CN110872246A - Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) - Google Patents
Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) Download PDFInfo
- Publication number
- CN110872246A CN110872246A CN201911224258.9A CN201911224258A CN110872246A CN 110872246 A CN110872246 A CN 110872246A CN 201911224258 A CN201911224258 A CN 201911224258A CN 110872246 A CN110872246 A CN 110872246A
- Authority
- CN
- China
- Prior art keywords
- mercaptopropionate
- high content
- pentaerythritol
- content according
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
Abstract
The invention belongs to the field of chemical industry, and particularly relates to a preparation method of high-content pentaerythritol tetra (3-mercaptopropionic acid) ester.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content.
Background
Pentaerythritol tetra (3-mercaptopropionate), also known as pentaerythritol tetra-3-mercaptopropionate, pentaerythritol tetra (3-mercaptopropionate) (PETMP), colorless liquids, water-insoluble, and widely used as intermediates for organic synthesis, modifiers in polymerization reactions such as UV coatings, inks, adhesives, etc., crosslinking agents, acidic ion exchange catalysts, low-temperature curing agents, etc. At present, the main production mode is catalytic esterification of pentaerythritol and mercaptopropionic acid, such as Japanese patent publication No. 56-20530 and U.S. Pat. No. 5,794, the catalysts used are mostly methanesulfonic acid, p-toluenesulfonic acid and the like, and the synthesized product has a tetraester content of less than 70%. With the higher requirements in the field of adhesives for curing time, gel time, tensile strength and shear strength, the demand for pentaerythritol tetrakis (3-mercaptopropionate) with higher principal contents is becoming more and more urgent. In the conventional production process of a polymercaptocarboxylic ester, the residue of the starting mercaptocarboxylic acid results in a product having a strong unpleasant odor. With the enhancement of environmental awareness of people, the environmental requirements for daily necessities are higher and higher, and the odor problem of the multi-mercapto carboxylic ester becomes an important factor for limiting the application of the multi-mercapto carboxylic ester. The pentaerythritol tetra-3-mercaptopropionate prepared by the prior art has low main content, and a water removing agent is added to remove water from a solvent of a reflux system, so that the complexity of equipment is increased.
With the development of production, higher requirements are made on the content, smell, color and the like of pentaerythritol tetrakis (3-mercaptopropionate), so that a new method for preparing pentaerythritol tetrakis (3-mercaptopropionate) suitable for development is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of pentaerythritol tetra (3-mercaptopropionic acid) ester with high reaction rate, low product chromaticity, small smell and high main content so as to meet the application requirement of higher performance.
The invention is realized by the following steps: pentaerythritol, 3-mercaptopropionic acid and an acylation reagent are used as raw materials, organic base is used as a catalyst, the raw materials react in a certain solvent at a certain temperature, and finally the target product is obtained through alkali washing, acid washing, water washing and negative pressure solvent recovery.
The method comprises the following specific steps:
(1) a reaction stage: adding pentaerythritol, 3-mercaptopropionic acid, an acylating agent, an organic base catalyst and a solvent into a reactor, heating to a reaction temperature, and reacting;
(2) and (3) post-treatment: adding a weak base solution into the reaction solution, washing to light pink, separating liquid, pickling the organic phase for 1 time, adjusting the pH to 2-3, separating liquid, washing the organic phase for 1 time, and finally removing the solvent under negative pressure to obtain the target product.
Preferably, the acylating agent in step (1) is one of thionyl chloride, phosphorus oxychloride, phosphorus trichloride and phosphorus pentachloride.
Preferably, the organic base catalyst is one of 4-Dimethylaminopyridine (DMAP), triethylamine, triethanolamine and 1, 8-Diazabicyclo (DBU), and more preferably DMAP.
Preferably, the mass ratio of the pentaerythritol, the 3-mercaptopropionic acid, the acylating agent and the organic base catalyst in the step (1) is 1: 3.9-4.3: 4.5-8: 0.4 to 2, more preferably 1: 4: 7: 0.4.
preferably, the reaction temperature in step (1) is 60 to 110 ℃, more preferably 80 ℃.
Preferably, the weak base solution in step (2) is one of sodium bicarbonate and sodium bisulfite, and more preferably sodium bicarbonate.
Preferably, the mass concentration of the weak base solution is 2-8%.
Preferably, the acid used for acid washing is one of hydrochloric acid and sulfuric acid, and hydrochloric acid is further preferred.
Preferably, the solvent is one of dichloroethane, chloroform, and toluene, and more preferably toluene.
Preferably, the mass of the solvent in the step (1) is 1 to 3 times of the mass of pentaerythritol.
In the traditional production method, excessive residue of raw material mercaptocarboxylic acid can cause the product to have strong unpleasant odor, but in the process of the invention, an acylating reagent reacts with 3-mercaptopropionic acid, and then a weak alkaline solution is added in the post-treatment process to react with the residual 3-mercaptopropionic acid to remove part of the odor of the 3-mercaptopropionic acid. According to the invention, an acylation reagent reacts with 3-mercaptopropionic acid to form acyl chloride, the reactivity of the acyl chloride is far higher than that of the 3-mercaptopropionic acid to generate acyl chloride, the reactivity is improved, and the acyl chloride reacts with four hydroxyl groups of pentaerythritol quantitatively, so that the selectivity and the conversion rate of target tetraesters are improved, operations of carrying water by a solvent and dividing water are not needed, the equipment investment is simplified, the reaction time is greatly reduced, side reactions are reduced, and the chromaticity and the smell of a product are reduced.
The preparation method has the advantages of high reaction rate, low product chromaticity, small smell, high main content, short reaction period and the like, and is simple in equipment, easy to operate, short in reaction period and suitable for industrial application.
Detailed Description
The invention is further described below by way of examples, which are not intended to limit the present invention further. It will be understood by those skilled in the art that equivalent substitutions for the technical features of the present invention, or corresponding modifications, can be made within the scope of the present invention.
Example 1
A preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content comprises the following steps: the mass ratio of pentaerythritol, 3-mercaptopropionic acid, acylating agent and organic base catalyst is 1: 3.9-4.3: 4.5-8: 0.4-2
(1) A reaction stage: adding 1mol of pentaerythritol, 4mol of 3-mercaptopropionic acid, 7mol of thionyl chloride and 0.4mol of DMAP into a reactor, adding 200g of dichloroethane, heating to 80 ℃, and reacting for 2 hours;
(2) and (3) post-treatment: adding sodium sulfite solution into the reaction solution, washing to light pink, separating, washing the organic phase with hydrochloric acid for 1 time, adjusting the pH to 2-3, separating, washing the organic phase with water for 1 time, and finally removing the solvent under negative pressure to obtain the target product. The reaction yield is 98%, the content of tetraester as the main component is 97%, the odor is low, and the color is 4.1.
Example 2
A preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content is characterized by comprising the following steps:
(1) a reaction stage: adding 1mol of pentaerythritol, 3.9mol of 3-mercaptopropionic acid, 4.5mol of phosphorus oxychloride and 2mol of DMAP into a reactor, adding 200g of toluene, heating to 120 ℃, and reacting for 1.5 h;
(2) and (3) post-treatment: adding sodium bicarbonate solution into the reaction solution, washing to light pink, separating liquid, washing the organic phase for 1 time by sulfuric acid, adjusting the pH to 2-3, separating liquid, washing the organic phase for 1 time, and finally removing the solvent under negative pressure to obtain the target product. The reaction yield is 97%, the content of tetraester as the main component is 96%, the odor is low, and the color is 4.3.
Example 3
A preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content is characterized by comprising the following steps:
(1) a reaction stage: adding 1mol of pentaerythritol, 4.3mol of 3-mercaptopropionic acid, 8mol of phosphorus trichloride and 1mol of DMAP into a reactor, adding 200g of chloroform, heating to 65 ℃, and reacting for 2.5 hours;
(2) and (3) post-treatment: adding sodium bicarbonate solution into the reaction solution, washing to light pink, separating liquid, washing the organic phase for 1 time by sulfuric acid, adjusting the pH to 2-3, separating liquid, washing the organic phase for 1 time, and finally removing the solvent under negative pressure to obtain the target product. The reaction yield is 98%, the content of tetraester as the main component is 94%, the odor is low, and the color is 5.3.
Example 4
A preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content is characterized by comprising the following steps:
(1) a reaction stage: adding 1mol of pentaerythritol, 4mol of 3-mercaptopropionic acid, 6mol of phosphorus pentachloride and 1mol of DMAP into a reactor, adding 200g of dichloroethane, heating to 80 ℃, and reacting for 2 hours;
(2) and (3) post-treatment: adding sodium bisulfite solution into the reaction solution, washing to light pink, separating, washing the organic phase with hydrochloric acid for 1 time, adjusting the pH to 2-3, separating, washing the organic phase with water for 1 time, and finally removing the solvent under negative pressure to obtain the target product.
The reaction yield is 98%, the content of tetraester as the main component is 96%, the odor is low, and the color is 5.1.
Comparative example
(1) A reaction stage: adding 1mol of pentaerythritol, 4mol of 3-mercaptopropionic acid, 6.8g of methanesulfonic acid and 200g of cyclohexane into a reactor, heating to 80 ℃, and carrying out a water-splitting reaction for 7 hours;
(2) and (3) post-treatment: separating the reaction solution, adding sodium sulfite solution into the lower layer, washing to light pink, separating, washing the organic phase with hydrochloric acid for 1 time, adjusting the pH to 2-3, separating, washing the organic phase with water for 1 time, and finally removing the solvent under negative pressure to obtain the target product.
The reaction yield was 95%, the tetraester content of the main component was 67%, the odor was pungent, and the chroma was 15.
In the comparative example, pentaerythritol tetrakis (3-mercaptopropionate) was produced in a yield comparable to that of examples 1 to 4 in the present invention by a conventional method, but it was apparent that the tetraester content of the main component of the comparative example was inferior to that of the present invention and was inferior to that of the present invention in terms of odor and chroma. The pentaerythritol tetra (3-mercaptopropionic acid) ester prepared by the method has the yield of more than 97 percent, the content of the main component tetraester of more than 94 percent, low smell, even no smell and low chroma. The method has the advantages of simple equipment, simple process, easy operation and short reaction period, and is suitable for industrial application.
Claims (10)
1. A preparation method of pentaerythritol tetra (3-mercaptopropionate) with high content is characterized by comprising the following steps:
(1) a reaction stage: adding pentaerythritol, 3-mercaptopropionic acid, an acylating agent, an organic base catalyst and a solvent into a reactor, heating to a reaction temperature, and reacting;
(2) and (3) post-treatment: adding a weak base solution into the reaction solution, washing to light pink, separating liquid, pickling the organic phase for 1 time, adjusting the pH to 2-3, separating liquid, washing the organic phase for 1 time, and finally removing the solvent under negative pressure to obtain the target product.
2. The method for preparing pentaerythritol tetra (3-mercaptopropionate) with high content according to claim 1, wherein the acylating agent in step (1) is one of thionyl chloride, phosphorus oxychloride, phosphorus trichloride and phosphorus pentachloride.
3. The method for preparing pentaerythritol tetrakis (3-mercaptopropionate) with a high content according to claim 1, wherein the organic base catalyst in the step (1) is one of 4-dimethylaminopyridine, triethylamine, triethanolamine and 1, 8-diaza-bicyclo ring.
4. The method for preparing pentaerythritol tetra (3-mercaptopropionate) ester with high content according to claim 1, wherein the amount ratio of the pentaerythritol, the 3-mercaptopropionic acid, the acylating agent and the organic base catalyst in the step (1) is 1: 3.9-4.3: 4.5-8: 0.4-2.
5. The method for preparing pentaerythritol tetra (3-mercaptopropionate) ester with a high content according to claim 4, wherein the amount ratio of the pentaerythritol, the 3-mercaptopropionic acid, the acylating agent and the organic base catalyst in the step (1) is 1: 4: 7: 0.4.
6. the method for preparing pentaerythritol tetrakis (3-mercaptopropionate) with a high content according to claim 1, wherein the reaction temperature in the step (1) is 60 to 110 ℃.
7. The method for preparing pentaerythritol tetrakis (3-mercaptopropionate) with a high content according to claim 1, wherein the weak base solution in the step (2) is one of a sodium bicarbonate solution and a sodium bisulfite solution.
8. The method for preparing pentaerythritol tetra (3-mercaptopropionate) with high content according to claim 1, wherein the mass concentration of the weak base solution in the step (2) is 2-8%.
9. The method for preparing pentaerythritol tetrakis (3-mercaptopropionate) with a high content according to claim 1, wherein the acid used in the acid washing in the step (2) is hydrochloric acid or sulfuric acid.
10. The method for preparing pentaerythritol tetrakis (3-mercaptopropionate) with a high content according to claim 1, wherein the solvent in the step (1) is one of dichloroethane, chloroform and toluene; the mass of the solvent in the step (1) is 1-3 times of that of pentaerythritol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911224258.9A CN110872246A (en) | 2019-12-02 | 2019-12-02 | Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911224258.9A CN110872246A (en) | 2019-12-02 | 2019-12-02 | Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110872246A true CN110872246A (en) | 2020-03-10 |
Family
ID=69718248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911224258.9A Pending CN110872246A (en) | 2019-12-02 | 2019-12-02 | Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110872246A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277967A (en) * | 2021-05-24 | 2021-08-20 | 烟台新特路新材料科技有限公司 | Method for synthesizing pentaerythritol tetra (3-lauryl thiopropionate) by one-pot method |
| KR20220090913A (en) * | 2020-12-23 | 2022-06-30 | 주식회사 신아티앤씨 | Nano-semiconductor particles comprising ligands formed of a compound comprising an ester group and a polythiol group, a self-luminous photosensitive resin composition and a color filter comprising the nano-semiconductor particles, a photo-conversion film and a backlight for a display device unit comprising the nano-semiconductor particles, and method for preparing the compound |
| CN115385833A (en) * | 2022-09-05 | 2022-11-25 | 益丰新材料股份有限公司 | Method for reducing odor of multi-sulfhydryl compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5523434A (en) * | 1995-03-15 | 1996-06-04 | The Procter & Gamble Company | Synthesis of bleach activators |
| US6201099B1 (en) * | 1998-11-12 | 2001-03-13 | National Starch & Chemical Investment Holding Corporation | Multireactivity polymercaptans, star polymers and methods of preparation |
| CN105529458A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel cobalt lithium manganate/lithium iron manganese phosphate composite cathode material for lithium ion battery |
| CN109575216A (en) * | 2017-12-28 | 2019-04-05 | Skc株式会社 | Plastic optics polythiol compositions |
| CN110041238A (en) * | 2019-05-24 | 2019-07-23 | 山东益丰生化环保股份有限公司 | A method of reducing more mercapto-carboxylic ester smells |
-
2019
- 2019-12-02 CN CN201911224258.9A patent/CN110872246A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5523434A (en) * | 1995-03-15 | 1996-06-04 | The Procter & Gamble Company | Synthesis of bleach activators |
| US6201099B1 (en) * | 1998-11-12 | 2001-03-13 | National Starch & Chemical Investment Holding Corporation | Multireactivity polymercaptans, star polymers and methods of preparation |
| CN105529458A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel cobalt lithium manganate/lithium iron manganese phosphate composite cathode material for lithium ion battery |
| CN109575216A (en) * | 2017-12-28 | 2019-04-05 | Skc株式会社 | Plastic optics polythiol compositions |
| CN110041238A (en) * | 2019-05-24 | 2019-07-23 | 山东益丰生化环保股份有限公司 | A method of reducing more mercapto-carboxylic ester smells |
Non-Patent Citations (6)
| Title |
|---|
| 周彦芳 等: "季戊四醇四苯甲酰甲酸酯的合成及光引发性能", 《应用化学》 * |
| 夏泽斌: "酞氯法合成季戊四醇三丙烯酸醋", 《化学工程师》 * |
| 彭顺金 等: "酰氯法制备丙烯酰化季戊四醇单硬脂酸酯", 《湖北化工》 * |
| 罗义芬 等: "3, 5-二硝基苯甲腈的合成与表征", 《化学试剂》 * |
| 邢其毅 等: "《基础有机化学 上》", 30 June 1980 * |
| 马楷 等: "季戊四醇酯合成工艺研究进展", 《合成润滑材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220090913A (en) * | 2020-12-23 | 2022-06-30 | 주식회사 신아티앤씨 | Nano-semiconductor particles comprising ligands formed of a compound comprising an ester group and a polythiol group, a self-luminous photosensitive resin composition and a color filter comprising the nano-semiconductor particles, a photo-conversion film and a backlight for a display device unit comprising the nano-semiconductor particles, and method for preparing the compound |
| KR102613011B1 (en) * | 2020-12-23 | 2023-12-13 | 주식회사 신아티앤씨 | Nano-semiconductor particles comprising ligands formed of a compound comprising an ester group and a polythiol group, a self-luminous photosensitive resin composition and a color filter comprising the nano-semiconductor particles, a photo-conversion film and a backlight for a display device unit comprising the nano-semiconductor particles, and method for preparing the compound |
| CN113277967A (en) * | 2021-05-24 | 2021-08-20 | 烟台新特路新材料科技有限公司 | Method for synthesizing pentaerythritol tetra (3-lauryl thiopropionate) by one-pot method |
| CN115385833A (en) * | 2022-09-05 | 2022-11-25 | 益丰新材料股份有限公司 | Method for reducing odor of multi-sulfhydryl compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110872246A (en) | Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) | |
| CN110041238B (en) | Method for reducing odor of multi-mercapto carboxylic ester | |
| CN113956135B (en) | Preparation method of high-yield 4,4' -biphenol | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| CN111018757B (en) | Method for synthesizing 3-mercaptopropionic acid from acidic waste gas | |
| CN105085335A (en) | Method for preparing 3-mercapto-propionate | |
| CN112142624A (en) | Method for synthesizing N, N' -diisopropylcarbodiimide by using oxygen as oxidant | |
| JPH0967306A (en) | Production of isobornyl (meth)acrylate | |
| CN111825549A (en) | Synthesis method of n-butyl glycolate | |
| CN112250600B (en) | Technological method for improving yield of N, N' -diisopropylcarbodiimide product | |
| CN110330428B (en) | Method for preparing diisobutyl phthalate | |
| CN110627641A (en) | Preparation method of isoamyl lactate based on supported sodium bisulfate catalyst | |
| CN110845440B (en) | Method for preparing 2-mercaptobenzothiazole | |
| CN108479801B (en) | Catalyst for synthesizing levulinate and application thereof | |
| CN112940740A (en) | Synthesis method of 4-substituent cyclohexanone liquid crystal material | |
| CN105348068B (en) | A kind of preparation method of sodium iso-octoate | |
| CN109400468B (en) | Preparation method of L-dibenzoyl dimethyl tartrate | |
| CN110655488A (en) | Method for catalytically synthesizing light stabilizer LS-770 | |
| CN102942479A (en) | Method for preparing propylene glycol methyl ether acetate through two-step coupling reaction | |
| CN110935436B (en) | Catalyst and preparation method and application thereof | |
| CN110935475B (en) | Preparation of recyclable supported catalyst and application method thereof in carbonyl oxidation reaction | |
| CN112079750A (en) | Preparation method of methanesulfonic acid | |
| CN109180610B (en) | Method for efficiently recovering propylene oxide catalyst and co-producing KA oil | |
| CN108727178A (en) | The method that ammonium tungstate catalysis cyclohexanol prepares cyclohexanone | |
| CN116478033A (en) | Carbonic acid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200310 |
|
| RJ01 | Rejection of invention patent application after publication |