction rate of isobornyl myristate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, tartaric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1), filtering the liquid product, transferring the liquid product into a water washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering the washing liquid, and transferring the washing liquid into the water washing tank, wherein the organic solvent a is ethyl acetate and toluene, and the mass ratio of the organic solvent a to the washing liquid is 2:1;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene turnover is a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene is 90%; the product was purified to obtain isocampholyl myristate 98.5% GC, fenchyl myristate 1.0%, terpinyl myristate 0.5%.
Example 7
A method for accelerating the synthesis reaction rate of isobornyl myristate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.6, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, tartaric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1), filtering the liquid product, transferring the liquid product into a water washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering the washing liquid, and transferring the washing liquid into the water washing tank, wherein the organic solvent a is methyl acetate and toluene, and the mass ratio of the methyl acetate to the toluene is 1:1;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass 2 times that of the mixture in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is absolute ethyl alcohol;
(5) And (3) solvent recovery: vacuum distilling to recover solvent to obtain long chain fatty acid isobornyl ester crude product;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene conversion is required as a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene is 90%; the product was purified to obtain isocampholyl myristate 98.5% GC, fenchyl myristate 1.0%, terpinyl myristate 0.5%.
Example 8
A method for accelerating the synthesis reaction rate of isobornyl myristate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.6, the mass ratio of the composite catalyst to the camphene is 0.15:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous ferric sulfate, tartaric acid and boric acid according to a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture obtained in the step (3) into the mixture for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) Solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene turnover is a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain 75% of camphene conversion rate; the product was purified to obtain isocampholyl myristate 98.5% GC, fenchyl myristate 1.0%, terpinyl myristate 0.5%.
Example 9
A method for accelerating the synthesis reaction rate of myristolin ester comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene with long-chain fatty acid according to a molar ratio of 1:1.2, the mass ratio of the composite catalyst to the camphene is 0.05:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous ferric sulfate, tartaric acid and boric acid according to a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing at the water temperature of 60 ℃ for 3 to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene conversion is required as a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 55%; the product was purified to obtain isocampholyl myristate 98.5% GC, fenchyl myristate 1.0%, terpinyl myristate 0.5%.
Example 10
A method for accelerating the synthesis reaction rate of isobornyl myristate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.2, the mass ratio of the composite catalyst to the camphene is 0.05:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous ferric sulfate, tartaric acid and boric acid according to a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 105 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 2 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 3 times at the water temperature of 60 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture obtained in the step (3) into the mixture for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the myristic acid feed is in excess, camphene conversion is required as a measure of the extent to which the reaction proceeds. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 55%; the product was purified to obtain isocampholyl myristate 98.5% GC, fenchyl myristate 1.0%, terpinyl myristate 0.5%.
Example 11
A method for accelerating the synthesis reaction rate of isobornyl palmitate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous ferric sulfate, tartaric acid and boric acid according to a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 4 times at the water temperature of 70 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture obtained in the step (3) into the mixture for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Because the palmitic acid is fed in an excessive amount, the reaction degree needs to be measured according to the camphene conversion condition. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 88 percent; the product, refined, had a GC content of 99.7% isocampholyl palmitate, 0.2% fenchyl palmitate, and 0.1% terpinyl palmitate.
Example 12
A method for accelerating the synthesis reaction rate of isobornyl palmitate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous titanium sulfate, tartaric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 4 times at the water temperature of 70 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture obtained in the step (3) into the mixture for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) Solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Because the palmitic acid is fed in an excessive amount, the reaction degree needs to be measured according to the camphene conversion condition. After the reaction is finished, the conversion rate of camphene is 87.9% through analysis of the product; the product, refined, had a GC content of 99.7% isocampholyl palmitate, 0.2% fenchyl palmitate, and 0.1% terpinyl palmitate.
Example 13
A method for accelerating the synthesis reaction rate of isobornyl palmitate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, citric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at the temperature of 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 4 times at the water temperature of 70 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Because the palmitic acid is fed in an excessive amount, the reaction degree needs to be measured according to the camphene conversion condition. After the reaction is finished, the conversion rate of camphene is 86.8% by analyzing the product; the product refined was 99.4% by GC, 0.3% by GC and 0.3% by GC.
Example 14
A method for accelerating the synthesis reaction rate of isobornyl palmitate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous zirconium sulfate, mandelic acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 4 times at the water temperature of 70 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Because the palmitic acid is fed in an excessive amount, the reaction degree needs to be measured according to the camphene conversion condition. After the reaction is finished, the conversion rate of camphene is 87.5 percent through product analysis; the product, refined, had a GC content of 99.6% isocampholyl palmitate, 0.3% fenchyl palmitate, and 0.1% terpinyl palmitate.
Example 15
A method for accelerating the synthesis reaction rate of isobornyl palmitate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous zirconium sulfate, citric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 4 times at the water temperature of 70 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 3 times that of the mixture obtained in the step (3) into the mixture for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: vacuum distilling to recover solvent to obtain long chain fatty acid isobornyl ester crude product;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Because the palmitic acid is fed in an excessive amount, the reaction degree needs to be measured according to the camphene conversion condition. After the reaction is finished, the conversion rate of camphene is 87% by analyzing the product; the product refined was 99.5% by GC, 0.3% by GC and 0.2% by GC.
Example 16
A method for accelerating the synthesis reaction rate of isobornyl stearate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared from anhydrous zirconium sulfate, citric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 5 times at the water temperature of 80 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 4 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the stearic acid feed is in excess, the degree of reaction progress needs to be measured according to the camphene conversion condition. After the reaction is finished, the conversion rate of camphene is 87.3% by analyzing the product; the product was purified to obtain isobornyl stearate having a GC content of 99.7%, fenchyl stearate 0.2%, and terpinyl stearate 0.1%.
Example 17
A method for accelerating the synthesis reaction rate of isobornyl stearate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.4, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous titanium sulfate, tartaric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid which is heated for 1 hour at the temperature of 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 5 times at the water temperature of 80 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass of 4 times into the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is absolute ethyl alcohol and ethyl acetate, and the mass ratio of the absolute ethyl alcohol to the ethyl acetate is 1:2;
(5) And (3) solvent recovery: vacuum distilling to recover solvent to obtain long chain fatty acid isobornyl ester crude product;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the stearic acid feed is in excess, the degree of reaction progress needs to be measured according to the camphene conversion condition. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 88 percent; after the purification, the content of isobornyl stearate in GC was 99.7%, fenchyl stearate was 0.2%, and terpinyl stearate was 0.1%.
Example 18
A method for accelerating the synthesis reaction rate of isobornyl oleate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene and long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous zirconium sulfate, citric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 4 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 5 times at the water temperature of 80 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass of 4 times into the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain a layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is absolute ethyl alcohol and ethyl acetate, and the mass ratio of the organic solvent b to the ethyl acetate is 1:5;
(5) And (3) solvent recovery: vacuum distilling to recover solvent to obtain long chain fatty acid isobornyl ester crude product;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5) to remove unreacted light components such as camphene, isomeric terpinene and the like, so as to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the oleic acid feed is in excess, the degree of reaction progress needs to be measured in terms of camphene conversion. After the reaction is finished, the conversion rate of camphene is 87.2% by analyzing the product; the product was purified to give isobornyl oleate with a GC content of 97.8%, fenchyl oleate 1.2%, terpinyl oleate 1.0%.
Example 19
A method for accelerating the synthesis reaction rate of isobornyl linoleate comprises the following steps:
(1) And (3) synthesis reaction: mixing camphene with long-chain fatty acid according to a molar ratio of 1:1.5, the mass ratio of the composite catalyst to the camphene is 0.3:1, adding the mixture into a reaction kettle, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours; the composite catalyst is prepared by mixing anhydrous zirconium sulfate, citric acid and boric acid in a mass ratio of 1; the boric acid is dehydrated boric acid heated for 1 hour at 110 ℃;
(2) And (3) filtering: standing after the reaction in the step (1) is finished, filtering a liquid product, transferring the liquid product into a washing tank, adding an organic solvent a into the reaction kettle, washing the solid catalyst at the bottom of the kettle for 3 times, filtering a washing liquid, and transferring the washing liquid into the washing tank, wherein the organic solvent a is ethyl acetate;
(3) Washing with water: adding water with the mass of 100 percent of camphene, washing for 5 times at the water temperature of 80 ℃ to obtain a mixture containing long-chain fatty acid and long-chain fatty acid isobornyl ester;
(4) And (3) product purification: adding an organic solvent b with the mass being 4 times that of the mixture obtained in the step (3) for dissolving, then dropwise adding a sodium hydroxide solution, filtering out generated soap, and finally adding water for washing to obtain layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium water solution, wherein the organic solvent b is ethyl acetate;
(5) And (3) solvent recovery: decompressing and distilling to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester;
(6) And (3) refining a product: and (4) fractionating the crude long-chain fatty acid isobornyl ester obtained in the step (5), and removing unreacted camphene, isomeric terpinene and other light components to obtain the high-purity long-chain fatty acid isobornyl ester.
Since the linoleic acid feed is in excess, the extent of reaction progress is measured in terms of camphene conversion. After the reaction is finished, analyzing the product to obtain the conversion rate of the camphene of 86 percent; the GC content of the product, i.e., purified isocamphol linoleate, was 98.5%, fenchyl linoleate was 1.0%, and terpinyl linoleate was 0.5%.
Comparative example 1
Blank experiment. And (3) synthesis reaction: adding camphene and oleic acid in a molar ratio of 1:1.5, adding the mixture into a reaction kettle, starting stirring, controlling the reaction temperature to be 90 ℃ and the reaction time to be 24 hours, wherein the rotating speed is 500 rpm; no catalyst is present. After the reaction is finished, sampling and carrying out GC analysis, wherein the GC content of camphene in the product is 86 percent, the GC content of tricyclene is 13 percent, and isobornyl oleate is not detected. It can be seen that in the absence of catalyst, camphene does not react with oleic acid.
Comparative example 2
Sulfuric acid is used as a catalyst. And (3) synthesis reaction: mixing camphene and stearic acid according to a molar ratio of 1:1.5, the mass ratio of sulfuric acid to camphene is 0.3:1, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature at 90 ℃ and the reaction time at 24h. After the reaction was complete, the product was black in color. After the reaction is finished, the product can be directly sampled, washed to be neutral by water, dissolved by ethyl acetate and then subjected to GC analysis. By GC analysis of the product, more isomeric limonene and polymerization by-products were found. The selectivity of the isobornyl stearate is 60 percent and is lower than that of the target product of the invention.
Comparative example 3
Titanium sulfate alone was used as the catalyst. And (3) synthesis reaction: mixing camphene and stearic acid according to a molar ratio of 1:1.5, the mass ratio of titanium sulfate to camphene is 0.3:1, starting stirring at the rotating speed of 500rpm, controlling the reaction temperature to be 80 ℃ and the reaction time to be 24 hours. After the reaction is finished, the product can be directly sampled, washed to be neutral by water, dissolved by ethyl acetate and then subjected to GC analysis. By GC analysis of the product, the conversion of camphene was 65%. Under the same reaction conditions, the conversion rate of camphene is 86% by using the titanium sulfate, tartaric acid and boric acid composite catalyst (the mass ratio is 1. In addition, compared with the composite catalyst, the single titanium sulfate catalyst uses titanium sulfate as the catalyst, and has the advantages of easy preparation and easy recycling, and the defect of slow reaction rate.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (10)
1. A method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester comprises the following steps: the method comprises the following steps of synthesis reaction, filtration, washing, product purification, solvent recovery and product refining, and is characterized in that the synthesis reaction step comprises the following steps:
adding camphene and long-chain fatty acid into a reaction kettle according to the mol ratio of 1.2-1.6, the mass ratio of the composite catalyst to camphene of 0.05-0.3, starting stirring, controlling the reaction temperature to be 80-90 ℃ and the reaction time to be 15-24 h; the composite catalyst consists of anhydrous sulfate, alpha-hydroxy acid and boric acid according to a mass ratio of 1.
2. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which is characterized in that: the anhydrous sulfate comprises one or more of ferric sulfate, zirconium sulfate and titanium sulfate.
3. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which comprises the following steps: the alpha-hydroxycarboxylic acid comprises one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid and glycolic acid.
4. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which is characterized in that: the boric acid is dehydrated boric acid which is heated for 1 hour at the temperature of 105-110 ℃.
5. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which comprises the following steps: the filtration steps are as follows: and standing the liquid product after the reaction is finished, filtering the liquid product, transferring the liquid product into a washing tank, adding an organic solvent into the reaction kettle, washing the solid catalyst at the bottom of the kettle, filtering the washing liquid, and transferring the washing liquid into the washing tank.
6. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which comprises the following steps: the water washing steps are as follows: adding a certain amount of water, and washing with controlled water temperature to obtain mixture of long chain fatty acid and long chain fatty acid isobornyl ester.
7. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which comprises the following steps: the product purification steps are as follows: adding an organic solvent into the mixture obtained by washing for dissolving, then dripping an alkali solution, filtering out generated soap, and finally adding water for washing to obtain the layered long-chain fatty acid isobornyl ester and long-chain fatty acid sodium aqueous solution.
8. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 7, which comprises the following steps: the alkali solution comprises one of potassium hydroxide solution and sodium hydroxide solution.
9. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which is characterized in that: the solvent recovery steps are as follows: and (3) distilling under reduced pressure to recover the solvent to obtain a crude product of the long-chain fatty acid isobornyl ester.
10. The method for accelerating the synthesis reaction rate of long-chain fatty acid isobornyl ester according to claim 1, which comprises the following steps: the product refining steps are as follows: and (3) carrying out reduced pressure fractionation on the crude product of the long-chain fatty acid isobornyl ester obtained in the solvent recovery step to remove light components of camphene and terpinene, thus obtaining a fine product of the long-chain fatty acid isobornyl ester.
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