CN111848403A - Preparation method of pentaerythritol tetraisostearate - Google Patents
Preparation method of pentaerythritol tetraisostearate Download PDFInfo
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- CN111848403A CN111848403A CN201910341787.0A CN201910341787A CN111848403A CN 111848403 A CN111848403 A CN 111848403A CN 201910341787 A CN201910341787 A CN 201910341787A CN 111848403 A CN111848403 A CN 111848403A
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The invention provides a preparation method of pentaerythritol tetraisostearate, which comprises the following steps: s1, taking materials of pentaerythritol and isostearic acid according to a molar ratio of 1: 3.8-4.8, taking materials of a catalyst and pentaerythritol according to a mass ratio of 0.01-0.3: 1, and putting the materials into a reaction kettle; s2, under the condition that the vacuum pressure is-0.1 to-0.05 MPa, the reaction temperature is 100 to 160 DEGoAnd C, reacting for 0.5-12 hours to obtain a pentaerythritol tetraisostearate product. The method has mild reaction conditions, greatly reduces the reaction temperature, and can be realized by a conventional enamel reaction kettle; the reaction time is short, and the energy consumption is low; the product has light color and high quality; the post-reaction treatment is simple and convenient, and is suitable for industrialization.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of pentaerythritol tetraisostearate.
Background
Pentaerythritol tetraisostearate is a large molecular weight liquid oil. Pentaerythritol tetraisostearate is basically odorless, has high thermal stability, has the functions of forming a film, resisting water, moistening skin and the like, and is a non-viscous humectant. Meanwhile, pentaerythritol tetraisostearate does not block pores, has good powder dispersibility and suspensibility, prevents sedimentation and has good skin adhesion, thus being an excellent cosmetic additive.
In the literature, pentaerythritol tetraisostearate is mainly prepared by dehydrating and esterifying pentaerythritol and isostearic acid at high temperature and normal pressure under the catalysis of protonic acid such as p-toluenesulfonic acid and the like or Lewis acid such as ferric trichloride and the like. Patent CN101293828 reports a method for preparing pentaerythritol tetraisostearate by performing dehydration esterification at 160-240 ℃ for 5-9 hours under the condition of stannous oxide or zinc chloride or ferric chloride accounting for 0.03-0.1% of total weight of pentaerythritol and isostearic acid, and the preparation examples are described briefly, no post-treatment/purification process is described, and no basic quality indexes such as color, purity and the like of the product are described. Patent CN105801407 reports that zinc-iron composite metal oxide reacts for 4-5 hours at 140-150 ℃ for dehydration and esterification, and the patent describes that the obtained product has excellent chroma and acid value. However, the preparation process of the composite metal oxide is complex, and the composite metal oxide needs to be subjected to rapid nucleation, microwave treatment, crystallization and drying and then is transferred to 600 ℃ for roasting. However, the esterification reaction was found to be very slow after repeated patent operations in the laboratory, and the technical effect described in the patent was far from being achieved. Patent CN101298417 reports that 0.1-1% of p-toluenesulfonic acid based on the weight of isostearic acid is used for catalyzing dehydration esterification for 10-24 hours at 160-240 ℃, nonpolar and polar solvents are added after the reaction is finished, alkaline water is added for neutralization, the solvent is removed by evaporation under reduced pressure after the reaction is washed to be neutral, and the product has excellent chroma and acid value. However, when the conditions were reproduced in the laboratory, the product was found to be darker in color and a large amount of isostearic acid remained in the reaction.
Therefore, it is urgently needed to provide a preparation method for preparing pentaerythritol tetraisostearate, which has the advantages of light color, high purity, stable process, simple and convenient operation and suitability for industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of pentaerythritol tetraisostearate, which is simple and feasible, stable in process, easy to control, convenient in post-reaction treatment, good in product yield, high in purity, light in color, and capable of being economically and conveniently used for industrial production.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of pentaerythritol tetraisostearate comprises the following steps:
s1, taking materials of pentaerythritol and isostearic acid according to a molar ratio of 1: 3.8-4.8, taking materials of a catalyst and pentaerythritol according to a mass ratio of 0.01-0.3: 1, and putting the materials into a reaction kettle;
s2, reacting for 0.5-12 hours under the vacuum pressure of-0.1-0.05 MPa and the reaction temperature of 100-160 ℃ to obtain pentaerythritol tetraisostearate product;
the reaction scheme is as follows:
wherein R ═ isostearoyl.
Preferably, the reaction takes place in the absence of a solvent.
Preferably, the feeding molar ratio of the pentaerythritol to the isostearyl chloride is 1: 4.0-4.4.
Preferably, the catalyst is one or more of stannous oxide, zinc oxide, stannous dichloride or zinc chloride.
Preferably, the catalyst is one or more of stannous oxide or stannous dichloride.
Preferably, the mass ratio of the catalyst to the pentaerythritol is 0.05-0.2: 1.
Preferably, the reaction temperature is 120-150 ℃.
Preferably, the reaction time is 2 to 6 hours.
Preferably, the vacuum pressure is-0.098 to-0.06 MPa.
Compared with the prior art, the invention has the following beneficial effects: the invention has mild reaction conditions, greatly reduces the reaction temperature, and can be realized by a conventional enamel reaction kettle; the reaction time is short, and the energy consumption is low; the product has light color and high quality; the post-reaction treatment is simple and convenient, and is suitable for industrialization.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention. These examples are not meant to impose any limitation on the invention. It will be apparent that those skilled in the art can make various changes and modifications to the present invention within the scope and spirit of the present invention. It is to be understood that the invention is intended to cover such alternatives and modifications as may be included within the scope of the appended claims.
EXAMPLE 1 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) is suspended in isostearic acid (230g, 809mmol), stannous oxide (2.5g, 18.4mmol) is added, air in a nitrogen gas replacement system is decompressed (vacuum degree: -0.098MPa), the temperature is increased to 140 ℃ and 150 ℃ for reaction for 4 hours, and the TLC detection reaction is basically finished. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water, mixing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing, separating liquid, adding activated carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 216.7g of colorless oily substance, wherein the yield is 98%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.10.
EXAMPLE 2 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) is suspended in isostearic acid (209g, 736mmol), stannous dichloride (25g, 184mmol) is added to replace the air in the system by nitrogen, the pressure is reduced (the vacuum degree is: -0.06MPa), the temperature is increased to 120 ℃ and 130 ℃ for reaction for 2 hours, and the TLC detection reaction is basically finished. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water, mixing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing, separating liquid, adding active carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 204.8g of colorless oily substance, wherein the yield is 98%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.10.
EXAMPLE 3 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) was suspended in isostearic acid (220g, 772.8mmol), zinc oxide (50g, 368mmol) was added to displace the air in the system with nitrogen, the pressure was reduced (degree of vacuum: -0.05MPa), the temperature was raised to 100 ℃ and 110 ℃ for reaction for 6 hours, and the reaction was almost completed by TLC detection. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water, mixing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing, separating liquid, adding activated carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 217.8g of colorless oily substance, wherein the yield is 99%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.10.
EXAMPLE 4 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) was suspended in isostearic acid (251g, 883.2mmol), zinc chloride (75g, 552mmol) was added to replace the air in the system with nitrogen, the pressure was reduced (degree of vacuum: -0.07MPa), the temperature was raised to 140 ℃ and 150 ℃ to react for 0.5 hour, and the reaction was almost completed by TLC detection. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water, mixing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing, separating liquid, adding active carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 246g of colorless oily matter, wherein the yield is 98%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.10.
EXAMPLE 5 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) is suspended in isostearic acid (198.7g, 699.2mmol), stannous oxide (1.25g, 9.2mmol) is added to replace the air in the system with nitrogen, the pressure is reduced (vacuum degree: -0.07MPa), the temperature is increased to 140 ℃ and 150 ℃ for reaction for 0.5 h, and the TLC detection reaction is basically completed. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water, mixing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing and separating liquid; adding 30mL of methanol into the upper layer, mixing, standing, separating liquid, adding activated carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 194.7g of colorless oily substance, wherein the yield is 98%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.10.
EXAMPLE 6 preparation of pentaerythritol Tetraisostearate
Pentaerythritol (25g, 184mmol) is suspended in isostearic acid (209.4g, 736mmol), stannous oxide (1.25g, 9.2mmol) is added to replace the air in the system with nitrogen, the pressure is reduced (vacuum degree: -0.08MPa), the temperature is increased to 140 ℃ and 150 ℃ for reaction for 0.5 h, and the TLC detection reaction is basically completed. Cooling to 30-40 ℃, adding 300mL of n-heptane and 30mL of 1M hydrochloric acid, mixing, standing and separating liquid; adding 30mL of water into the upper layer, mixing, separating liquid, adding active carbon into the upper layer, stirring for half an hour at 50-60 ℃, filtering, and concentrating to obtain 121.2g of colorless oily matter, wherein the yield is 100%, the chroma is less than 1, the dry loss is less than or equal to 0.5%, and the acid value is 0.20.
Comparative example 1 preparation of pentaerythritol tetraisostearate
Pentaerythritol (25g, 184mmol) is suspended in isostearic acid (230g, 809mmol), stannous oxide (2.5g, 18.4mmol) is added to replace the air in the system with nitrogen, the temperature is raised to 140 ℃ and 150 ℃ for reaction for 6 hours, and about half of isostearic acid is remained after TLC detection reaction.
In this comparative example, as compared with example 1, no vacuum condition was used in the preparation of pentaerythritol tetraisostearate, and even if the reaction time was prolonged, the reaction was still incomplete and about half of isostearic acid remained in the product.
Comparative example 2 preparation of pentaerythritol tetraisostearate
Pentaerythritol (25g, 184mmol) was suspended in isostearic acid (204g, 717mmol), ferric chloride (0.184g, 1.1mmol) was added to replace the air in the system with nitrogen, the temperature was raised to 220 ℃ to react for 7 hours, TLC detected that about 10% of isostearic acid remained, about 20% of pentaerythritol triisostearate intermediate remained, and the reaction mixture was dark brown in color.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A preparation method of pentaerythritol tetraisostearate is characterized by comprising the following steps:
s1, feeding pentaerythritol and isostearic acid according to a molar ratio of 1: 3.8-4.8, feeding a catalyst and pentaerythritol according to a mass ratio of 0.01-0.3: 1, and putting into a reaction kettle;
s2, reacting for 0.5-12 hours under the vacuum pressure of-0.1-0.05 MPa and the reaction temperature of 100-160 ℃ to obtain pentaerythritol tetraisostearate;
the reaction route is as follows:
wherein R ═ isostearoyl.
2. The method of claim 1, wherein the reaction is carried out in the absence of a solvent.
3. The method of claim 1, wherein the molar ratio of pentaerythritol to isostearic acid added is preferably 1: 4.0-4.4.
4. The method of claim 1, wherein the catalyst is one or more of stannous oxide, zinc oxide, stannous dichloride, or zinc chloride.
5. The method of claim 1, wherein the catalyst is one or more of stannous oxide or stannous dichloride.
6. The method of claim 1, wherein the mass ratio of the catalyst to pentaerythritol is preferably 0.05 to 0.2: 1.
7. The method according to claim 1, wherein the reaction temperature is 120 to 150 ℃.
8. The method of claim 1, wherein the reaction time is 2 to 6 hours.
9. The method of producing pentaerythritol tetraisostearate according to claim 1, wherein the vacuum pressure is from-0.098 to-0.06 MPa.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212816A (en) * | 1977-12-29 | 1980-07-15 | Bayer Aktiengesellschaft | Carboxylic acid esters of pentaerythritol |
| US4477383A (en) * | 1982-05-05 | 1984-10-16 | National Distillers And Chemical Corporation | Di- and tripentaerythritol esters of isostearic acid |
| CN101293828A (en) * | 2008-05-16 | 2008-10-29 | 王伟松 | Method for synthesizing pentaerythritol isostearate |
| CN101298417A (en) * | 2008-05-30 | 2008-11-05 | 广州市星业科技发展有限公司 | Preparation of pentaerythritol tetraoctyl stearate |
| CN104086417A (en) * | 2014-07-28 | 2014-10-08 | 中国石油化工股份有限公司 | Esterification method of pentaerythritol |
| CN105753698A (en) * | 2016-04-26 | 2016-07-13 | 广州煌垅生物科技有限公司 | Method for preparing pentaerythritol stearate from hydrogenated oil |
| CN105801407A (en) * | 2016-04-26 | 2016-07-27 | 广州煌垅生物科技有限公司 | Method for preparing pentaerythritol tetraisostearate |
| CN106631782A (en) * | 2016-10-17 | 2017-05-10 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol tetrabasic acid ester |
| CN106905854A (en) * | 2017-02-24 | 2017-06-30 | 青岛科技大学 | A kind of preparation method of pentalyn |
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
-
2019
- 2019-04-26 CN CN201910341787.0A patent/CN111848403A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212816A (en) * | 1977-12-29 | 1980-07-15 | Bayer Aktiengesellschaft | Carboxylic acid esters of pentaerythritol |
| US4477383A (en) * | 1982-05-05 | 1984-10-16 | National Distillers And Chemical Corporation | Di- and tripentaerythritol esters of isostearic acid |
| CN101293828A (en) * | 2008-05-16 | 2008-10-29 | 王伟松 | Method for synthesizing pentaerythritol isostearate |
| CN101298417A (en) * | 2008-05-30 | 2008-11-05 | 广州市星业科技发展有限公司 | Preparation of pentaerythritol tetraoctyl stearate |
| CN104086417A (en) * | 2014-07-28 | 2014-10-08 | 中国石油化工股份有限公司 | Esterification method of pentaerythritol |
| CN105753698A (en) * | 2016-04-26 | 2016-07-13 | 广州煌垅生物科技有限公司 | Method for preparing pentaerythritol stearate from hydrogenated oil |
| CN105801407A (en) * | 2016-04-26 | 2016-07-27 | 广州煌垅生物科技有限公司 | Method for preparing pentaerythritol tetraisostearate |
| CN106631782A (en) * | 2016-10-17 | 2017-05-10 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol tetrabasic acid ester |
| CN106905854A (en) * | 2017-02-24 | 2017-06-30 | 青岛科技大学 | A kind of preparation method of pentalyn |
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
Non-Patent Citations (3)
| Title |
|---|
| 滕江波等: "季戊四醇油酸酯的合成新工艺研究" * |
| 苏娜等: "无溶剂法合成季戊四醇四异辛酸酯的研究" * |
| 马楷等: "氧化亚锡催化合成四庚酸季戊四醇酯的研究" * |
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