A preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin

Abstract

This invention discloses a preparation process for the co-production of alicyclic epoxy resin and glycidyl ester epoxy resin, comprising the following steps: mixing epoxy resin raw materials, solvent, and hydrogen peroxide; adding acid anhydride to the reaction system in batches; filtering the reaction system after the reaction is completed to separate the liquid phase and by-product acid solid; obtaining alicyclic epoxy resin through a series of operations on the liquid phase; adding wet by-product acid solid and continuing to react with epichlorohydrin to finally obtain the corresponding glycidyl ester epoxy resin; and performing an epoxidation reaction by using cyclic anhydrides such as hexahydrophthalic anhydride and phthalic anhydride in combination with hydrogen peroxide to generate corresponding peroxy acids. The generated by-product dicarboxylic acid and excess raw material anhydride can be directly filtered out from the reaction system and used directly as raw materials for the production of glycidyl ester epoxy resin, thereby achieving the co-production of alicyclic epoxy resin and glycidyl ester epoxy resin.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, and in particular to a preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin. Background Technology

[0002] Alicyclic epoxy resins and their products possess excellent comprehensive properties such as processability, thermal stability, electrical insulation, and UV resistance, and have been widely used in important industrial fields such as coatings / inks, microelectronic packaging, and motor insulation. In response to the increasingly demanding performance and functionalization requirements of polymer materials in modern industry, research on the synthesis and performance of alicyclic epoxy resins has been very active in recent years. Unlike bisphenol A type epoxy resins, alicyclic epoxy resins are generally obtained from unsaturated alicyclic compounds through the epoxidation reaction of peroxides. Therefore, they have very low chlorine content, which is of great concern to the electronics industry. Furthermore, alicyclic epoxy resins have definite molecular weights and molecular structures, diverse synthesis methods, and strong structural designability, making it easy to modify their chemical composition according to actual needs. The structure allows for the adjustment of the resin's physical properties. A key characteristic of alicyclic epoxy resins is that they are generally liquid at room temperature before curing and have low viscosity, often allowing for direct application in coatings and electronic encapsulation without solvent dilution. This facilitates processes such as potting, casting, or vacuum injection. The rigid structure of the alicyclic resin and the high crosslinking density of the cured product give it excellent adhesion strength to different substrates, high heat distortion temperature, excellent chemical resistance, and superior mechanical and electrical properties. These excellent comprehensive properties have led to the widespread application of alicyclic epoxy resins in recent years in fields such as ultra-large-scale integrated circuit packaging, printed circuit board manufacturing, special photocurable coatings, and high-capacity and high-temperature resistant motor insulation materials for vacuum pressure impregnation technology. The mainstream synthesis processes for commercially available alicyclic epoxy resins and their shortcomings are as follows: 1. Catalyst (phosphotungstic acid / manganese / magnesium and other metal catalysts) - hydrogen peroxide process: The reaction temperature is 50-70℃, which can easily cause secondary decomposition of high-concentration hydrogen peroxide, bringing huge safety risks. In addition, the catalyst cannot be recovered, which puts a huge burden on subsequent wastewater treatment. The residue of heavy metals tungsten / manganese (50-300ppm) will greatly limit the application scenarios of the product. 2. Electrocatalytic in-situ hydrogen peroxide generation oxidation method: This process is a variant of the catalyst-hydrogen peroxide process. The principle is that, under the catalysis of metal catalysts such as phosphotungstic acid / manganese-based / magnesium-based catalysts, hydrogen peroxide, directly synthesized from water and air (or oxygen), undergoes an epoxidation reaction through an electrochemical oxidation-reduction reaction. However, its efficiency is currently low, requiring specially designed long-lasting electrodes and reactors. Furthermore, the generation of hydrogen gas during the process poses significant safety hazards.

[0003] 3. Peracetic acid process: The reaction process involves the preparation and storage of 16-30% peracetic acid, which requires strict control of safety risks. In addition, the acetic acid generated after the oxidation of peracetic acid will further undergo ring-opening esterification and other side reactions with the prepared epoxy compounds. The acetic acid generated in this process needs to be neutralized into sodium acetate by-product in the post-processing. The crude sodium acetate requires complicated post-processing operations (such as removing impurities, multi-effect evaporation, and recrystallization) to achieve the recycling of sodium acetate by-product, and the economic value of this sodium acetate by-product is not ideal. 4. Peracetic acid on-site oxidation process: This process is an improved version of the peracetic acid process. The principle is to use acetic acid (or acetic anhydride) and hydrogen peroxide to generate low-concentration peracetic acid on-site to participate in the epoxidation reaction. Although this process avoids the preparation and storage of high-concentration peracetic acid, the problems of the peracetic acid process itself still exist. Currently, peracetic acid process is the mainstream process for preparing alicyclic epoxy resins. How to retain the high safety advantage of peracetic acid instant oxidation process and avoid the generation of a large number of by-products is a problem worthy of attention. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a preparation process for the co-production of alicyclic epoxy resin and glycidyl ester epoxy resin, comprising the following steps: mixing epoxy resin raw materials, solvent, and hydrogen peroxide; adding acid anhydride in batches as solid to the reaction system; filtering the reaction system after the reaction is complete to separate the liquid phase and by-product acid solid; subjecting the liquid phase of the reaction liquid to phase separation, water washing, and solvent removal to obtain alicyclic epoxy resin; adding the by-product acid solid wet material and continuing to react with epichlorohydrin to finally obtain the corresponding hydroglycerol ester epoxy resin; an example is shown below (using tetrahydrobenzoic acid-tetrahydrobenzyl ester and phthalic anhydride as examples): As a further supplement to this technical solution, the epoxy resin raw material includes substrate one, which is any one of tetrahydrobenzoic acid-tetrahydrobenzyl ester, 3,4,3',4'-bi[cyclohexene], 2,2-di(3',4'-cyclohexenyl)propane, limonene, 4-vinylcyclohexene, diglycidyl tetrahydrophthalate, dicyclopentadiene, bis((3,4-cyclohexene)methyl)adipate, tetrahydroindene, 2,6-diallylphenylglycidyl ether, 2,6-diallylphenylallyl ether, methyl 3-cyclohexene methacrylate, methyl 3-cyclohexene acrylate, tetrahydrobenzyl ether, and 3-ethyl-3-[(tetrahydrobenzyloxy)methyl]oxetane.

[0005] As a further supplement to this technical solution, the acid anhydride is any one of phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

[0006] As a further supplement to this technical solution, the amount of acid anhydride used in the epoxidation reaction is 1.02-1.30 eq / carbon-carbon double bond, and the epoxidation reaction temperature is 20-70℃, preferably 25-50℃.

[0007] As a further supplement to this technical solution, the amount of hydrogen peroxide used is 1.05-2.0 eq / carbon-carbon double bond, and the concentration of hydrogen peroxide is 27%-70%, preferably 50%.

[0008] As a further supplement to this technical solution, the solvent for the epoxidation reaction is any one of dichloromethane, dichloroethane, chlorobenzene, benzene, ethyl acetate, butyl acetate, and dimethyl carbonate.

[0009] As a further supplement to this technical solution, the catalyst for the reaction between the by-product acid and epichlorohydrin is a quaternary ammonium salt, specifically one of tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, dodecyltrimethylammonium chloride, and dodecyltrimethylammonium bromide.

[0010] As a further supplement to this technical solution, the esterification reaction temperature of glycidyl ester epoxy resin is 70-110℃, preferably 80-100℃; the liquid alkali used for the ring-closing reaction of the glycidyl ester epoxy resin is 30%-48% liquid alkali, preferably 45-48% liquid alkali.

[0011] As a further supplement to this technical solution, the reaction ring-closing temperature of glycidyl ester epoxy resin is T=20-50℃, preferably T=30-40℃.

[0012] Its beneficial effect lies in the fact that by using cyclic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride in combination with hydrogen peroxide to generate corresponding peroxy acids for epoxidation reaction, the by-product dicarboxylic acid and excess raw material anhydride can be directly filtered out from the reaction system and used directly as raw materials for the production of glycidyl ester epoxy resin, thus realizing the co-production of alicyclic epoxy resin and glycidyl ester epoxy resin. Detailed Implementation

[0013] To facilitate a clearer understanding of this technical solution by those skilled in the art, the technical solution of the present invention will be described in detail below: Implementation Case 1: Add 400g of dichloroethane, 110.2g of tetrahydrobenzoic acid-tetrahydrobenzyl ester, and 122.4g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 181.6g of hexahydrophthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a product conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 60g of 5% alkali solution at T=10-20℃, then wash twice with 110g of water until pH=7-8. After solvent removal, 116.0g of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester is obtained with a purity of 95.1%. Implementation Case 2: Add 1000g of dichloroethane, 334.5g of bis((3,4-cyclohexene)methyl)adipate, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 343.4g of product is obtained, with a yield of 93.7% and a purity of 93.9%. Implementation Case 3: Add 500g of dichloroethane, 136.2g of limonene, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 153.9g of product is obtained, with a yield of 91.5% and a purity of 93.1%.

[0014] Implementation Case 4: Add 500g of dichloroethane, 108.18g of 4-vinylcyclohexene, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 123.2g of product is obtained, with a yield of 87.9% and a purity of 93.4%.

[0015] Implementation Case 5: Add 600g of dichloroethane, 204.4g of 2,2-bis(3,4-cyclohexene)propane, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 224.5g of product is obtained, with a yield of 95.0% and a purity of 95.2%.

[0016] Implementation Case Six: Add 600g of dichloroethane, 132.3g of dicyclopentadiene, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a raw material conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 153.2g of product is obtained, with a yield of 93.3% and a purity of 94.2%.

[0017] Implementation Case Seven: Add 600g of dichloroethane, 120.2g of tetrahydroindene, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 143.1g of product is obtained, with a yield of 94.0% and a purity of 94.5%.

[0018] Implementation Case 8: Add 600g of dichloroethane, 162.3g of 3,4,3',4'-bi[cyclohexene], and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride addition within 2-3 hours. After addition, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 184.0g of product is obtained, with a yield of 94.7% and a purity of 92.1%.

[0019] Implementation Case Nine: Add 900g dichloroethane, 230.3g 2,6-diallylphenyl glycidyl ether, and 244.8g 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 348g phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride addition within 2-3 hours. After addition, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g 5% alkali solution at T=10-20℃, then wash twice with 220g water until pH=7-8. After solvent removal, 241.1g of product is obtained, with a yield of 91.9% and a purity of 93.3%.

[0020] Implementation Case 10: Add 900g of dichloroethane, 214.3g of 2,6-diallylphenylallyl ether, and 367.2g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 522g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 4 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 150g of 5% alkali solution at T=10-20℃, then wash twice with 300g of water until pH=7-8. After solvent removal, 243.4g of product is obtained, with a yield of 92.8% and a purity of 93.7%.

[0021] Implementation Case Eleven: Add 900g of dichloroethane, 282.3g of tetrahydrophthalic acid diglycidyl ether, and 122.4g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 174.8g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 257.2g of product is obtained, with a yield of 91.1% and a purity of 93.9%.

[0022] Implementation Case Twelve: Add 600g of dichloroethane, 180.2g of methyl 3-cyclohexene methacrylate, and 122.4g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃. Add 174.8g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride addition within 2-3 hours. After addition, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 184.9g of product is obtained, with a yield of 94.2% and a purity of 96.6%.

[0023] Implementation Case Thirteen: Add 600g of dichloroethane, 166.2g of methyl 3-cyclohexene acrylate, and 122.4g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃. Add 174.8g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride addition within 2-3 hours. After addition, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 171.1g of product is obtained, with a yield of 93.9% and a purity of 96.3%.

[0024] Implementation Case Fourteen: Add 700g of dichloroethane, 206.3g of bis[tetrahydrobenzyl] ether, and 244.8g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃. Add 362.4g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 227.6g of product is obtained, with a yield of 95.5% and a purity of 96.1%.

[0025] Implementation Case 15: Add 700g of dichloroethane, 210.3g of 3-ethyl-3-[(tetrahydrobenzyloxy)methyl]oxetane, and 122.4g of 50% hydrogen peroxide to a 2000ml three-necked flask equipped with a mechanical stirrer, thermometer, and solid feeder. Maintain the reaction system at 25-30℃, and add 174.8g of phthalic anhydride in 6-10 batches under vigorous stirring. Complete the solid anhydride feeding within 2-3 hours. After feeding, maintain the reaction at 25-50℃ for 10-14 hours. Sampling and testing show a conversion rate ≥95%. After passing the test, centrifuge at high speed. Wash the centrifuged liquid once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=7-8. After solvent removal, 214.3g of product is obtained, with a yield of 94.7% and a purity of 94.3%.

[0026] Implementation Case Sixteen: 193.7g of wet hexahydrophthalic acid (11.1% moisture content), a byproduct of the epoxidation reaction, 620g of epichlorohydrin, and 4.13g of TBAB were mixed and stirred under nitrogen protection. The mixture was heated to 70℃ and held at that temperature. The reaction temperature was controlled between 70-100℃ until reflux. After refluxing for 0.5 hours, the temperature was rapidly lowered and held at 80-95℃ while monitoring the acidity. The reaction was considered complete when the acidity was ≤0.05mg / g.

[0027] After removing epichlorohydrin under reduced pressure, add 350g of dichloroethane to the reaction flask and stir to dissolve. Control the temperature at 20-25℃ and slowly add 211.0g of 45% liquid alkali to the reaction flask. After the addition is completed in 3-4 hours, keep the temperature at 40-50℃ for 2 hours. Take a sample to test the product content. If it is ≥95%, stop the reaction.

[0028] 1000g of water was added to the reaction flask, and the mixture was stirred and washed. The lower organic phase was separated and washed twice with 200g of water. Dichloroethane was removed under reduced pressure to obtain 270.1g of hexahydrophthalic acid diglycidyl ether, with a yield of 95% and a purity of 93.8%.

[0029] Implementation Case Seventeen: 188.8g of wet phthalic acid (12.0% moisture content), a byproduct of the epoxidation reaction, 620g of epichlorohydrin, and 4.13g of TBAB were mixed and stirred under nitrogen protection. The mixture was heated to 70℃ and held at that temperature. The reaction temperature was controlled between 70-100℃ until reflux. After refluxing for 0.5 hours, the temperature was rapidly lowered and held at 80-95℃ while monitoring the acidity. The reaction was considered complete when the acidity was ≤0.05mg / g.

[0030] After removing epichlorohydrin under reduced pressure, add 350g of dichloroethane to the reaction flask and stir to dissolve. Control the temperature at 20-25℃ and slowly add 45% liquid alkali to the reaction flask. After the addition is completed in 3-4 hours, keep the temperature at 40-50℃ for 2 hours. Take a sample to test the product content. If it is ≥95%, stop the reaction.

[0031] 1000g of water was added to the reaction flask, and the mixture was stirred and washed. The lower organic phase was separated and washed twice with 200g of water. Dichloroethane was removed under reduced pressure to obtain 262.7g of diglycidyl phthalate, with a yield of 94.4% and a purity of 94.1%.

[0032] Comparison Case 1: 660g of dichloroethane was added to a 2000ml three-necked flask, followed by 220.3g of tetrahydrobenzoic acid-tetrahydrobenzyl ester. The mixture was stirred until dissolved. The temperature was lowered to T=0-5℃, and 244.8g of 50% hydrogen peroxide was added. The temperature was maintained at 5-10℃, and 303.8g of phthalic anhydride was added in batches. Solid addition was completed within 3-4 hours. After addition, the reaction was maintained at this temperature for 10 hours. A sample was taken for testing, and the product conversion rate was 64%. After continuing the reaction for 24 hours, the conversion rate reached 71%. Phthalic anhydride was added to bring the total to 2.05 eq, and the reaction was maintained at this temperature for another 12 hours, resulting in a conversion rate of 94.9%. This indicates that reducing the amount of anhydride and lowering the reaction temperature slowed the reaction conversion too much.

[0033] Comparison Case 2: Add 660g of dichloroethane to a 2000ml three-necked flask, along with 220.3g of 3,4-cyclohexenic acid-3',4'-cyclohexene methyl ester and 612g of 20% hydrogen peroxide. Maintain the temperature at 20-30℃. Add 348.27g of phthalic anhydride in batches, completing the solid addition in 3-4 hours. After addition, maintain the reaction temperature for 10 hours. Sample testing showed a product conversion rate of 85%. Continue maintaining the temperature for another 20 hours, resulting in a conversion rate of 93%. Filter the solution at room temperature to obtain the filtrate. Wash the filter cake with 50g of dichloroethane. Combine the filtrates and separate the phases. Wash the organic phase once with 110g of 5% alkali solution at T=10-20℃, then wash twice with 220g of water until pH=6-7. Dichloroethane was removed under reduced pressure at T=30-70℃ to yield 216.6 g of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, with a yield of 85.9% and a purity of 91.3%. Decreasing the hydrogen peroxide concentration and extending the reaction time resulted in more byproducts and a lower yield.

[0034] Comparison Case 3: Add 660g of dichloroethane to a 2000ml three-necked flask, along with 220.3g of 3,4-cyclohexenic acid-3',4'-cyclohexene methyl ester and 244.8g of 50% hydrogen peroxide. Maintain the temperature at 40-50℃, then add 348.27g of phthalic anhydride in batches. Solid feeding is completed within 3-4 hours. After feeding, maintain the reaction temperature for 6 hours. Samples were taken to test the product conversion rate, which was 72%. The product was filtered at room temperature to obtain the filtrate. The filter cake was washed with 50g of dichloroethane. The filtrates were combined and the phases separated. The organic phase was washed once with 110g of 5% alkali solution at T=10-20℃, and then washed twice with 220g of water until pH=6-7. Dichloroethane was removed under reduced pressure at T = 30-70℃ to yield 211.6 g of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, with a yield of 84.0% and a purity of 70.5%. The side reactions increased significantly and the yield decreased when the epoxidation reaction temperature exceeded 40℃.

[0035] The above technical solutions only embody the preferred technical solutions of the present invention. Any modifications that may be made by those skilled in the art to certain parts thereof embody the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin, characterized in that, The process includes the following steps: mixing epoxy resin raw materials, solvents, and hydrogen peroxide; adding acid anhydride to the reaction system in batches; filtering the reaction system after the reaction is complete to separate the liquid phase and by-product acid solids; separating the liquid phase of the reaction liquid, washing it with water, and removing the solvent to obtain alicyclic epoxy resin; adding the wet by-product acid solids and continuing to react with epichlorohydrin to finally obtain the corresponding glycidyl ester epoxy resin.

2. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 1, characterized in that, The epoxy resin raw material includes substrate one, which is any one of tetrahydrobenzoic acid-tetrahydrobenzyl ester, 3,4,3',4'-bi[cyclohexene], 2,2-di(3',4'-cyclohexenyl)propane, limonene, 4-vinylcyclohexene, diglycidyl tetrahydrophthalate, dicyclopentadiene, bis((3,4-cyclohexene)methyl)adipate, tetrahydroindene, 2,6-diallylphenylglycidyl ether, 2,6-diallylphenylallyl ether, 3-ethyl-3-[(tetrahydrobenzyloxy)methyl]oxetane, and bis[tetrahydrobenzyl] ether.

3. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 2, characterized in that, The acid anhydride is any one of phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

4. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 3, characterized in that, The amount of acid anhydride used in the epoxidation reaction is 1.02-1.30 eq / carbon-carbon double bond, and the epoxidation reaction temperature is 20-70℃.

5. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 1, characterized in that, The amount of hydrogen peroxide used is 1.05-2.0 eq / carbon-carbon double bond, and the concentration of hydrogen peroxide is 27%-70%.

6. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 1, characterized in that, The solvent for the epoxidation reaction is any one of dichloromethane, dichloroethane, chlorobenzene, benzene, ethyl acetate, butyl acetate, and dimethyl carbonate.

7. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 5, characterized in that, The catalyst for the reaction between the by-product acid and epichlorohydrin is a quaternary ammonium salt, specifically one of tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, dodecyltrimethylammonium chloride, and dodecyltrimethylammonium bromide.

8. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 7, characterized in that, The esterification reaction temperature of glycidyl ester epoxy resin is 70-110℃; the reaction cyclization of the glycidyl ester epoxy resin is carried out using an aqueous solution of sodium hydroxide and potassium hydroxide.

9. The preparation process for co-producing alicyclic epoxy resin and glycidyl ester epoxy resin according to claim 8, characterized in that, The reaction ring-closing temperature of glycidyl ester epoxy resin is T = 20-50℃.

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