CN113429544A - Method for synthesizing epoxy resin by olefin oxidation - Google Patents
Method for synthesizing epoxy resin by olefin oxidation Download PDFInfo
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- CN113429544A CN113429544A CN202110296563.XA CN202110296563A CN113429544A CN 113429544 A CN113429544 A CN 113429544A CN 202110296563 A CN202110296563 A CN 202110296563A CN 113429544 A CN113429544 A CN 113429544A
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- China
- Prior art keywords
- catalyst
- epoxy resin
- olefin
- acid
- buffer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for synthesizing epoxy resin by olefin oxidation, and relates to the technical field of epoxy resin synthesis. The method comprises the following steps: carrying out solid-carried reaction on peroxyacetic acid to form solid-carried organic acid as a catalyst; dissolving a buffering agent in a solvent, and adjusting the pH value to form a buffering system; dissolving alpha-hydroxy propionic acid, olefin and catalyst in a buffer system, and heating while stirring to obtain a mixture; cooling sufficiently to separate out the catalyst, filtering, placing the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery; and (4) washing the reactant with water and alkali until the reactant is neutral to obtain the product. The invention has the advantages that: the catalyst is immobilized, the catalytic efficiency is higher, a buffer system is formed by a buffering agent, the peroxide is prevented from being hydrolyzed under a double oxidation system, the catalytic effect is better, the catalyst can be completely separated out from an organic phase, and the catalyst can be completely recycled, so that the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of epoxy resin synthesis, in particular to a method for synthesizing epoxy resin by olefin oxidation.
Background
The epoxy resin is a high molecular polymer, has a molecular formula of (C11H12O3) n, and is a general name of a polymer containing more than two epoxy groups in a molecule. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin.
The olefin reaction conversion needs to be carried out by catalyst catalysis, the catalyst usually uses heteropoly acid compounds or special catalysts for synthesis, the synthetic process of the synthetic catalyst is complex, the reaction time is long, and the production efficiency required in industrial production is difficult to meet, when the heteropoly acid compounds are catalyzed, the catalyst can not be completely separated out from an organic phase, the catalyst remained in the organic phase product can cause the product to be discolored or polymerized into a product with large molecular weight in the rectification and purification stage, the product quality is seriously influenced, the product reaction efficiency is low, and the catalyst can not be recycled for cyclic utilization.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing epoxy resin by olefin oxidation, which can solve the problems that the catalyst in the prior art is low in catalytic efficiency and product reaction efficiency during catalysis, the catalyst cannot be completely separated out from an organic phase, the product quality is influenced, and the catalyst cannot be recycled.
In order to solve the technical problems, the technical scheme of the invention is as follows: the method comprises the following steps:
s1, carrying out solid-carrying on the peroxyacetic acid to form solid-carrying organic acid as a catalyst;
s2, dissolving a buffer in a solvent, and adjusting the pH value to 3-4 to form a medium acid buffer system;
s3, dissolving alpha-hydroxypropionic acid, olefin and a catalyst in a buffer system, and heating to 50-100 ℃ under stirring to obtain a mixture;
s4, cooling to 20-50 ℃, fully cooling to separate out the catalyst, filtering, putting the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery;
and S5, washing the reactant with water and alkali until the reactant is neutral to obtain the product.
Further, the buffer is sodium dihydrogen phosphate.
Further, the solvent is a halogenated hydrocarbon.
Further, the olefin is styrene.
Further, the immobilization temperature of the peroxyacetic acid is 90-100 ℃.
Further, the mass ratio of the olefin to the peroxyacetic acid to the buffering agent to the alpha-hydroxypropionic acid to the halogenated hydrocarbon solvent is 100 (2-4): (1-3): (6-9): (120-150).
The invention has the advantages that: carry out the solid-borne with the catalyst, catalytic efficiency is higher, forms buffer system through the buffer, prevents that peroxide from hydrolysising under the dual oxidation system, and catalytic effect is better, and product reaction efficiency is higher, and the catalyst can be followed organic phase completely and is appeared, avoids remaining the catalyst in organic phase product to influence the product quality, and the catalyst can be retrieved completely and circulate and recycle, and high-usage reduces manufacturing cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
The first embodiment is as follows:
s1, carrying out solid-carrying on the peroxyacetic acid to form solid-carried organic acid as a catalyst, wherein the solid-carrying temperature is 90 ℃;
s2, dissolving a buffer in a halogenated hydrocarbon solvent, and adjusting the pH value to 3 to form a medium acid buffer system, wherein the buffer is sodium dihydrogen phosphate;
s3, dissolving alpha-hydroxypropionic acid, olefin and a catalyst in a buffer system, heating to 50 ℃ under stirring to obtain a mixture, wherein the olefin is styrene, and the mass ratio of the styrene, the peroxyacetic acid, the sodium dihydrogen phosphate, the alpha-hydroxypropionic acid and the halogenated hydrocarbon solvent is (100: 2): 1: 6: 120 of a solvent;
s4, cooling to 20 ℃, fully cooling to separate out the catalyst, filtering, putting the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery;
and S5, washing the reactant with water and alkali until the reactant is neutral to obtain the product.
Example two:
s1, carrying out solid-carrying on the peroxyacetic acid to form solid-carried organic acid as a catalyst, wherein the solid-carrying temperature is 100 ℃;
s2, dissolving a buffer in a halogenated hydrocarbon solvent, and adjusting the pH value to 4 to form a medium acid buffer system, wherein the buffer is sodium dihydrogen phosphate;
s3, dissolving alpha-hydroxypropionic acid, olefin and a catalyst in a buffer system, heating to 100 ℃ under stirring to obtain a mixture, wherein the olefin is styrene, and the mass ratio of the styrene, the peroxyacetic acid, the sodium dihydrogen phosphate, the alpha-hydroxypropionic acid and the halogenated hydrocarbon solvent is 100: 4: 3: 9: 150;
s4, cooling to 50 ℃, fully cooling to separate out the catalyst, filtering, putting the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery;
and S5, washing the reactant with water and alkali until the reactant is neutral to obtain the product.
Example three:
s1, carrying out solid-carrying on the peroxyacetic acid to form solid-carried organic acid as a catalyst, wherein the solid-carrying temperature is 95 ℃;
s2, dissolving a buffer in a halogenated hydrocarbon solvent, and adjusting the pH value to 4 to form a medium acid buffer system, wherein the buffer is sodium dihydrogen phosphate;
s3, dissolving alpha-hydroxypropionic acid, olefin and a catalyst in a buffer system, heating to 70 ℃ under stirring to obtain a mixture, wherein the olefin is styrene, and the mass ratio of the styrene, the peroxyacetic acid, the sodium dihydrogen phosphate, the alpha-hydroxypropionic acid and the halogenated hydrocarbon solvent is 100: 3: 2: 7: 130, 130;
s4, cooling to 30 ℃, fully cooling to separate out the catalyst, filtering, putting the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery;
and S5, washing the reactant with water and alkali until the reactant is neutral to obtain the product.
The color number of the epoxy resin prepared in each example is 60-50 determined according to standard GBT3143-1982, while the color number of the alicyclic epoxy resin prepared in the prior art is 80-100, and the determination result shows that the alicyclic epoxy resin prepared by the preparation method of the epoxy resin provided by the invention has good color and luster, the purity of the epoxy resin is more than 96.1%, the product yield is more than 96.3%, the utilization rate is high, the production cost is reduced, the reaction efficiency of the product is higher, the catalyst can be completely precipitated from the organic phase, in addition, the purity of the epoxy resin obtained in the second example is 98% at the highest, the product yield is 97.5%, and the purity and the product yield are the highest, which is the best example.
The catalyst is immobilized, the catalytic efficiency is higher, a buffer system is formed by the buffer agent, the peroxide is prevented from being hydrolyzed under a double oxidation system, the catalytic effect is better, the reaction efficiency of the product is higher, the catalyst can be completely separated out from the organic phase, the influence of the catalyst remained in the organic phase product on the product quality is avoided, the catalyst can be completely recovered for recycling, the utilization rate is high, and the production cost is reduced.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for synthesizing epoxy resin by olefin oxidation is characterized in that: the method comprises the following steps:
s1, carrying out solid-carrying on the peroxyacetic acid to form solid-carrying organic acid as a catalyst;
s2, dissolving a buffer in a solvent, and adjusting the pH value to 3-4 to form a medium acid buffer system;
s3, dissolving alpha-hydroxypropionic acid, olefin and a catalyst in a buffer system, and heating to 50-100 ℃ under stirring to obtain a mixture;
s4, cooling to 20-50 ℃, fully cooling to separate out the catalyst, filtering, putting the filtered filtrate into a separating funnel, standing for separating liquid, separating an upper aqueous phase, taking an organic phase, and performing suction filtration and desolventizing for recovery;
and S5, washing the reactant with water and alkali until the reactant is neutral to obtain the product.
2. The method for synthesizing epoxy resin by olefin oxidation according to claim 1, wherein: the buffer is sodium dihydrogen phosphate.
3. The method for synthesizing epoxy resin by olefin oxidation according to claim 1, wherein: the solvent is a halogenated hydrocarbon.
4. The method for synthesizing epoxy resin by olefin oxidation according to claim 1, wherein: the olefin is styrene.
5. The method for synthesizing epoxy resin by olefin oxidation according to claim 1, wherein: the solid-carrying temperature of the peroxyacetic acid is 90-100 ℃.
6. The method for synthesizing epoxy resin by olefin oxidation according to claim 1, wherein: the mass ratio of the olefin to the peroxyacetic acid to the buffer to the alpha-hydroxypropionic acid to the halogenated hydrocarbon solvent is 100 (2-4): (1-3): (6-9): (120-150).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110296563.XA CN113429544A (en) | 2021-03-19 | 2021-03-19 | Method for synthesizing epoxy resin by olefin oxidation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110296563.XA CN113429544A (en) | 2021-03-19 | 2021-03-19 | Method for synthesizing epoxy resin by olefin oxidation |
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| CN113429544A true CN113429544A (en) | 2021-09-24 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250169A (en) * | 2008-04-08 | 2008-08-27 | 大连天源基化学有限公司 | Method for synthesizing aliphatic diepoxides |
| CN101485990A (en) * | 2009-03-10 | 2009-07-22 | 睿鹰制药（苏州）有限公司 | Solid supported heteropoly acid catalyst and preparation method thereof |
| CN101492528A (en) * | 2009-03-10 | 2009-07-29 | 睿鹰制药（苏州）有限公司 | Method for synthesis of alicyclic epoxy resin with catalysis of solid supported heteropoly acid catalyst |
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
| CN106967012A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of styrene oxidation method |
-
2021
- 2021-03-19 CN CN202110296563.XA patent/CN113429544A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250169A (en) * | 2008-04-08 | 2008-08-27 | 大连天源基化学有限公司 | Method for synthesizing aliphatic diepoxides |
| CN101485990A (en) * | 2009-03-10 | 2009-07-22 | 睿鹰制药（苏州）有限公司 | Solid supported heteropoly acid catalyst and preparation method thereof |
| CN101492528A (en) * | 2009-03-10 | 2009-07-29 | 睿鹰制药（苏州）有限公司 | Method for synthesis of alicyclic epoxy resin with catalysis of solid supported heteropoly acid catalyst |
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
| CN106967012A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of styrene oxidation method |
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