CN111592478B - Method for reducing chroma of pentaerythritol ester - Google Patents
Method for reducing chroma of pentaerythritol ester Download PDFInfo
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- CN111592478B CN111592478B CN202010438850.5A CN202010438850A CN111592478B CN 111592478 B CN111592478 B CN 111592478B CN 202010438850 A CN202010438850 A CN 202010438850A CN 111592478 B CN111592478 B CN 111592478B
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- pentaerythritol ester
- pentaerythritol
- borane
- reducing agent
- chroma
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- 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
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Abstract
The invention relates to the field of thiol compounds, in particular to a method for reducing chroma of pentaerythritol ester. The method can be applied to the synthesis reaction to produce the pentaerythritol ester with low chroma, and can also treat the pentaerythritol ester with high chroma caused by the problems of raw material quality and the like. The method is very suitable for industrial production of pentaerythritol ester, improves the quality of the pentaerythritol ester, has simple operation method, greatly reduces the process difficulty and reduces the production cost.
Description
Technical Field
The invention relates to the field of thiol compounds, in particular to a method for reducing chroma of pentaerythritol ester.
Background
Optical resins have a clear superiority in the manufacture of spectacles compared with inorganic glasses: light weight, impact resistance, easy processing and forming, etc. The optical resin material on the market at present is mainly polyurethane resin, pentaerythritol ester with active hydrogen at the end group is an important raw material for synthesizing the polyurethane resin, and the synthesized polyurethane resin has low dispersion, high refractive index and strong impact resistance, and is one of plastic lens resins with excellent performance.
The yellowness index is an important index of optical resins, and the key factor determining the base color of optical resins is the chroma of pentaerythritol ester.
Pentaerythritol ester is generally synthesized by an esterification method and is already industrialized, pentaerythritol is one of important synthetic raw materials of pentaerythritol ester, and the quality of pentaerythritol ester directly determines the quality and market competitiveness of pentaerythritol ester products. However, due to high decoloring cost and complex technology, the product of pentaerythritol sold in domestic markets at present has a single-season content of about 90%, wherein impurities mainly comprise di-season, multi-season and pentaerythritol methanol ether and trace acetal and ester organic matters, the impurities cause more side reactions in the process of synthesizing pentaerythritol ester, the product has dark color, and the quality of the pentaerythritol ester is greatly reduced. The industrial use of membrane separation, extraction and adsorption and recrystallization processes is common to improve the quality of pentaerythritol and further to obtain low color pentaerythritol esters. However, the process is complex to operate and high in cost. It is therefore particularly important to find a low-cost method for reducing the color of pentaerythritol esters.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for reducing the chroma of pentaerythritol ester, which can be applied to the synthesis reaction to produce the pentaerythritol ester with low chroma and can also treat the pentaerythritol ester with high chroma caused by the problems of raw material quality and the like. The method is very suitable for industrial production of pentaerythritol ester, improves the quality of the pentaerythritol ester, has simple operation method, greatly reduces the process difficulty and reduces the production cost.
The technical scheme of the invention is as follows: adding solvent and reductant into industrial pentaerythritol ester compound, reaction at certain temperature, filtering and evaporating to eliminate solvent to obtain pentaerythritol ester compound with very small chroma2)n—SH)}4And n is an integer of 1 to 3.
The specific process steps comprise:
adding polar solvent and reducing agent into industrial pentaerythritol ester compound, reacting at 60-90 deg.C, filtering, and evaporating to remove solvent.
The solvent is selected from one or more of ethanol, methanol and isopropanol;
preferred solvents are selected from ethanol;
the reducing agent is selected from one or more of borane pyridine complex, catechol borane, 2-methylpyridine borane, N, N-diethylaniline borane, triethylboron, diethyl (3-pyridine) borane, aluminum powder, zinc powder, iron powder, magnesium powder, red aluminum and sodium hydrosulfite;
the preferable reducing agent is selected from one or more of 2-methylpyridine borane, N, N-diethylaniline borane, aluminum powder, zinc powder and sodium hydrosulfite;
more preferably, the reducing agent is selected from one of zinc powder and sodium hydrosulfite;
in the process, the dosage of the polar solvent is 10 to 30 percent of the mass of the pentaerythritol ester compound; the dosage of the reducing agent is 0.5 to 5 percent of the mass of the pentaerythritol ester compound;
the amount of the polar solvent is preferably 15 to 25% by mass, more preferably 15 to 20% by mass, based on the mass of the pentaerythritol ester compound; the amount of the reducing agent is 1 to 4 percent, more preferably 2 to 3 percent of the mass of the pentaerythritol ester compound;
preferably, the reaction time is from 1 to 3 hours, preferably from 1.5 to 2.5, more preferably 2 hours.
The invention has the beneficial effects that:
in general industrial production, after a pentaerythritol ester compound is synthesized through reaction, in order to obtain a high-quality product, steps such as washing with water and alkali are generally carried out for many times before color removal, the operation is complex, and a large amount of wastewater is generated; the pentaerythritol ester compound can be directly reacted in the method without washing and removing impurities for many times, and the reducing agent has high reducing activity and simple operation and reduces the generation of waste water.
The sulfhydryl of the pentaerythritol ester containing sulfhydryl groups is easily oxidized into disulfide bonds, impurities are formed to further influence the chromaticity, and the compound is more difficult to decolor than other compounds containing no sulfhydryl groups.
Generally, the crude pentaerythritol ester is acidic and contains a certain amount of water, potassium borohydride is decomposed and cannot have a corresponding reduction effect when being used as a reducing agent in the prior art, and the reducing agent can fully exert the reduction effect and cannot be influenced by the water or other impurities.
The solvent selected in the invention has certain solubility to the corresponding reducing agent, and provides a reducing atmosphere, thereby improving the integral reducing activity and reducing the process difficulty.
In conclusion, the method can be applied to the synthesis reaction to produce the pentaerythritol ester with low chroma, and can also treat the pentaerythritol ester with high chroma caused by abnormal production. The method is very suitable for industrial production, improves the quality of the pentaerythritol ester, and simultaneously has simple operation method, greatly reduces the process difficulty, reduces the production cost and improves the market competitiveness.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention. Except as otherwise noted, the following examples were carried out using conventional techniques.
Example 1
To 100g of pentaerythritol mercaptopropionate was added 10g of ethanol, and then 1g of 2-methylpyridine borane was added, and the mixture was stirred at 65 ℃ for 3 hours, filtered, and then the solvent was distilled off.
| Pentaerythritol mercaptopropionate color | Content/% | Curing | |
| Before treatment | 16 | 69 | Qualified |
| After treatment | 9 | 69.1 | Qualified |
Example 2
Adding 18g of methanol into 120g of pentaerythritol mercaptobutyrate, adding 1.8g of aluminum powder, stirring at 70 ℃ for 2 hours, filtering, and evaporating the solvent.
| Pentaerythritol mercaptobutyrate color | Content/% | Curing | |
| Before treatment | 17 | 68.4 | Qualified |
| After treatment | 10 | 68.3 | Qualified |
Example 3
Adding 20g of ethanol into 100g of pentaerythritol mercaptoacetate compound, adding 1g N and N-diethylaniline borane, stirring at 85 ℃ for 1.5h, filtering, and evaporating the solvent.
| Pentaerythritol thioglycolate color | Content/% | Curing | |
| Before treatment | 15 | 67.9 | Qualified |
| After treatment | 8 | 68 | Qualified |
Example 4
Adding 18g of isopropanol into 120g of pentaerythritol mercaptopropionate compound, adding 2.4g of sodium hydrosulfite, stirring at 80 ℃ for 1 hour, filtering, and evaporating to remove the solvent.
| Pentaerythritol mercaptopropionate color | Content/% | Curing | |
| Before treatment | 14 | 70.1 | Qualified |
| After treatment | 6 | 70.2 | Qualified |
Example 5
Adding 18g of ethanol into 120g of pentaerythritol mercaptopropionate compound, adding 2.4g of zinc powder, stirring at 80 ℃ for 1 hour, filtering, and evaporating to remove the solvent.
| Pentaerythritol mercaptopropionate color | Content/% | Curing | |
| Before treatment | 14 | 70.1 | Qualified |
| After treatment | 5 | 70.3 | Qualified |
The embodiment shows that the method can greatly reduce the over-high chroma of the pentaerythritol ester, improve the quality of the pentaerythritol ester, reduce the process difficulty, reduce the production cost and improve the market competitiveness.
Claims (8)
1. A method for reducing chroma of pentaerythritol ester is characterized in that a polar solvent and a reducing agent are added into a pentaerythritol ester compound, the mixture is filtered after reaction at 60-90 ℃, and then the solvent is evaporated;
the polar solvent is selected from one or more of ethanol, methanol and isopropanol;
the reducing agent is selected from one or more of borane pyridine complex, catechol borane, 2-methylpyridine borane, N, N-diethylaniline borane, triethylboron, diethyl (3-pyridine) borane, aluminum powder, zinc powder, iron powder, magnesium powder, red aluminum and sodium hydrosulfite;
the pentaerythritol ester compound is pentaerythritol thioglycolate or pentaerythritol mercaptopropionate or pentaerythritol mercaptobutyrate;
the dosage of the polar solvent is 10 to 30 percent of the mass of the pentaerythritol ester compound; the dosage of the reducing agent is 0.5 to 5 percent of the mass of the pentaerythritol ester compound; the reaction time is 1-3 h.
2. The method of claim 1, wherein the solvent is selected from the group consisting of ethanol.
3. The method of claim 1, wherein the reducing agent is selected from one or more of 2-methyl pyridine borane, N, N-diethyl aniline borane, aluminum powder, zinc powder, and sodium hydrosulfite.
4. The method of claim 3, wherein the reducing agent is selected from the group consisting of zinc powder and sodium hydrosulfite.
5. The method for reducing the chroma of the pentaerythritol ester according to claim 1, wherein the amount of the polar solvent is 15 to 25 percent of the mass of the pentaerythritol ester compound.
6. The method for reducing the chroma of the pentaerythritol ester according to claim 5, wherein the amount of the polar solvent is 15 to 20 percent of the mass of the pentaerythritol ester compound.
7. The method for reducing the chroma of the pentaerythritol ester according to claim 1, wherein the reducing agent is used in an amount of 1 to 4 percent based on the mass of the pentaerythritol ester compound.
8. The method of claim 7, wherein the amount of the reducing agent is 2-3% by mass of the pentaerythritol ester compound.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2930345A1 (en) * | 1979-07-26 | 1981-02-19 | Degussa | METHOD FOR PURIFYING PENTAERYTHRITE |
| JP3562918B2 (en) * | 1996-10-22 | 2004-09-08 | 三井化学株式会社 | Process for producing pentaerythritol mercaptocarboxylate |
| JPH1180117A (en) * | 1997-09-04 | 1999-03-26 | Asahi Denka Kogyo Kk | Production of mercaptocarboxylic acid ester |
| JP4339181B2 (en) * | 2004-05-27 | 2009-10-07 | 三井化学株式会社 | Polymerizable composition for optical element and optical element obtained by curing the composition |
| JPWO2007052329A1 (en) * | 2005-10-31 | 2009-04-30 | 三井化学株式会社 | Method for producing pentaerythritol mercaptocarboxylic acid ester, pentaerythritol mercaptocarboxylic acid ester obtained thereby, and use thereof |
| EP2899181A1 (en) * | 2006-04-21 | 2015-07-29 | Mitsui Chemicals, Inc. | Process for producing pentaerythritol mercaptocarboxylic esters and polymerizable compositions containing the esters |
| CN103819337B (en) * | 2013-09-29 | 2016-01-20 | 安庆飞凯高分子材料有限公司 | A kind of trifunctional pentaerythritol acrylate preparation method |
| WO2016208707A1 (en) * | 2015-06-24 | 2016-12-29 | 三井化学株式会社 | Method for manufacturing pentaerythritol mercapto carboxylic acid ester, polymerizable composition, resin, optical material, and lens |
| CN107311899B (en) * | 2017-06-30 | 2019-03-08 | 山东益丰生化环保股份有限公司 | A method of reducing optical resin multi-thioalcohol compound coloration |
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