A two-step process for the preparation of allyl phenolic glycidyl ethers
By employing a two-step process and molecular distillation purification, the problem of low yield in the synthesis of allylphenol glycidyl ethers was solved, enabling the preparation of high-purity, low-chlorine-content allylphenol glycidyl ethers, thus expanding their application range and demonstrating excellent performance characteristics.
Patent Information
- Authority / Receiving Office
- CN Β· China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI LONGDAO MATERIAL TECHNOLOGY CO LTD
- Filing Date
- 2026-06-11
- Publication Date
- 2026-07-31
AI Technical Summary
The current technology for synthesizing allylphenol glycidyl ethers has a low yield and no electronic-grade industrial products have been found, which cannot meet the needs of the electronics industry.
A two-step process was adopted. First, the substrate was etherified with epichlorohydrin at low temperature under catalytic conditions. Then, an epoxidation reaction was carried out under alkaline conditions. Combined with vacuum reflux water separation and molecular distillation purification, the reaction temperature and time were controlled to obtain allylphenol glycidyl ethers with low hydrolyzable chlorine and low total chlorine.
It improves the synthesis yield and purity of allylphenol glycidyl ethers, expands their application fields, and has excellent mechanical, chemical, electrical and adhesion properties, making it suitable for a variety of applications. It also has low viscosity and low hygroscopicity, making it suitable for diluents, adhesives, BMI modified curing agents, etc.
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Figure CN122483014A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of epoxy resin materials technology, specifically a two-step method for preparing allylphenol glycidyl ethers. Background Technology
[0002] Epoxy resins can be cured by methods such as heat, light, or moisture. The epoxy groups in epoxy resins can undergo ring-opening addition polymerization or ring-opening polymerization with the curing agent to achieve curing. Allylphenol glycidyl ethers are a type of functional epoxy resin monomer with a special allyl and epoxy group structure, and are often used in high-performance composite materials, adhesives, and electronic packaging materials.
[0003] Current research shows that the yield of this type of epoxy resin synthesis is relatively low, and no electronic-grade industrial products have yet been synthesized to meet the needs of the electronics industry. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention provides a two-step method for preparing allylphenol glycidyl ethers, thus solving the problems mentioned in the background section.
[0005] A two-step method for preparing allylphenol glycidyl ethers, comprising the following steps: Step 1: Place the substrate and epichlorohydrin in a four-necked flask, stir to dissolve, and then heat to the etherification ring-opening temperature, specifically 50β~100β. Add the catalyst to carry out the reaction, and the etherification ring-opening time is 2~5 hours.
[0006] Step 2: Weigh the alkaline solution and slowly add it dropwise to a four-necked flask through a constant pressure funnel to carry out the reaction. Separate the water under vacuum reflux. After the addition is complete, continue to keep the temperature for the reaction. Step 3: After the heat preservation reaction is completed, ECH is recovered. After the ECH is recovered, solvent is added to mix and dilute, and the temperature is raised to 70~90β for purification. Alkali solution is added, and the reaction is carried out for 1~4 hours. Then, the product is washed with water, separated, and the solvent is removed by vacuum evaporation to obtain crude allylphenol glycidyl ether. Taking 2,6'-diallylphenol (Example 1) as an example, its reaction equation is as follows: Step 4: Preheat the obtained crude resin and perform molecular distillation to obtain electronic-grade allylphenol glycidyl ethers; Furthermore, the substrates involved include, but are not limited to, 2,6-diallylphenol, 2-allylphenol, 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone, 2,2'-diallyl-4,4'-biphenol, 2,2'-diallylbisphenol A, and 2,2'-diallylbisphenol F; Furthermore, in step one, the molar ratio of the substrate to epichlorohydrin is 1:(5~20).
[0007] Furthermore, in step one, the catalyst is one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide or benzyltriethylammonium bromide, and the amount of catalyst used is 0.1 to 3.0% of the substrate mass.
[0008] Furthermore, in step two, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration of the alkaline solution is 10%~50%, and the molar ratio of the alkaline solution to the phenolic hydroxyl group is (0.8~1.3):1.
[0009] Furthermore, in step two, the reaction temperature is 50β~90β, the reaction time is 2~6h, the vacuum degree is -0.06MPa~-0.09MPa, the heat preservation reaction temperature is 60~90β, and the heat preservation reaction time is 1~4h.
[0010] Furthermore, in step three, the temperature for recovering ECH is 110~130β, and the solvent is one or more of toluene, xylene, methyl isobutyl ketone, and isopropanol.
[0011] Furthermore, in step three, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the molar ratio of the alkaline solution to the phenolic hydroxyl group is (0.05~0.4):1.
[0012] Furthermore, in step three, the vacuum degree for descaling the solvent is -0.1MPa to -0.05MPa, and the temperature for descaling the solvent is 120 to 140β. Furthermore, in step four, the molecular distillation temperature is 120β~230β, the saponifiable chlorine content of electronic-grade allylphenol glycidyl ether is <100ppm, and the total chlorine content is <800ppm.
[0013] This invention provides a two-step method for preparing allylphenol glycidyl ethers, which has the following advantages: 1. The two-step method for preparing allylphenol glycidyl ethers employs a two-step process, in which the substrate is first etherified with epichlorohydrin at low temperature under catalytic conditions, followed by an epoxidation reaction under alkaline conditions using epichlorohydrin as the solvent. By controlling the reaction temperature and reaction time, adjusting the amount and method of adding alkali, and performing depressurized reflux to remove water, an allylphenol glycidyl ether with low hydrolyzable chlorine and low total chlorine is obtained. Compared with ordinary bisphenol A type epoxy resin, this invention introduces an allyl structure on the benzene ring, increasing the active functional groups in the molecular chain and expanding the application field of this epoxy resin.
[0014] 2. The two-step preparation method of allylphenol glycidyl ether further improves the monomer purity of allylphenol glycidyl ether through molecular distillation purification process, and further reduces the hydrolyzable chlorine, total chlorine and viscosity of the obtained allylphenol glycidyl ether. Moreover, the diallylphenol glycidyl ether of the present invention can be cured with a variety of curing agents at room temperature or high temperature, and has excellent mechanical, chemical, electrical and adhesion properties, making it suitable for a variety of applications. In addition, its low viscosity and low hygroscopicity bring good convenience to the formulation design, and it can be used as a diluent, adhesive, BMI modified curing agent, raw material for low CTE silicone modified epoxy resin, and flame retardant epoxy resin raw material, etc. Attached Figure Description
[0015] Figure 1 This is a schematic flowchart of a two-step method for preparing allylphenol glycidyl ethers according to the present invention. Figure 2 This is a schematic diagram of the HPLC chromatographic test results of electronic-grade diallylphenol diglycidyl ether purified by molecular distillation according to the present invention.
[0016] Specific implementation examples: like Figures 1-2 As shown in Example 1: 174g of 2,6-diallylphenol and 558g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.44g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0017] Weigh 127g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is complete, the reaction is kept at 65β for 2h.
[0018] After the heat preservation reaction was completed, the temperature was raised to 120β to recover ECH. After the ECH recovery was completed, a total of 522g of methyl isobutyl ketone and isopropanol was added and mixed and diluted. The temperature was raised to T=80β, and 40g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 2,6-diallyl glycidyl ether was obtained, with an epoxy equivalent of 237.3g / mol, 176ppm of easily saponifiable chlorine, and a total chlorine of <1280ppm. The obtained diallylphenol glycidyl ether was preheated and then subjected to molecular distillation at a temperature of 140β to obtain electronic grade 2,6-diallyl glycidyl ether with an epoxy equivalent of 230.8 g / mol, 71 ppm of readily saponifiable chlorine, and 710 ppm of total chlorine.
[0019] like Figure 2 As shown, this HPLC chromatogram is the chromatographic test result of electronic-grade 2,6-diallylphenol diglycidyl ether purified by molecular distillation. Its purity is 99.1%. The main peak in the figure is symmetrical and sharp, with no obvious impurity peaks or tailing phenomenon, indicating that the product has a uniform molecular structure. This verifies the effect of molecular distillation process on improving product purity, which is consistent with the core performance requirements of low chlorine and high purity for electronic-grade products.
[0020] Example 2: 134.2g of 2-allylphenol and 558g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.44g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0021] Weigh 127g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is complete, the reaction is kept at 65β for 2h.
[0022] After the heat preservation reaction was completed, the temperature was raised to 120β to recover ECH. After the ECH was recovered, a total of 403g of methyl isobutyl ketone and isopropanol was added and diluted. The temperature was raised to T=80β, and 40g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 2-allyl glycidyl ether was obtained with an epoxy equivalent of 200.5g / mol, 155ppm of saponifiable chlorine, and 1255ppm of total chlorine. The obtained diallylphenol glycidyl ether was preheated and then subjected to molecular distillation at a temperature of 125Β°C to obtain electronic-grade 2-allyl glycidyl ether with an epoxy equivalent of 191.1 g / mol, 56 ppm of readily saponifiable chlorine, and 718 ppm of total chlorine.
[0023] Example 3: 330g of 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone and 744g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.83g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0024] Weigh 254g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is completed, the reaction is kept at 65β for 2h.
[0025] After the heat treatment reaction was completed, the temperature was raised to 120Β°C to recover ECH. After the ECH recovery was completed, a total of 990g of methyl isobutyl ketone and isopropanol was added and diluted. The temperature was raised to T=80Β°C, and 80g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 3,3'-diallylbisphenol S diglycidyl ether was obtained, with an epoxy equivalent of 232.6g / mol, easily saponifiable chlorine of 187ppm, and total chlorine <1364ppm. The obtained diallylphenol glycidyl ether was preheated and subjected to molecular distillation at 200β to obtain electronic grade 3,3'-diallyl-4,4'-diglycidyl ether diphenyl sulfone, with an epoxy equivalent of 222.3 g / mol, 61 ppm of readily saponifiable chlorine, and 772 ppm of total chlorine.
[0026] Example 4: 266g of 2,2'-diallyl-4,4'-biphenol and 744g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.67g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0027] Weigh 254g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is completed, the reaction is kept at 65β for 2h.
[0028] After the heat preservation reaction was completed, the temperature was raised to 120β to recover ECH. After the ECH was recovered, 800g of methyl isobutyl ketone and isopropanol were added and mixed and diluted. The temperature was raised to T=80β, and 80g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 2,2'-diallyl-4,4'-biphenol diglycidyl ether was obtained, with an epoxy equivalent of 198.3g / mol, easily saponifiable chlorine of 175ppm, and total chlorine of <1370ppm. The obtained diallylphenol glycidyl ether was preheated and subjected to molecular distillation at a temperature of 198Β°C to obtain electronic grade 2,2'-diallyl-4,4'-biphenol diglycidyl ether with an epoxy equivalent of 191.3 g / mol, 79 ppm of readily saponifiable chlorine, and 754 ppm of total chlorine.
[0029] Example 5: 308.4g of 2,2'-diallylbisphenol A and 744g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.77g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0030] Weigh 254g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is completed, the reaction is kept at 65β for 2h.
[0031] After the heat treatment reaction was completed, the temperature was raised to 120β to recover ECH. After the ECH recovery was completed, a total of 925g of methyl isobutyl ketone and isopropanol was added and diluted. The temperature was raised to T=80β, and 80g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 2,2'-diallyl bisphenol A diglycidyl ether was obtained, with an epoxy equivalent of 225.1g / mol, easily saponifiable chlorine of 191ppm, and total chlorine of <1325ppm. The obtained diallylphenol glycidyl ether was preheated and subjected to molecular distillation at a temperature of 205β to obtain electronic grade 2,2'-diallylbisphenol A diglycidyl ether with an epoxy equivalent of 210.8 g / mol, 74 ppm of readily saponifiable chlorine, and 761 ppm of total chlorine.
[0032] Example 6: 280.3g of 2,2'-diallylbisphenol F and 744g of epichlorohydrin were placed in a four-necked flask, stirred and dissolved, and then heated to the etherification ring-opening temperature of 50Β°C. 0.70g of tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2h.
[0033] Weigh 254g of 30% sodium hydroxide aqueous solution and slowly add it dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50β and the addition time is 4h. A vacuum is established at -0.07MPa while adding the alkali. The solution is refluxed to separate water. After the addition is completed, the reaction is kept at 65β for 2h.
[0034] After the heat preservation reaction was completed, the temperature was raised to 120β to recover ECH. After the ECH recovery was completed, a total of 840g of methyl isobutyl ketone and isopropanol was added and mixed and diluted. The temperature was raised to T=80β, and 80g of 10% sodium hydroxide aqueous solution was added and reacted for 2h. After the reaction was completed, the phases were separated, washed with water, separated into liquids, and the solvent was removed by vacuum evaporation. The vacuum degree of the solvent removal was -0.095MPa, and 2,2'-diallylbisphenol F diglycidyl ether was obtained, with an epoxy equivalent of 208.7g / mol, easily saponifiable chlorine of 182ppm, and total chlorine <1317ppm. The obtained diallylphenol glycidyl ether was preheated and subjected to molecular distillation at 200β to obtain electronic grade 2,2'-diallylbisphenol F diglycidyl ether with an epoxy equivalent of 197.6 g / mol, 75 ppm of readily saponifiable chlorine, and 719 ppm of total chlorine.
[0035] Based on the above description, this invention employs a two-step process, first etherifying the substrate allylphenol compound with epichlorohydrin under catalytic conditions at low temperature, and then carrying out an epoxidation reaction under alkaline conditions. Using epichlorohydrin as a solvent, by controlling the reaction temperature and reaction time, adjusting the amount and method of adding alkali, and performing depressurized reflux to remove water, a crude glycidyl ether product with low hydrolyzable chlorine, low total chlorine, and high yield is obtained. Compared with ordinary bisphenol A type epoxy resin, this invention introduces an allyl structure on the benzene ring, increasing the active functional groups in the molecular chain and expanding the application field of this epoxy resin.
[0036] The purity of the monomer is further improved through molecular distillation purification, which further reduces the hydrolyzable chlorine, total chlorine and viscosity of the resulting product. Moreover, the allyl glycidyl ether resin of this invention can be cured with a variety of curing agents at room temperature or high temperature, and has excellent mechanical, chemical, electrical and adhesion properties, making it suitable for a variety of applications. In addition, its low viscosity and low hygroscopicity bring good convenience to the formulation design, and it can be used as a diluent, adhesive, BMI modified curing agent, raw material for low CTE silicone modified epoxy resin, raw material for flame retardant epoxy resin, etc.
[0037] The embodiments of the present invention are given for illustrative and descriptive purposes only, and are not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention, and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.
Claims
1. A process for the preparation of allyl phenolic glycidyl ethers in a two-step process, characterized by: Includes the following steps: Step 1: Place the substrate and epichlorohydrin in a four-necked flask, stir to dissolve, heat to the etherification ring-opening temperature, specifically 50β~100β, add the catalyst to carry out the reaction, and the etherification ring-opening time is 2~5h; Step 2: Weigh the alkaline solution and slowly add it dropwise to a four-necked flask through a constant pressure funnel to carry out the reaction. Separate the water under vacuum reflux. After the addition is complete, continue to keep the temperature for the reaction. Step 3: After the heat preservation reaction is completed, ECH is recovered. After the ECH is recovered, solvent is added to mix and dilute, and the temperature is raised to 70~90β for purification. Alkali solution is added, and the reaction is carried out for 1~4 hours. Then, the product is washed with water, separated, and the solvent is removed by vacuum evaporation to obtain crude allylphenol glycidyl ether. The reaction equation is as follows: Step 4: Preheat the obtained crude resin and perform molecular distillation to obtain electronic-grade allylphenol glycidyl ether.
2. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: The substrates involved include, but are not limited to, 2,6-diallylphenol, 2-allylphenol, 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone, 2,2'-diallyl-4,4'-biphenol, 2,2'-diallylbisphenol A, and 2,2'-diallylbisphenol F.
3. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step one, the molar ratio of substrate to epichlorohydrin is 1:(5~20).
4. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step one, the catalyst is one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide or benzyltriethylammonium bromide, and the amount of catalyst used is 0.1 to 3.0% of the substrate mass.
5. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step two, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration of the alkaline solution is 10%~50%. The molar ratio of the alkaline solution to the phenolic hydroxyl group is (0.8~1.3):
1.
6. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step two, the reaction temperature is 50β~90β, the reaction time is 2~6h, the vacuum degree is -0.06MPa~-0.09MPa, the heat preservation reaction temperature is 60~90β, and the heat preservation reaction time is 1~4h.
7. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step three, the temperature for recovering ECH is 110~130β, and the solvent is one or more of toluene, xylene, methyl isobutyl ketone, and isopropanol.
8. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step three, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the molar ratio of the alkaline solution to the phenolic hydroxyl group is (0.05~0.4):
1.
9. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step three, the vacuum degree for solvent removal under reduced pressure is -0.1MPa to -0.05MPa, and the temperature for solvent removal under reduced pressure is 120 to 140β.
10. The two-step method for preparing allylphenol glycidyl ethers according to claim 1, characterized in that: In step four, the molecular distillation temperature is 120β~230β, the saponifiable chlorine content of electronic grade allylphenol glycidyl ether is <100ppm, and the total chlorine content is <800ppm.