CN114644557A - Preparation method of isostearyl alcohol isostearate - Google Patents
Preparation method of isostearyl alcohol isostearate Download PDFInfo
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- CN114644557A CN114644557A CN202210296650.XA CN202210296650A CN114644557A CN 114644557 A CN114644557 A CN 114644557A CN 202210296650 A CN202210296650 A CN 202210296650A CN 114644557 A CN114644557 A CN 114644557A
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- isostearyl isostearate
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- isostearate
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- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 16
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229940060384 isostearyl isostearate Drugs 0.000 claims abstract description 54
- 239000000047 product Substances 0.000 claims abstract description 47
- 238000005886 esterification reaction Methods 0.000 claims abstract description 36
- 238000000199 molecular distillation Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
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- 230000035484 reaction time Effects 0.000 claims description 9
- 238000007790 scraping Methods 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 6
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
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- 238000007127 saponification reaction Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of isostearyl alcohol isostearate. The preparation method of isostearyl isostearate comprises the following steps: 1) mixing isostearyl alcohol, isostearic acid, a catalyst and a water carrying agent, and carrying out esterification reaction to obtain a reaction solution containing ester; 2) extracting ester from the reaction liquid containing ester, and distilling under reduced pressure to obtain a crude product; 3) and (3) performing molecular distillation on the crude product to obtain an isostearyl isostearate product. The isostearyl isostearate product has high purity, the acid value is lower than 1mgKOH/g, the hydroxyl value is lower than 5mgKOH/g, the chroma is lower than 70Hazen, no peculiar smell exists, the irritation is low, the preparation process is simple, efficient and environment-friendly, and the isostearyl isostearate is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and refining, and particularly relates to a preparation method of isostearyl isostearate.
Background
Isostearyl alcohol isostearate is long-carbon-chain fatty acid ester with a relatively large molecular weight, is colorless and transparent light yellow liquid at normal temperature, has no pungent smell, has a branched chain structure of isostearic acid and isostearyl alcohol, well inherits the low-temperature fluidity of isostearic acid, can be used as an emollient, a binder and a repairing agent applied to various skin care products or color cosmetics products, provides soft and smooth skin feel, has good air permeability and excellent waterproofness, is a preferred substitute of natural jojoba oil, not only has the advantages of the jojoba oil, but also has more excellent oxidation stability. Along with the increasing attention paid to the necessity of daily nursing and cleaning, the market of personal care products is gradually expanded, the demand of the market for high-quality isostearyl alcohol isostearate products with low chroma, small acidity, small saponification value and small irritation is gradually increased, and the personal care products have considerable economic value.
In order to increase the esterification rate and purity of isostearyl isostearate, a more acidic catalyst (such as concentrated sulfuric acid) is usually added, and the reaction temperature is increased and the reaction time is prolonged. However, the use of a large amount of an acidic catalyst tends to result in a high acid value and strong irritation in the final product, and an increase in the esterification reaction temperature tends to produce a by-product, which may result in a decrease in the purity and a darkening in the color of isostearyl isostearate, and the obtained isostearyl isostearate may not satisfy the requirements for use as a raw material for cosmetics.
Alkali refining, using strong base such as NaOH and KOH to perform saponification reaction with unreacted fatty acid, and further separating, and adsorbing colored substances generated by side reaction by using adsorbents such as activated carbon and activated clay. At present, the processes of alkali refining and adsorption deacidification decoloration can be adopted to improve the purity of the crude product of isostearyl isostearate, reduce the chromaticity and effectively reduce the acid value of the product, but a large amount of soap base can be generated, the irritation to skin is large, the yield of the product is influenced, the great waste is caused, and the treatment effect of the adsorption decoloration on a system with approximate structural properties is limited, the process is complex and the economical efficiency is poor.
Therefore, there is a need to develop a preparation method of isostearyl isostearate with high purity, small acid value and low chroma, which is simple in process, efficient, environment-friendly, suitable for large-scale preparation.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a preparation method of isostearyl isostearate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of isostearyl alcohol isostearate, which comprises the following steps:
1) mixing isostearyl alcohol, isostearic acid, a catalyst and a water carrying agent, and carrying out esterification reaction to obtain a reaction solution containing ester;
2) extracting ester from the reaction liquid containing ester, and distilling under reduced pressure to obtain a crude product;
3) and (3) performing molecular distillation on the crude product to obtain an isostearyl isostearate product.
Preferably, the method for preparing isostearyl isostearate comprises the following steps:
1) mixing isostearyl alcohol, isostearic acid, a catalyst and a water carrying agent, and carrying out esterification reaction to obtain a reaction solution containing ester;
2) adding water and cyclohexane into the reaction solution containing ester, extracting, separating liquid, and distilling an organic phase under reduced pressure to obtain a crude product;
3) and carrying out primary molecular distillation on the crude product, and then carrying out secondary molecular distillation to obtain an isostearyl isostearate product.
Preferably, the mass ratio of the isostearyl alcohol, the isostearic acid and the catalyst in the step 1) is 10: 9-11: 2-4.
More preferably, the mass ratio of the isostearyl alcohol, the isostearic acid and the catalyst in the step 1) is 10: 9.5-10.5: 2.8-3.2.
Preferably, the volume ratio of the water carrying agent to the isostearyl alcohol in the step 1) is 1: 1-1: 10.
Further preferably, the volume ratio of the water-carrying agent to the isostearyl alcohol in the step 1) is 1:2 to 1: 6.
Preferably, the catalyst in the step 1) is p-benzenesulfonic acid.
Preferably, the water carrying agent in step 1) is cyclohexane or n-hexane.
Preferably, the temperature of the esterification reaction in the step 1) is 120-135 ℃.
Further preferably, the temperature of the esterification reaction in the step 1) is 125 to 133 ℃.
Preferably, the esterification reaction time in the step 1) is 90min to 140 min.
Further preferably, the esterification reaction time in the step 1) is 100min to 120 min.
Preferably, an inert gas is kept continuously purged during the esterification reaction in step 1).
Preferably, the inert gas is one or more of nitrogen, argon, neon and helium.
Preferably, the inert gas is nitrogen.
Preferably, the reaction solution containing ester in the step 2) is cooled to 50-70 ℃, and then water and cyclohexane are added.
Preferably, the volume ratio of the water to the cyclohexane in the step 2) is 3: 1-5: 1.
Preferably, step 2) further comprises washing the separated oil layer with water.
Preferably, the reduced pressure distillation in the step 2) is carried out at the temperature of 80-95 ℃ and the vacuum degree of 0.1 MPa.
More preferably, the reduced pressure distillation in the step 2) is carried out at a temperature of 85 to 90 ℃ and a vacuum degree of 0.1 MPa.
Preferably, the time of the reduced pressure distillation treatment in the step 2) is 20min to 40 min.
Preferably, the number of times of the primary molecular distillation treatment in the step 3) is 2.
Preferably, the number of times of the secondary molecular distillation treatment in step 3) is 1.
Preferably, the first-stage molecular distillation treatment in the step 3) is carried out under the conditions that the temperature is 135-160 ℃, the vacuum degree is 3-5 Pa, the film scraping rotation speed is 200-400 r/min, and the feeding rate is 100-300 mL/h.
Further preferably, the first-stage molecular distillation treatment in the step 3) is carried out under the conditions that the temperature is 140-150 ℃, the vacuum degree is 3.5-4.5 Pa, the rotating speed of a film scraper is 300r/min, and the feeding rate is 150-200 mL/h.
Preferably, the secondary molecular distillation treatment in the step 3) is carried out under the conditions that the temperature is 180-225 ℃, the vacuum degree is 3-5 Pa, the film scraping rotation speed is 200-400 r/min, and the feeding rate is 80-180 mL/h.
Further preferably, the secondary molecular distillation treatment in the step 3) is carried out under the conditions that the temperature is 190-220 ℃, the vacuum degree is 3.5-4.5 Pa, the rotating speed of a film scraper is 300r/min, and the feeding rate is 140-160 mL/h.
The invention also provides an isostearyl isostearate product prepared by the preparation method.
Preferably, the purity of the isostearyl alcohol isostearate product is 95 to 99.9 percent.
Preferably, the isostearyl isostearate product has an acid number of less than 1 mgKOH/g.
Preferably, the isostearyl isostearate product has a hydroxyl number of less than 5 mgKOH/g.
Preferably, the isostearyl isostearate product has a color of less than 70 Hazen.
The beneficial effects of the invention are: the invention provides a preparation method of isostearyl isostearate, which has the advantages of simple process, high efficiency, environmental protection, suitability for large-scale production, high purity, small acid value and low chroma. The method specifically comprises the following steps:
(1) the method for preparing isostearyl isostearate provided by the invention can realize higher esterification rate in a short time (20min) under the condition of no strong acid in the esterification reaction, the esterification rate can reach 95.67 percent at the time of esterification reaction for 40min and 98.63 percent at the time of esterification reaction for 100min, and the acid value of an esterified crude product can reach below 2 mgKOH/g;
(2) according to the preparation method of isostearyl alcohol isostearate, the operation of alkali washing deacidification, adsorption decoloration deodorization and the like is not needed for the esterification crude product, the unreacted raw materials and the dark color substances generated by side reaction can be separated only by secondary molecular distillation treatment, the process is simple, the treatment cost is low, and the method is suitable for industrial production, wherein the isostearyl alcohol and the isostearic acid separated by primary molecular distillation can be used as the raw materials for esterification reaction for reapplication, and is green and economic;
(3) the isostearyl isostearate product obtained by the preparation method provided by the invention has high purity, low chroma, no peculiar smell and small irritation, is suitable for being used as a raw material of cosmetics with higher requirements, and the purity of the product can reach 97.23 percent through a gas chromatography normalization method and according to national standards, the acid value can be reduced to 0.067mgKOH/g, the hydroxyl value is 1.04mgKOH/g, the saponification value is 107.3mgKOH/g, and the chroma is 50 Hazen.
Drawings
FIG. 1 is a graph showing the relationship between the yield of isostearyl isostearate and the acid value and the esterification reaction time in example 1.
FIG. 2 is a gas chromatogram of the isostearyl isostearate product of example 1.
FIG. 3 is a chart of the infrared absorption spectrum of the isostearyl isostearate product of example 1.
FIG. 4 is a NMR chart of the isostearyl isostearate product of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The embodiment provides a method for preparing isostearyl alcohol isostearate, which specifically comprises the following steps:
1) weighing 100g of isostearyl alcohol, 95.51g of isostearic acid and 2.93g of p-toluenesulfonic acid in a 1000mL three-neck round-bottom flask, adding 50mL of cyclohexane as a water carrying agent, setting the heating temperature of an oil bath kettle to be 130 ℃, heating for reaction for 40min, keeping nitrogen continuously blown in during the heating reaction process, stopping heating after the reaction is finished, and continuously keeping stirring to obtain a mixed liquid after the reaction;
2) cooling the reacted mixed liquid to 70 ℃, adding 200mL of deionized water into the reacted mixed liquid, continuously stirring 50mL of cyclohexane for 10min, transferring the feed liquid in the three-neck flask into a separating funnel, standing for layering, discharging the lower-layer water phase after layering, adding 500mL of deionized water into the upper-layer oil phase (namely organic phase), and repeatedly washing for 2-3 times to obtain the washed upper-layer oil phase (namely organic phase);
3) pouring the washed upper oil phase into a three-neck flask, and carrying out reduced pressure distillation for 30min under the conditions that the temperature is set to be 90 ℃ and the vacuum degree is 0.1MPa to obtain an esterification crude product (the esterification rate is 95.67 percent when the acid value of reactants before and after the reaction is measured);
4) performing primary molecular distillation treatment on the esterification crude product (i.e. the esterification crude product subjected to deacidification and dehydration treatment) in the step 3) for 2 times, setting the distillation temperature to be 140 ℃, the vacuum degree to be 4Pa, the film scraping rotation speed to be 300r/min, the feeding rate to be 200mL/h, observing the film forming condition of the feed liquid on the heating wall in the distillation process, properly adjusting the feeding amount, and collecting heavy-phase components (components with heavy mass);
5) performing secondary molecular distillation treatment on the heavy phase component collected in the step 4), setting the distillation temperature to be 190 ℃, the vacuum degree to be 4Pa, the film scraping rotation speed to be 300r/min, the feeding rate to be 100mL/h, observing the film forming condition of the feed liquid on a heating wall in the distillation process, properly adjusting the feeding amount, and collecting the light phase after the distillation is finished to obtain an isostearyl isostearate product;
wherein, the first molecular distillation needs to be distilled for 2 times, and the second molecular distillation only needs to be distilled for 1 time.
Example 2
The embodiment provides a preparation method of isostearyl isostearate, which specifically comprises the following steps:
1) weighing 250g of isostearyl alcohol, 262.92g of isostearic acid and 7.69g of p-toluenesulfonic acid in a 1000mL three-neck round-bottom flask, adding 50mL of cyclohexane as a water carrying agent, setting the heating temperature of an oil bath kettle to be 130 ℃, reacting for 100min, keeping nitrogen continuously blown in during the heating reaction process, stopping heating after the reaction is finished, and continuously keeping stirring to obtain a mixed liquid after the reaction;
2) cooling the reacted mixed liquid to 70 ℃, adding 200mL of deionized water into the mixed liquid, continuously stirring 50mL of cyclohexane for 10min, transferring the material liquid in the three-neck flask into a separating funnel, standing for layering, removing the lower-layer water phase after layering, adding 500mL of deionized water, and repeating the washing operation for 2-3 times to obtain the washed upper-layer oil phase (namely the organic phase);
3) pouring the washed upper oil phase into a three-neck flask, and carrying out reduced pressure distillation for 30min under the conditions that the temperature is set to be 90 ℃ and the vacuum degree is 0.1MPa to obtain an esterification crude product (the esterification rate is 98.63 percent when the acid values of reactants before and after the reaction are measured);
4) performing primary molecular distillation treatment on the esterified crude product (namely the esterified crude product subjected to deacidification and dehydration treatment) in the step 3) for 2 times, setting the distillation temperature to be 140 ℃, the vacuum degree to be 4Pa, the film scraping rotation speed to be 300r/min, the feeding speed to be 200mL/h, observing the film forming condition of the feed liquid on a heating wall in the distillation process, properly adjusting the feeding amount, and collecting heavy-phase components;
5) performing secondary molecular distillation treatment on the heavy phase collected in the step 4), setting the distillation temperature to be 200 ℃, the vacuum degree to be 4Pa, the film scraping rotation speed to be 300r/min, the feeding rate to be 150mL/h, observing the film forming condition of the feed liquid on a heating wall in the distillation process, properly adjusting the feeding amount, and collecting the light phase after the distillation is finished to obtain an isostearyl isostearate product;
wherein, the first molecular distillation needs to be distilled for 2 times, and the second molecular distillation only needs to be distilled for 1 time.
Example 3
The embodiment provides a method for preparing isostearyl alcohol isostearate, which specifically comprises the following steps:
1) weighing 900g of isostearyl alcohol, 901.44g of isostearic acid and 27.02g of p-toluenesulfonic acid in a reaction kettle, adding 200mL of cyclohexane as a water carrying agent, setting the heating temperature of the reaction kettle at 130 ℃, setting the reaction time at 100min, keeping nitrogen continuously blown in during the heating reaction process, stopping heating after the reaction is finished, and continuously keeping stirring to obtain a mixed liquid after the reaction;
2) cooling the reacted mixed liquid to 60 ℃, adding 1000mL of deionized water, continuously stirring 200mL of cyclohexane for 10min, discharging the water phase from the lower opening of the reaction kettle after standing and layering, adding 1000mL of deionized water, and repeating the water washing operation for 2-3 times to obtain a washed oil phase (namely an organic phase);
3) distilling the washed oil phase under reduced pressure at 85 deg.C and 0.1MPa for 30min to obtain yellow oily esterified crude product (the esterification rate is 97.16% calculated by measuring acid value of reactant before and after reaction);
4) performing primary molecular distillation treatment on the esterification crude product (namely the esterification crude product subjected to deacidification and dehydration treatment) in the step 3) for 2 times, setting the distillation temperature to be 150 ℃, the vacuum degree to be 4Pa, the film scraping rotation speed to be 300r/min, the feeding speed to be 200mL/h, observing the film forming condition of the feed liquid on a heating wall in the distillation process, properly adjusting the feeding amount, and collecting heavy-phase components;
5) performing secondary molecular distillation treatment on the heavy phase collected in the step 4), setting the distillation temperature at 220 ℃, the vacuum degree at 4Pa, the film scraping rotation speed at 300r/min and the feeding rate at 150mL/h, observing the film forming condition of the feed liquid on a heating wall in the distillation process, properly adjusting the feeding amount, collecting the light phase after the distillation is finished, and obtaining the isostearyl isostearate product,
wherein, the first molecular distillation needs to be distilled for 2 times, and the second molecular distillation only needs to be distilled for 1 time.
Performance testing
1) The yield and acid value of isostearyl isostearate in example 1 are shown in FIG. 1 as a graph of the esterification reaction time.
As can be seen from fig. 1: along with the increase of the reaction time, the esterification rate gradually increases and becomes gentle after 100min and is kept at the esterification rate of 99.0-99.5 percent, and the acid value of the corresponding reactant gradually decreases along with the increase of the reaction time and is kept stable at 5-10 mgKOH/g after 100 min. It can be seen that, due to the reasonable proportion of the reaction raw materials used in example 1 and the strong catalytic ability of the homogeneous catalyst, and the fact that the water generated by the reaction is blown off from the reaction system by the inert gas in time, the esterification reaction of example 1 can reach an esterification rate of 90% within a short time (20 min). After 100min of reaction, the reaction rate was then gradually decreased, because most of the acid and alcohol in the reactants had been reacted and the content of unreacted acid and alcohol was smaller, corresponding to the reactants being diluted, as the reaction gradually reached equilibrium, resulting in this result.
2) The gas chromatogram of the isostearyl isostearate product of example 1 is shown in FIG. 2.
As can be seen from fig. 2: the signal peak of isostearyl alcohol can be determined within the retention time range of 6.5min to 8min, the signal peak of isostearic acid within the retention time range of 8min to 10min and the signal peak of the target product isostearyl alcohol isostearate within the retention time range of 12min to 15.5min through gas chromatography tests by adding a standard substance. Since the starting materials isostearyl alcohol and isostearic acid are mixtures of isomers with indeterminate isomeric structures, the product isostearyl isostearate is also not a pure compound because of the indeterminate isomeric structures and their peaks in the gas chromatograph are randomly asymmetric. Thus, the internal and external standards are not suitable for the determination of the ester content and the product isostearyl isostearate is 97.23% pure by normalization.
3) The IR absorption spectrum of the isostearyl isostearate product of example 1 is shown in FIG. 3.
As can be seen from fig. 3: the isostearyl isostearate product of example 1 was 724.2cm each-1、1167.7cm-1、1375.1cm-1、1463.3cm-1、1739.9cm-1、2855.6cm-1、2924.8cm-1、3435cm-1Has an absorption peak. The analysis shows that the density is 724.2cm-1Long-chain saturated hydrocarbon- (CH)2)nThe characteristic peak of bending vibration (n is more than or equal to 4); 1167.7cm-1The asymmetric stretching vibration peak is C-O; 1375.1cm-1Is represented by-CH3Characteristic peak of symmetric bending vibration of 1463.3cm-1Is represented by-CH3An asymmetric flexural vibration signature peak; 1739.9cm-1C ═ O characteristic absorption peak at ester group; 2855.6cm-1Symmetric stretching vibration is carried out at-CH 2; 2924.8cm-1Is represented by-CH2Asymmetric stretching vibration; 3454cm-1the-OH absorption peak of the remaining isostearyl alcohol was obtained. According to the analysis of the attribution of the infrared absorption characteristic peak groups, the product conforms to the structure of isostearyl alcohol isostearate, and no abnormal absorption peak is found except for an-OH absorption peak.
4) The NMR spectrum of the isostearyl isostearate product of example 1 is shown in FIG. 4.
From the analysis of fig. 4, it can be seen that: the structural parameters of the product are as follows: delta 4.04-4.07 (t, -COOCH)2-,2H)；δ2.27～2.30(t,-CH2CO-,2H)；δ1.61～1.72(m，-CH2-CH2CO-and-OCH2-CH2-,4H)；δ1.59～1.60(m，-CH2-(CH2)2-CO-、-O(CH2)2-CH2-and-CH (CH)3)-，6H)；δ1.05～1.29(m，-CH2-CH2-,46H；δ0.81～0.89(m，-CH3And 12H). The peak analysis confirmed that the product was isostearyl isostearate.
Tests show that the reaction law, gas chromatography, infrared spectrum and nuclear magnetic resonance hydrogen spectrum of the isostearyl isostearate prepared in the examples 2-3 are very close to those of the isostearyl isostearate product prepared in the example 1.
5) Since the isostearyl alcohol isostearate products obtained in examples 1 to 3 were mixtures of isomers, the product purity was calculated as follows by gas chromatography normalization. The acid value of the product is determined by a hot ethanol indicator titration method in GB 5009.229-2016 acid value determination in food safety national standard food; measuring the hydroxyl value of the product by adopting a phthalic anhydride method in GB/T7383 and 2020 non-ionic surfactant hydroxyl value measurement; measuring the saponification value of the product by adopting a method in GB/T5534-2008 determination of animal and vegetable oil saponification values; the color of the product is determined by a platinum-cobalt color number method in GB/T3143-1982 liquid chemical product color determination method.
TABLE 1 physicochemical parameters of isostearyl isostearate products of examples 1 to 3
As can be seen from Table 1: the isostearyl isostearate products prepared by the preparation methods of examples 1-3 have the purity of more than 96%, the acid value of less than 0.30mgKOH/g, the hydroxyl value of less than 2.0mgKOH/g, the chroma of less than 65Hazen, the saponification value of 105 mgKOH/g-155 mgKOH/g, no special odor and good comprehensive physical and chemical properties, so the isostearyl isostearate products are suitable for being used as raw materials of cosmetics with high requirements on purity, chroma, acid value and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing isostearyl isostearate is characterized by comprising the following steps:
1) mixing isostearyl alcohol, isostearic acid, a catalyst and a water carrying agent, and performing esterification reaction to obtain reaction liquid containing ester;
2) extracting ester from the reaction liquid containing ester, and distilling under reduced pressure to obtain a crude product;
3) and (3) performing molecular distillation on the crude product to obtain an isostearyl isostearate product.
2. The method of producing isostearyl isostearate according to claim 1, which comprises the steps of:
1) mixing isostearyl alcohol, isostearic acid, a catalyst and a water carrying agent, and performing esterification reaction to obtain reaction liquid containing ester;
2) adding water and cyclohexane into the reaction solution containing ester, extracting, separating liquid, and distilling an organic phase under reduced pressure to obtain a crude product;
3) and carrying out primary molecular distillation on the crude product, and then carrying out secondary molecular distillation to obtain an isostearyl isostearate product.
3. The method for producing isostearyl isostearate according to claim 1 or 2, which comprises: the mass ratio of the isostearyl alcohol, the isostearic acid and the catalyst in the step 1) is 10: 9-11: 2-4.
4. The method of producing isostearyl isostearate according to claim 3, which comprises: the catalyst in the step 1) is p-toluenesulfonic acid; the water carrying agent in the step 1) is cyclohexane or normal hexane.
5. The method for producing isostearyl isostearate according to claim 1 or 2, which comprises: the temperature of the esterification reaction in the step 1) is 120-135 ℃.
6. The method of producing isostearyl isostearate according to claim 5, which comprises: the esterification reaction time in the step 1) is 90-140 min.
7. The method of producing isostearyl isostearate according to claim 2, which comprises: the volume ratio of the water to the cyclohexane in the step 2) is 3: 1-5: 1.
8. The method of producing isostearyl isostearate according to claim 2, which comprises: the frequency of the primary molecular distillation treatment in the step 3) is 2 times; the number of times of the secondary molecular distillation treatment in the step 3) is 1.
9. The method of producing isostearyl isostearate according to claim 8, which comprises: the first-stage molecular distillation treatment of the step 3) is carried out under the conditions that the temperature is 135-160 ℃, the vacuum degree is 3 Pa-5 Pa, the rotating speed of the knifing is 200 r/min-400 r/min, and the feeding rate is 100 mL/h-300 mL/h.
10. The method of producing isostearyl isostearate according to claim 8, which comprises: and 3) performing secondary molecular distillation treatment under the conditions that the temperature is 180-225 ℃, the vacuum degree is 3-5 Pa, the film scraping rotation speed is 200-400 r/min, and the feeding rate is 80-180 mL/h.
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