CN114573789A - Preparation method of bisphenol A type liquid epoxy resin - Google Patents
Preparation method of bisphenol A type liquid epoxy resin Download PDFInfo
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- CN114573789A CN114573789A CN202210274276.3A CN202210274276A CN114573789A CN 114573789 A CN114573789 A CN 114573789A CN 202210274276 A CN202210274276 A CN 202210274276A CN 114573789 A CN114573789 A CN 114573789A
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- bisphenol
- epoxy resin
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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
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
Abstract
The invention provides a preparation method of bisphenol A type liquid epoxy resin, and relates to the technical field of epoxy resin preparation. The invention is prepared under anhydrous condition, firstly, the etherification reaction is carried out under the protective atmosphere, the phenolic hydroxyl in the bisphenol A can be prevented from being oxidized and denatured, the conversion rate of the bisphenol A and the yield of the bisphenol A type liquid epoxy resin product are improved, and the generation amount of byproducts is reduced. Then, carrying out cyclization reaction (hydrogen chloride removal) on the etherification intermediate in the presence of anhydrous methanol and water carbonate without generating water, so that no water participates and is generated in the whole reaction process, and industrial wastewater is avoided; the industrial salt is easy to dissolve in water but is easy to separate out in anhydrous methanol, so that the separated industrial salt is free from interference of organic matters after being washed by the methanol, a fine industrial salt byproduct is formed, and the generation of solid waste industrial salt is avoided; reduces the environmental protection cost caused by the treatment of high-salt inorganic wastewater and inorganic salt solid waste.
Description
Technical Field
The invention relates to the technical field of epoxy resin preparation, in particular to a preparation method of bisphenol A type liquid epoxy resin.
Background
The bisphenol A liquid epoxy resin has the characteristics of high epoxy value, high purity, low chlorine content, no color or light color, low curing volume shrinkage, high bonding strength, high electrical insulation, high chemical resistance and the like. The liquid bisphenol A epoxy resin can be used as coating, adhesive, casting material, molding material, textile material, building material and other composite materials, and is widely applied to the technical fields of manufacturing, machinery, electronics, building, aerospace and the like.
The synthesis of the bisphenol A type liquid epoxy resin is mainly divided into an etherification stage of bisphenol A and epichlorohydrin and a cyclization reaction stage of removing hydrogen chloride from an etherification intermediate under the action of alkali. For example, chinese patent CN1118788A discloses a method for preparing liquid epoxy resin, comprising the following steps: a first step of adding a portion of NaOH to a mixture of bisphenol A, epichlorohydrin, water and isopropanol; secondly, stopping adding the sodium hydroxide; thirdly, adding the residual NaOH; in the fourth step, isopropanol, water and epichlorohydrin are separated, the epoxide is dissolved in a solvent to form a solution, and then a sodium hydroxide solution is added to continue the reaction. Chinese patent CN104710597A discloses a method for preparing liquid epoxy resin, comprising: contacting a polyhydric phenol with an epihalohydrin in the presence of an ionic catalyst to form a halohydrin intermediate reaction product; simultaneously carrying out the following steps: reacting a portion of the halohydrin intermediate reaction product with an alkali metal hydroxide to form a solid salt suspended in a liquid mixture comprising the dehydrohalogenation product and unreacted halohydrin intermediate; and removing water and epihalohydrin from the reaction mixture as a vapor; separating the solid salt from the liquid mixture; reacting at least a portion of the unreacted halohydrin intermediate with an alkali metal hydroxide in the presence of water to form an organic mixture comprising the epoxy resin and unreacted epihalohydrin and an aqueous solution comprising a salt; separating the organic mixture from the aqueous mixture; and separating unreacted epihalohydrin from the liquid epoxy resin, which can be carried out without adding any organic solvent, achieves a relatively high conversion of raw materials, and has a relatively low content of hydrolyzable chlorine in the product. Chinese patent CN101613458A discloses a preparation method of bisphenol A type liquid epoxy resin, quaternary ammonium salt phase transfer catalyst is added in the etherification stage, sodium hydroxide aqueous solution is dripped in the ring-closing reaction stage, toluene is used for dispersing and dissolving resin and precipitating a mixture of industrial salt in the post-treatment stage, and the bisphenol A type liquid epoxy resin prepared by the method is transparent, has low viscosity and has an epoxy value of about 0.55-0.56. Japanese patent JP2004211048 discloses a post-treatment process for reducing the chlorine content in epoxy resin, and a large amount of alkali is added in the post-treatment refining stage of epoxy resin to reduce the chlorine content, so as to prepare high-purity epoxy resin with low organic chlorine. Chinese patent CN102816295A discloses a process for refining bisphenol a liquid epoxy resin, which comprises adding sodium hydroxide solution and organic solvent, adding sodium hydroxide solution and cocatalyst to remove residual hydrolyzable chlorine, washing with mixed solution of resolving water and pure water, and washing with resolving water and pure water.
However, in order to reduce the content of hydrolyzable chlorine in bisphenol a liquid epoxy resin in the prior art, most of the prior art adopts alkali metal aqueous solution or alkaline earth metal aqueous solution to remove hydrogen chloride, and uses a large amount of water to wash the byproduct industrial salt generated in the reaction, so that a large amount of high-salt high-COD wastewater and solid waste industrial salt are generated in the production process, and the green clean production is not facilitated.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing bisphenol a type liquid epoxy resin, which does not generate high-salt high-COD wastewater and solid waste industrial salt, and is green and environment-friendly.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bisphenol A type liquid epoxy resin, which is prepared under the anhydrous condition and comprises the following steps:
under the protective atmosphere, mixing bisphenol A and epichlorohydrin, and carrying out etherification reaction to obtain an etherification intermediate;
mixing the etherification intermediate, anhydrous methanol and anhydrous carbonate, carrying out cyclization reaction, and then carrying out solid-liquid separation to obtain a crude product liquid and industrial salt; washing the industrial salt with hot methanol to obtain a fine industrial salt;
and refining the crude product liquid to obtain the bisphenol A type liquid epoxy resin.
Preferably, the molar ratio of the bisphenol A to the epichlorohydrin is 1: 6 to 10.
Preferably, the temperature of the etherification reaction is 75-85 ℃ and the time is 6.5-9 h.
Preferably, the method further comprises removing epichlorohydrin in the etherification intermediate mixture obtained by the etherification reaction after the etherification reaction.
Preferably, the mass ratio of the etherification intermediate to the anhydrous methanol is 1: 3 to 5.
Preferably, the molar ratio of the bisphenol A to the anhydrous carbonate is 1: 2.5 to 3.
Preferably, the temperature of the cyclization reaction is 70-75 ℃, and the time is 3-4 h.
Preferably, the industrial salt is washed with hot methanol to obtain a fine industrial salt;
the temperature of the hot methanol is 65-75 ℃;
the mass ratio of the hot methanol to the etherification intermediate is 1: 3 to 5.
Preferably, the refining comprises: and distilling the crude product liquid, cooling the obtained crude bisphenol A type liquid epoxy resin to room temperature, diluting by adopting anhydrous methanol, carrying out solid-liquid separation on the diluted feed liquid, and carrying out secondary distillation on the obtained liquid product to obtain the bisphenol A type liquid epoxy resin.
Preferably, the volume ratio of the crude bisphenol A liquid epoxy resin to the anhydrous methanol for dilution is 1: 1 to 2.5.
The invention provides a preparation method of bisphenol A type liquid epoxy resin, which is prepared under the anhydrous condition and comprises the following steps: under the protective atmosphere, mixing bisphenol A and epichlorohydrin, and carrying out etherification reaction to obtain an etherification intermediate; mixing the etherification intermediate, anhydrous methanol and anhydrous carbonate, carrying out cyclization reaction, and then carrying out solid-liquid separation to obtain a crude product liquid and industrial salt; and refining the crude product liquid to obtain the bisphenol A type liquid epoxy resin. The preparation method provided by the invention has the advantages that the etherification reaction is carried out under the protective atmosphere, the phenolic hydroxyl in the bisphenol A can be prevented from being oxidized and denatured, the conversion rate of the bisphenol A and the yield of bisphenol A type liquid epoxy resin products are improved, and the generation amount of byproducts is reduced. The etherification intermediate carries out cyclization reaction (removal of hydrogen chloride) in the presence of anhydrous methanol and water carbonate, and water is not generated, so that no water participates in the whole reaction process and no water is generated, and the generation of industrial wastewater is avoided; the industrial salt is easy to dissolve in water but is easy to separate out in anhydrous methanol, so that the separated industrial salt is free from interference of organic matters after being washed by the methanol, a fine industrial salt byproduct is formed, and the generation of solid waste industrial salt is avoided; reduces the environmental protection cost caused by high-salt inorganic wastewater and inorganic salt solid waste treatment in the production process of the bisphenol A liquid epoxy resin. The purity of the bisphenol A type liquid epoxy resin is improved by subsequent refining. Moreover, the preparation method provided by the invention is simple to operate, low in cost, less in three wastes, green and environment-friendly, and suitable for industrial production.
As shown in the test results of the embodiment, the yield of the bisphenol A liquid epoxy resin obtained by the preparation method provided by the invention is 90.2-91.4%, the purity is more than or equal to 99.5%, the epoxy equivalent is 180-189 g/eq, the content of inorganic chlorine is less than or equal to 0.05 wt%, the viscosity (25 ℃) is less than or equal to 8000 mpa.s, the volatile (110 ℃, 3h) is less than or equal to 1.2 wt%, the chroma is less than or equal to 3, and the product quality of the bisphenol A liquid epoxy resin is excellent and meets the requirements of electronic-grade products.
Drawings
FIG. 1 is a flow chart of the preparation of bisphenol A type liquid epoxy resin.
Detailed Description
The invention provides a preparation method of bisphenol A type liquid epoxy resin, which is prepared under the anhydrous condition and comprises the following steps:
under the protective atmosphere, mixing bisphenol A and epichlorohydrin, and carrying out etherification reaction to obtain an etherification intermediate;
mixing the etherification intermediate, anhydrous methanol and anhydrous carbonate, carrying out cyclization reaction, and then carrying out solid-liquid separation to obtain a crude product liquid and industrial salt; washing the industrial salt with hot methanol to obtain a fine industrial salt;
and refining the crude product liquid to obtain the bisphenol A type liquid epoxy resin.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, under the protective atmosphere, bisphenol A and epichlorohydrin are mixed for etherification reaction to obtain an etherification intermediate.
In the present invention, the molar ratio of bisphenol a to epichlorohydrin is preferably 1: 6-10, more preferably 1: 7-9, more preferably 1: 7.5 to 8. According to the invention, the dosage ratio of the bisphenol A and the epoxy resin is controlled within the range, and the excessive epoxy chloropropane can ensure the complete consumption of the bisphenol A, so that the occurrence of side reaction is avoided, and the conversion rate of the bisphenol A material and the yield of the bisphenol A type liquid epoxy resin product are improved.
The mixing method of the invention is not particularly limited, and the raw materials can be uniformly mixed.
In the invention, the temperature of the etherification reaction is preferably 75-85 ℃, more preferably 77-82 ℃, and further preferably 78-80 ℃; the time of the etherification reaction is preferably 6.5 to 9 hours, more preferably 7 to 8.5 hours, and even more preferably 7.5 to 8 hours. In the specific embodiment of the invention, the etherification reaction is preferably carried out by detecting the content of bisphenol A through a high performance liquid chromatography, the etherification reaction stage is considered to be complete when the residual amount of bisphenol A in the system is less than or equal to 0.1 wt%, and then the temperature is kept for 0.5-1 h, more preferably 0.6-0.9 h, and further preferably 0.7-0.8 h. The detection conditions of the high performance liquid chromatography are not particularly limited in the present invention, and the detection conditions of the high performance liquid chromatography for detecting bisphenol a, which are well known to those skilled in the art, may be employed.
After the etherification reaction, the method preferably further comprises the step of removing epichlorohydrin in the etherification intermediate mixture obtained by the etherification reaction. In the invention, the epoxy chloropropane is preferably removed by distillation, and the distillation preferably comprises the steps of raising the temperature at normal pressure and then carrying out heat preservation and reduced pressure distillation; the temperature after the normal pressure temperature rise is preferably 130-140 ℃, and more preferably 135-138 ℃; the pressure of the heat-preservation reduced pressure distillation is preferably less than or equal to 600 mmHg; the time of the heat preservation and reduced pressure distillation is not specially limited, and the heat preservation and reduced pressure distillation is carried out until the distilled product is not increased any more. In the invention, the removed epichlorohydrin can be reused for the etherification reaction.
After the etherification intermediate is obtained, the etherification intermediate, anhydrous methanol and anhydrous carbonate are mixed, and solid-liquid separation is carried out after cyclization reaction to obtain crude product liquid and industrial salt.
Mixing the etherified intermediate, anhydrous methanol and anhydrous carbonate, carrying out cyclization reaction, and then carrying out solid-liquid separation to obtain bisphenol A type liquid epoxy resin and industrial salt; the industrial salt is washed with hot methanol to obtain a fine industrial salt.
In the present invention, the mass ratio of the etherification intermediate to anhydrous methanol is preferably 1: 3-5, more preferably 1: 3.5 to 4.5, and more preferably 1: 3.5-4.
In the present invention, the molar ratio of bisphenol a to anhydrous carbonate is preferably 1: 2.5-3, more preferably 1: 2.6 to 2.9, and more preferably 1: 2.7 to 2.8.
The mixing mode of the invention is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing. In the present invention, the order of mixing is preferably such that the etherified intermediate is mixed with anhydrous methanol, and the resultant anhydrous methanol solution of the etherified intermediate is mixed with anhydrous carbonate.
In the invention, the temperature of the cyclization reaction is preferably 70-75 ℃, more preferably 71-74 ℃, and further preferably 72-73 ℃, and the time of the cyclization reaction is preferably 3-4 h, more preferably 3.2-3.8 h, and further preferably 3.5-3.6 h; the cyclization reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 50-100 rpm, more preferably 60-80 rpm.
The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be employed.
In the present invention, the industrial salt is washed with hot methanol to obtain a fine industrial salt. In the invention, the temperature of the hot methanol is preferably 65-75 ℃, and more preferably 70 ℃; the mass ratio of the hot methanol to the etherification intermediate is preferably 1: 3 to 5, more preferably 1: 3.5 to 4.5, and more preferably 1: 3.5 to 4. In the present invention, the washing results in a fine industrial salt and methanol wash.
After the crude product liquid is obtained, the invention refines the crude product liquid to obtain the bisphenol A type liquid epoxy resin. In the present invention, the refining preferably includes: and distilling the crude product liquid, cooling the obtained crude bisphenol A type liquid epoxy resin to room temperature, diluting by adopting anhydrous methanol, carrying out solid-liquid separation on the diluted feed liquid, and carrying out secondary distillation on the obtained liquid product to obtain the bisphenol A type liquid epoxy resin. In the present invention, the methanol washing liquid is preferably combined with the crude product liquid before distillation. In the present invention, the distillation is not particularly limited, and methanol may be removed. The cooling method of the present invention is not particularly limited, and may be any cooling method known to those skilled in the art, specifically, natural cooling. In the present invention, the volume ratio of the crude bisphenol a type liquid epoxy resin to the anhydrous methanol for dilution is preferably 1: 0.5 to 1.5, more preferably 1: 1. the solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be employed. In the present invention, the secondary distillation is preferably distillation under reduced pressure; the pressure of the reduced pressure distillation is preferably 0.5 atm. In the invention, the methanol, the residual epichlorohydrin and the residual industrial salt can be removed through the refining, and the purity of the bisphenol A liquid epoxy resin is improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Bisphenol a type liquid epoxy resin was prepared according to the flow diagram shown in fig. 1.
(1) Under the protection of nitrogen, 347kg of epoxy chloropropane and 114kg of bisphenol A (the molar ratio of the two is 7.5: 1) are added into a reactor, the reaction is carried out for 6.5h at the temperature of 80 ℃, then the content of the bisphenol A is detected by high performance liquid chromatography, after the content of the bisphenol A is less than or equal to 0.1 wt%, the etherification reaction stage tends to be complete, and the temperature is kept for 0.75h continuously to obtain an etherification intermediate mixture; heating the etherification intermediate mixture to 135 ℃ under normal pressure, then preserving heat and carrying out vacuum distillation (the pressure is less than or equal to 600mmHg) in a clearance, receiving the distilled epichlorohydrin by a receiver, and obtaining the distillation residue as the etherification intermediate (207 kg).
(2) 725kg of anhydrous methanol (3.5 times the mass of the residue) was added to the residue to obtain a homogeneous anhydrous methanol solution of the etherification intermediate. Adding 140kg of anhydrous sodium carbonate (the molar ratio of the anhydrous sodium carbonate to the bisphenol A is 2.4: 1) into the etherification intermediate anhydrous methanol solution, stirring for 3.5h at 75 ℃ and 80rpm, and filtering to obtain a crude product liquid and industrial salt; the industrial salt was washed with 65kg of hot anhydrous methanol at 75 ℃ to give a methanol wash and a fine industrial salt.
(3) And (3) combining the crude product liquid and the methanol washing liquid, and distilling to obtain methanol and crude bisphenol A liquid epoxy resin, wherein the obtained methanol can be reused in the step (2).
(4) And (2) filtering the crude bisphenol A type liquid epoxy resin, cooling the obtained liquid product to room temperature, adding equal volume of anhydrous methanol for dilution, filtering to remove residual industrial salt, carrying out reduced pressure distillation on the obtained secondary liquid product under the condition of 0.5atm, removing a mixture of methanol and a small amount of epoxy chloropropane, and obtaining the bisphenol A type liquid epoxy resin (155.5kg, the yield is 91.4%, the purity is 99.5%), wherein the obtained methanol can be reused in the step (2).
The bisphenol A type liquid epoxy resin has the epoxy equivalent of 180-189 g/eq, the inorganic chlorine content of less than or equal to 0.05 wt%, the viscosity (25 ℃) of less than or equal to 8000mpa & s, the volatile matter (110 ℃, 3h) of less than or equal to 1.2 wt% and the chroma number of less than or equal to 3, and meets the requirements of electronic-grade products.
Example 2
A bisphenol A type liquid epoxy resin was prepared according to the method of example 1, differing from example 1 in that,
in the step (1), 694kg of epichlorohydrin and 228kg of bisphenol A are respectively adopted to obtain an etherified intermediate (414 kg);
in the step (2), the mass of the anhydrous methanol is 1450kg, and the mass of the anhydrous sodium carbonate is 275 kg; the mass of hot anhydrous methanol was 135 kg.
In the step (4), bisphenol A type liquid epoxy resin (307.3Kg, yield 90.2%, purity 99.5%) was obtained.
The bisphenol A type liquid epoxy resin has the epoxy equivalent of 180-189 g/eq, the inorganic chlorine content of less than or equal to 0.04 wt%, the viscosity (25 ℃) of less than or equal to 8000mpa & s, the volatile matter (110 ℃, 3h) of less than or equal to 1.0 wt% and the chroma number of less than or equal to 3, and meets the requirements of electronic-grade products.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the bisphenol A type liquid epoxy resin is characterized by being prepared under anhydrous conditions and comprising the following steps:
under the protective atmosphere, mixing bisphenol A and epichlorohydrin, and carrying out etherification reaction to obtain an etherification intermediate;
mixing the etherification intermediate, anhydrous methanol and anhydrous carbonate, carrying out cyclization reaction, and then carrying out solid-liquid separation to obtain a crude product liquid and industrial salt;
and refining the crude product liquid to obtain the bisphenol A type liquid epoxy resin.
2. The process according to claim 1, characterized in that the molar ratio of bisphenol A to epichlorohydrin is 1: 6 to 10.
3. The preparation method according to claim 1 or 2, characterized in that the etherification reaction temperature is 75-85 ℃ and the time is 6.5-9 h.
4. The preparation method according to claim 1, characterized by further comprising removing epichlorohydrin from the etherified intermediate mixture obtained by the etherification reaction after the etherification reaction.
5. The preparation method according to claim 1, wherein the mass ratio of the etherified intermediate to the anhydrous methanol is 1: 3 to 5.
6. The method according to claim 1, wherein the molar ratio of bisphenol A to anhydrous carbonate is 1: 2.5 to 3.
7. The process according to claim 1, 5 or 6, wherein the cyclization reaction is carried out at a temperature of 70 to 75 ℃ for 3 to 4 hours.
8. The method of claim 1, wherein the industrial salt is washed with hot methanol to obtain a fine industrial salt;
the temperature of the hot methanol is 65-75 ℃;
the mass ratio of the hot methanol to the etherification intermediate is 1: 3 to 5.
9. The production method according to claim 1, wherein the refining includes: and distilling the crude product liquid, cooling the obtained crude bisphenol A type liquid epoxy resin to room temperature, diluting by adopting anhydrous methanol, carrying out solid-liquid separation on the diluted feed liquid, and carrying out secondary distillation on the obtained liquid product to obtain the bisphenol A type liquid epoxy resin.
10. The method according to claim 9, wherein the volume ratio of the crude bisphenol a type liquid epoxy resin to the diluting anhydrous methanol is 1: 1 to 2.5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1278737A (en) * | 1969-06-10 | 1972-06-21 | Shell Int Research | Polyglycidyl ethers with a low molecular weight |
| CN1546548A (en) * | 2003-12-03 | 2004-11-17 | 青岛帝科精细化学有限公司 | High purity low molecule biphenol A epoxy resin synthetic process |
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN102040568A (en) * | 2010-11-05 | 2011-05-04 | 河北科技大学 | Synthesis method of low-molecular weight epoxy resin |
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2022
- 2022-03-21 CN CN202210274276.3A patent/CN114573789A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1278737A (en) * | 1969-06-10 | 1972-06-21 | Shell Int Research | Polyglycidyl ethers with a low molecular weight |
| CN1546548A (en) * | 2003-12-03 | 2004-11-17 | 青岛帝科精细化学有限公司 | High purity low molecule biphenol A epoxy resin synthetic process |
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN102040568A (en) * | 2010-11-05 | 2011-05-04 | 河北科技大学 | Synthesis method of low-molecular weight epoxy resin |
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