CN110845376B - Preparation method of pentaerythritol mercaptocarboxylic ester - Google Patents
Preparation method of pentaerythritol mercaptocarboxylic ester Download PDFInfo
- Publication number
- CN110845376B CN110845376B CN201911164825.6A CN201911164825A CN110845376B CN 110845376 B CN110845376 B CN 110845376B CN 201911164825 A CN201911164825 A CN 201911164825A CN 110845376 B CN110845376 B CN 110845376B
- Authority
- CN
- China
- Prior art keywords
- mercaptopropionate
- reaction
- pentaerythritol
- crude product
- negative pressure
- 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.)
- Active
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention discloses a preparation method of pentaerythritol tetra-3-mercaptopropionate, which takes methyl mercaptopropionate and pentaerythritol as raw materials to carry out catalytic reaction to obtain the product pentaerythritol tetra-3-mercaptopropionate, and solves the problems of slow reaction speed, more side reactions and inevitable generation of impurity A in the prior art. The preparation method has the advantages of high reaction speed, reduction of side reactions and reduction of the content of impurities in the product.
Description
Technical Field
The invention belongs to the field of chemical technology, and particularly relates to a preparation method of pentaerythritol mercaptocarboxylic ester.
Background
At present, the mature process of literature and industry is that pentaerythritol and mercaptopropionic acid are subjected to esterification reaction in the presence of a catalyst and a water-carrying agent to generate a target product pentaerythritol tetra-3-mercaptopropionate, then the mercaptopropionic acid and the catalyst which are not completely reacted are removed by extraction, and the final product pentaerythritol tetra-3-mercaptopropionate is obtained by refining. For example, CN200780009306.1 and CN201210046431.2 are the main synthesis processes at present, but there are technical disadvantages: (1) the esterification reaction speed is low, water generated in the reaction is usually removed by adopting a water-carrying agent, but the water-carrying efficiency is low, and water in the water-carrying agent is difficult to remove quickly, so that the reaction is difficult to carry out in the forward direction, and the effect is more obvious particularly after the production is amplified; (2) the formation of impurity A, which is described in CN200780009306.1, is required to be less than 5% in the raw material mercaptopropionic acid, but the formation of such impurity is unavoidable in the preparation process. This is because mercaptopropionic acid is susceptible to self-esterification reaction in the presence of a catalyst at high temperature to produce thioester compounds as shown below:
the thioesterification product is esterified with pentaerythritol to produce impurity A, which has the following formula:
pentaerythritol tetra-3-mercaptopropionate is mainly applied to the industries of optical resins and cross-linking agents, and the influence of the impurity A is mainly reflected in the following two aspects: (1) the reduction of the mercapto content means that the number of active groups is reduced, the reaction speed in the application of the rapid curing agent is influenced, and even the requirement of rapid curing cannot be met; (2) the optical resin industry has extremely high requirements on light transmittance, and the impurities affect the uniformity of the material in the curing process, so that the transparency of the resin material is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of pentaerythritol tetra-3-mercaptopropionate, which is characterized in that methyl mercaptopropionate and pentaerythritol are used as raw materials to carry out catalytic reaction to obtain the product pentaerythritol tetra-3-mercaptopropionate, and solves the problems of slow reaction speed, more side reactions and inevitable impurity A generation in the prior art. The preparation method has the advantages of high reaction speed, reduction of side reactions and reduction of the content of impurities in the product.
The specific technical scheme of the invention is realized as follows:
a preparation method of pentaerythritol tetra-3-mercaptopropionate comprises the step of carrying out catalytic reaction on methyl mercaptopropionate and pentaerythritol to obtain the product pentaerythritol tetra-3-mercaptopropionate. The method comprises the following specific steps:
(1) adding methyl mercaptopropionate, pentaerythritol and a catalyst into a four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, starting stirring, and heating by adopting a heating jacket for reaction;
(2) separating the methanol generated in the reaction process out of the reaction system through a negative pressure condensation system, enabling the reaction to be carried out in the forward direction, sampling and detecting, and stopping the reaction when the mass fraction of the methyl mercaptopropionate is less than or equal to 0.1%;
(3) and (3) removing the residual methanesulfonic acid from the reacted mixture through alkali washing and water washing, and then heating under negative pressure to remove residual water and unreacted methyl mercaptopropionate to obtain the target product pentaerythritol tetra-3-mercaptopropionate.
The catalyst is a methanesulfonic acid solution with the mass fraction of 70%.
The dosage of the catalyst is 0.8-1.2%, preferably 0.9-1.1% of the mass sum of the methyl mercaptopropionate and the pentaerythritol.
The molar ratio of methyl mercaptopropionate to pentaerythritol is from 3.8 to 4.2, preferably from 3.9 to 4.1.
The reaction conditions in the step (1): the reaction temperature is 70-100 ℃, and the vacuum degree is-0.05 MPa to-0.08 MPa; preferably, the reaction temperature is 80-90 ℃ and the vacuum degree is-0.06 MPa to-0.07 MPa.
The invention has the beneficial effects that:
(1) ester exchange is adopted to replace esterification reaction, and methanol is removed by adopting a high-temperature negative pressure mode, so that the reaction speed can be improved, and the reaction time is obviously shortened;
(2) the side reaction is reduced, and the content of impurities in the product is reduced.
Detailed Description
Example 1
480g of methyl mercaptopropionate, 136g of pentaerythritol and 6.16g of methanesulfonic acid are added into a 1000mL four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, stirring is started, the temperature is raised to 80-85 ℃ by adopting a heating jacket, a vacuum system is started, and the vacuum degree is controlled below-0.06 MPa to start the reaction. Sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.1%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 473g of pentaerythritol tetra-3-mercaptopropionate with the purity of 99.50 wt% is obtained.
Example 2
A1000 mL four-neck flask equipped with a glass stirrer, a thermometer and a negative pressure condensation system is added with 492g of methyl mercaptopropionate, 136g of pentaerythritol and 6.91g of methanesulfonic acid, stirring is started, the temperature is raised to 85-90 ℃ by a heating jacket, a vacuum system is started, and the vacuum degree is controlled below-0.07 MPa to start the reaction. Sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.3%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 479g of pentaerythritol tetra-3-mercaptopropionate with the purity of 98.4 wt% is obtained.
Example 3
468g of methyl mercaptopropionate, 136g of pentaerythritol and 5.44g of methanesulfonic acid are added into a 1000mL four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, stirring is started, the temperature is raised to 70-75 ℃ by adopting a heating jacket, a vacuum system is started, and the vacuum degree is controlled below-0.05 MPa to start the reaction. Sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.1%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 464g of pentaerythritol tetra-3-mercaptopropionate with the purity of 95.7 wt% is obtained.
Example 4
Adding 456g of methyl mercaptopropionate, 136g of pentaerythritol and 4.74g of methanesulfonic acid into a 1000mL four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, starting stirring, heating to 80-85 ℃ by adopting a heating jacket, starting a vacuum system, and controlling the vacuum degree to be below-0.08 MPa to start reaction. Sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.1%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 458g of pentaerythritol tetra-3-mercaptopropionate with the purity of 95.4 wt% is obtained.
Example 5
504g of methyl mercaptopropionate, 136g of pentaerythritol and 7.68g of methanesulfonic acid are added into a 1000mL four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, stirring is started, the temperature is raised to 90-100 ℃ by adopting a heating jacket, a vacuum system is started, and the vacuum degree is controlled below-0.06 MPa to start the reaction. Sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.5%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 481g of pentaerythritol tetra-3-mercaptopropionate with the purity of 97 wt% is obtained.
Comparative example
Adding 136g of pentaerythritol, 445g of 3-mercaptopropionic acid, 5.8g of 70% methanesulfonic acid aqueous solution and 290g of cyclohexane into a 1000ml four-neck flask provided with a mechanical stirring device, a thermometer, a reflux condenser tube and a water separator, heating by a heating jacket, carrying out reflux water separation at 78-85 ℃, reacting for 8 hours, stopping the reaction after the theoretical water yield is reached, and cooling. Placing the reacted mixture into a separating funnel, standing for layering, and recovering 120g of supernatant cyclohexane; the lower crude product was extracted three times with 200g of absolute ethanol each time. The product is decompressed and removed with low boiling point substance to obtain 448g of pentaerythritol tetra-3-mercaptopropionate with purity of 92.4 wt%.
The purity and impurity content of the final products obtained in the above examples 1 to 5 and comparative example were examined by analysis by liquid chromatography. The results are shown in Table 1.
TABLE 1 comparison of product impurity content
| Pentaerythritol tetra-3-mercaptopropionate content | Impurity content% wt | |
| Example 1 | 99.5 | 0.5 |
| Example 2 | 98.4 | 1.6 |
| Example 3 | 95.7 | 4.3 |
| Example 4 | 95.4 | 4.6 |
| Example 5 | 97.0 | 3.0 |
| Comparative example | 92.4 | 7.6 |
Claims (1)
1. A preparation method of pentaerythritol tetra-3-mercaptopropionate is characterized by comprising the following steps: the method comprises the following steps: adding 480g of methyl mercaptopropionate, 136g of pentaerythritol and 6.16g of methanesulfonic acid into a 1000mL four-neck flask provided with a glass stirrer, a thermometer and a negative pressure condensation system, starting stirring, heating to 80-85 ℃ by adopting a heating jacket, starting a vacuum system, controlling the vacuum degree to be below-0.06 MPa, and starting reaction; sampling and detecting after 6 hours of reaction, and stopping the reaction when the mass fraction of the raw material methyl mercaptopropionate is less than or equal to 0.1%; 488g of sodium carbonate solution with the mass fraction of 2% is added into the reacted crude product for stirring and alkali washing, the crude product is separated after the alkali washing is finished and is washed by 1 time of ultrapure water, and the finished crude product is heated under negative pressure to remove residual water and unreacted methyl mercaptopropionate, so that 473g of pentaerythritol tetra-3-mercaptopropionate with the purity of 99.50 wt% is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911164825.6A CN110845376B (en) | 2019-11-25 | 2019-11-25 | Preparation method of pentaerythritol mercaptocarboxylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911164825.6A CN110845376B (en) | 2019-11-25 | 2019-11-25 | Preparation method of pentaerythritol mercaptocarboxylic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110845376A CN110845376A (en) | 2020-02-28 |
| CN110845376B true CN110845376B (en) | 2022-01-04 |
Family
ID=69604020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911164825.6A Active CN110845376B (en) | 2019-11-25 | 2019-11-25 | Preparation method of pentaerythritol mercaptocarboxylic ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110845376B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225683B (en) * | 2020-10-27 | 2021-07-27 | 山东益丰生化环保股份有限公司 | Preparation method and application of pentaerythritol tetra-mercapto carboxylic ester |
| CN115368859A (en) * | 2022-09-13 | 2022-11-22 | 深圳市凯迪高科技有限公司 | High-light-transmittance epoxy resin optical fiber adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906095A (en) * | 2010-07-06 | 2010-12-08 | 天津久日化学工业有限公司 | Thioxathone-4-carboxylic ester and preparation method as well as photoinitiator composition and application |
| CN105085335A (en) * | 2015-09-10 | 2015-11-25 | 山西其右建材科技有限公司 | Method for preparing 3-mercapto-propionate |
| CN108164443A (en) * | 2017-12-29 | 2018-06-15 | 利安隆（中卫）新材料有限公司 | Ester-interchange method antioxidant pentaerythrite four（3- lauryl thiopropionates）Method |
| CN108558719A (en) * | 2018-05-21 | 2018-09-21 | 烟台新秀化学科技股份有限公司 | A kind of preparation method of pentaerythritol ester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5711959A (en) * | 1980-06-24 | 1982-01-21 | Asahi Denka Kogyo Kk | Preparation of polyhydric alcohol ester with mercaptocarboxylic acid |
-
2019
- 2019-11-25 CN CN201911164825.6A patent/CN110845376B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906095A (en) * | 2010-07-06 | 2010-12-08 | 天津久日化学工业有限公司 | Thioxathone-4-carboxylic ester and preparation method as well as photoinitiator composition and application |
| CN105085335A (en) * | 2015-09-10 | 2015-11-25 | 山西其右建材科技有限公司 | Method for preparing 3-mercapto-propionate |
| CN108164443A (en) * | 2017-12-29 | 2018-06-15 | 利安隆（中卫）新材料有限公司 | Ester-interchange method antioxidant pentaerythrite four（3- lauryl thiopropionates）Method |
| CN108558719A (en) * | 2018-05-21 | 2018-09-21 | 烟台新秀化学科技股份有限公司 | A kind of preparation method of pentaerythritol ester |
Non-Patent Citations (1)
| Title |
|---|
| 低温快速固化环氧树脂胶粘剂的研制;沈灿军等;《云南大学学报 (自然科学版)》;20081231;第348页 左栏 1.3 PCM的合成和表征 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845376A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110845376B (en) | Preparation method of pentaerythritol mercaptocarboxylic ester | |
| CN110845424B (en) | Preparation method of 5-acetoacetylaminobenzimidazolone | |
| CN112812019A (en) | Preparation method of o-phenylenediamine | |
| CN111825549B (en) | Synthesis method of n-butyl glycolate | |
| CN111574327A (en) | Process for the preparation of 3-heptanol from a mixture comprising 2-ethylhexanol and 3-heptanoate formate | |
| JP6503227B2 (en) | Purification method of 4-hydroxybenzoic acid long chain ester | |
| CN110590702B (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| CN110272546B (en) | Method for synthesizing polyether sulfone resin | |
| CN110272451B (en) | Preparation method of tetraphenylphenol phosphonium salt | |
| CN111646904A (en) | Method for synthesizing p-nitroanisole | |
| CN108546232B (en) | Preparation method of mono-substituted or di-substituted benzoate compound | |
| CN112250569A (en) | Method for preparing functional mixed plasticizer through pressure swing esterification | |
| CN115872841B (en) | Method for synthesizing 4,4' -dihydroxybiphenyl by disproportionation method | |
| CN108203385B (en) | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone | |
| CN113698355B (en) | Synthesis method of 4, 5-dihydroxypyridazine | |
| CN107417533B (en) | Dimethyl isophthalate and process for producing the same | |
| CN108358820B (en) | Preparation method of high-quality fudosteine raw material medicine | |
| CN111822046B (en) | Span series products and preparation method thereof | |
| CN111777524B (en) | Post-treatment method for preparing naphthol AS-PH | |
| CN110526950B (en) | Preparation method of alpha-five-O-acetyl mannose | |
| CN109400468B (en) | Preparation method of L-dibenzoyl dimethyl tartrate | |
| CN106749053B (en) | The preparation method of Lormetazepam rearrangement product | |
| CN116063167A (en) | Method and device for preparing 2-propyl-2-heptenal and obtained 2-propyl-2-heptenal | |
| CN105085263A (en) | Preparation method and intermediate of 2-alkylacylmethyl-1,4-succinic acid derivative | |
| CN117304226A (en) | Synthesis method of ethyl bis (2, 4-di-tert-butyl-6-methylphenyl) phosphite |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 256599 Shandong Yifeng biochemical environmental protection Co., Ltd., Boxing County Economic Development Zone, Binzhou City, Shandong Province Applicant after: Yifeng New Material Co.,Ltd. Address before: 256599 Shandong Yifeng biochemical environmental protection Co., Ltd., Boxing County Economic Development Zone, Binzhou City, Shandong Province Applicant before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |