A two-step process for the preparation of diallyl bisphenol a diglycidyl ether

Abstract

This invention discloses a two-step method for preparing diallyl bisphenol A diglycidyl ether, relating to the field of epoxy resin materials technology. The method involves steps one to four to prepare electronic-grade diallyl bisphenol A diglycidyl ether with a viscosity of 1300-2500 mPa·s (25℃), an epoxy equivalent of 210-240 g / mol, readily saponifiable chlorine <100 ppm, and total chlorine <700 ppm. This two-step method for preparing diallyl bisphenol A diglycidyl ether utilizes a two-step process to obtain a diallyl bisphenol A diglycidyl ether with low hydrolyzable chlorine, low total chlorine, and high yield. Compared to ordinary bisphenol A type epoxy resins, this invention introduces an allyl structure onto the benzene ring, increasing the active functional groups in the molecular chain and expanding the application fields of this epoxy resin.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin materials technology, specifically a two-step method for preparing diallyl bisphenol A diglycidyl ether. 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. Diallyl bisphenol A diglycidyl ether is a functional epoxy resin monomer with a special allyl and epoxy group structure, and is often used in high-performance composite materials, adhesives, and electronic packaging materials.

[0003] In current research, the yield of diallyl bisphenol A diglycidyl ether synthesis is relatively low, and electronic-grade diallyl bisphenol A diglycidyl ether has not 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 diallyl bisphenol A diglycidyl ether, which solves the problems mentioned in the background section.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a two-step method for preparing diallyl bisphenol A diglycidyl ether, comprising the following steps: Step 1: Place diallyl bisphenol A and epichlorohydrin in a four-necked flask, stir to dissolve, and then heat to the etherification ring-opening temperature, specifically 40℃~100℃. Add a catalyst to carry out the reaction. The etherification ring-opening time is 2~6 hours. The specific process route is as follows: 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. Establish a vacuum, reflux to separate the water, and continue to keep the temperature for reaction after the addition is complete. Step 3: After the heat treatment reaction is complete, recover ECH. After ECH recovery, add solvent to mix and dilute, heat to 70~100℃ for purification, add alkaline solution, react for 1~4 hours, then wash with water, separate, and remove solvent under reduced pressure to obtain diallyl bisphenol A diglycidyl ether with viscosity, epoxy equivalent, easily saponifiable chlorine, and total chlorine. Its structure is shown in the following formula: In the formula, n = 0, 1, 2, 3, 4, 5.

[0006] Step 4: Preheat the obtained diallyl bisphenol A diglycidyl ether and perform molecular distillation to obtain electronic-grade diallyl bisphenol A diglycidyl ether, the structure of which is shown in the following formula: .

[0007] Furthermore, in step one, the molar ratio of diallyl bisphenol A and epichlorohydrin is 1:(4~20).

[0008] 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 mass of diallylbisphenol A.

[0009] 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.

[0010] Furthermore, in step two, the reaction temperature is 40℃~90℃, the reaction time is 2~8h, the vacuum degree is -0.06MPa~-0.09MPa, the heat preservation reaction temperature is 60~90℃, and the heat preservation reaction time is 1~4h.

[0011] Furthermore, in step three, the temperature for recovering ECH is 110~135℃, and the solvent is one or more of toluene, xylene, methyl isobutyl ketone, isopropanol, and n-butanol.

[0012] 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.

[0013] 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 125 to 150℃. The viscosity of diallyl bisphenol A diglycidyl ether is 1500~3500 mPa·s (25℃), the epoxy equivalent is 210~250 g / mol, the saponifiable chlorine is <300 ppm, and the total chlorine is <1400 ppm.

[0014] Furthermore, in step four, the molecular distillation temperature is 180℃~250℃, the viscosity of electronic grade diallyl bisphenol A diglycidyl ether is 1300~2500 mPa·s (25℃), the epoxy equivalent is 210~240 g / mol, the saponifiable chlorine is <100 ppm, and the total chlorine is <700 ppm.

[0015] This invention provides a two-step method for preparing diallyl bisphenol A diglycidyl ether, which has the following advantages: 1. The two-step method for preparing diallyl bisphenol A diglycidyl ether employs a two-step process. Diallyl bisphenol A 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 time, adjusting the amount and method of alkali addition, and implementing depressurized reflux to remove water, a diallyl bisphenol A diglycidyl ether with low hydrolyzable chlorine, low total chlorine, and high yield is obtained. Compared to ordinary bisphenol A type epoxy resins, this invention introduces an allyl structure onto the benzene ring, increasing the active functional groups in the molecular chain and expanding the application fields of this type of epoxy resin.

[0016] 2. The two-step method for preparing diallyl bisphenol A diglycidyl ether further improves the monomer purity of diallyl bisphenol A diglycidyl ether through molecular distillation purification, and further reduces the hydrolyzable chlorine, total chlorine, and viscosity of the obtained diallyl bisphenol A diglycidyl ether. Moreover, the diallyl bisphenol A diglycidyl ether of this invention can be cured with various curing agents at room temperature or high temperature, and has excellent mechanical, chemical, electrical, and adhesion properties, making it suitable for various applications. In addition, its low viscosity and low hygroscopicity bring good convenience to 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 raw material for flame retardant epoxy resin, etc. Attached Figure Description

[0017] Figure 1 This is a schematic flowchart of the two-step preparation method of diallyl bisphenol A diglycidyl ether according to the present invention. Figure 2 This is a schematic diagram of the gel permeation chromatography test results of electronic-grade diallyl bisphenol A diglycidyl ether purified by molecular distillation according to the present invention. Detailed Implementation

[0018] The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0019] like Figures 1-2 As shown, the present invention provides a technical solution: a two-step method for preparing diallyl bisphenol A diglycidyl ether, comprising the following steps: Step 1: Place diallyl bisphenol A and epichlorohydrin in a four-necked flask, stir to dissolve, and then heat to the etherification ring-opening temperature, specifically 40℃~100℃. Add a catalyst to carry out the reaction. The etherification ring-opening time is 2~6 hours. The specific process route is as follows: The molar ratio of diallyl bisphenol A to epichlorohydrin is 1:(4~20), and the catalyst is one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, or benzyltriethylammonium bromide, and the amount of catalyst used is 0.1~3.0% of the mass of diallyl bisphenol A. 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. Establish a vacuum, reflux to separate the water, and continue to keep the temperature for reaction after the addition is complete. 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. The reaction temperature is 40℃~90℃, the reaction time is 2~8h, the vacuum degree is -0.06MPa~-0.09MPa, the heat preservation reaction temperature is 60~90℃, and the heat preservation reaction time is 1~4h. Step 3: After the heat treatment reaction is complete, recover ECH. After ECH recovery, add solvent to mix and dilute, heat to 70~100℃ for purification, add alkaline solution, react for 1~4 hours, then wash with water, separate, and remove solvent under reduced pressure to obtain diallyl bisphenol A diglycidyl ether with viscosity, epoxy equivalent, easily saponifiable chlorine, and total chlorine. Its structure is shown in the following formula: In the formula, n = 0, 1, 2, 3, 4, 5.

[0020] The temperature for recovering ECH is 110~135℃, the solvent is one or more of toluene, xylene, methyl isobutyl ketone, isopropanol, and n-butanol, the alkaline solution is sodium hydroxide solution or potassium hydroxide solution, the molar ratio of alkaline solution to phenolic hydroxyl groups is (0.05~0.4):1, the vacuum degree for removing the solvent by vacuum distillation is -0.1MPa~-0.05MPa, and the temperature for removing the solvent by vacuum distillation is 125~150℃; The viscosity of diallyl bisphenol A diglycidyl ether is 1500~3500 mPa·s (25℃), the epoxy equivalent is 210~250 g / mol, the saponifiable chlorine is <300 ppm, and the total chlorine is <1400 ppm. Step 4: Preheat the obtained diallyl bisphenol A diglycidyl ether and perform molecular distillation to obtain electronic-grade diallyl bisphenol A diglycidyl ether, the structure of which is shown in the following formula: The molecular distillation temperature is 180℃~250℃, the viscosity of electronic grade diallyl bisphenol A diglycidyl ether is 1300~2500 mPa·s (25℃), the epoxy equivalent is 210~240 g / mol, the saponifiable chlorine is <100 ppm, and the total chlorine is <700 ppm.

[0021] Example: Diallyl bisphenol A and epichlorohydrin were placed in a four-necked flask with a molar ratio of 1:8. After stirring to dissolve, the mixture was heated to the etherification ring-opening temperature of 50°C. Tetraethylammonium bromide was then added to carry out the reaction. The etherification ring-opening time was 2 hours. The amount of tetraethylammonium bromide used was 0.25% of the mass of diallyl bisphenol A. Weigh out a 25% sodium hydroxide solution with a molar ratio of 0.95:1 to phenolic hydroxyl groups. Slowly add the solution dropwise through a constant pressure funnel to a four-necked flask for reaction. The reaction temperature is 50℃ and the reaction time is 4h. Establish a vacuum with a vacuum degree of -0.07MPa. Reflux to separate water. After the addition is complete, continue to keep the reaction at 65℃ for 2h. After the heat treatment reaction is completed, ECH is recovered at a temperature of 120℃. After the ECH is recovered, methyl isobutyl ketone and isopropanol are added and diluted. The mixture is then heated to 80℃ for purification. A 10% sodium hydroxide solution is added, with a molar ratio of sodium hydroxide solution to phenolic hydroxyl groups of 0.1:1. The reaction is carried out for 2 hours. The mixture is then washed with water, separated, and the solvent is removed by vacuum evaporation at a vacuum degree of -0.095 MPa to obtain diallyl bisphenol A diglycidyl ether with a viscosity of 2500 mPa·s (25℃), an epoxy equivalent of 230 g / mol, saponifiable chlorine <200 ppm, and total chlorine <1250 ppm. The obtained diallyl bisphenol A diglycidyl ether was preheated and subjected to molecular distillation at a temperature of 190℃ to obtain electronic grade diallyl bisphenol A diglycidyl ether with a viscosity of 1800 mPa·s (25℃), an epoxy equivalent of 220 g / mol, easily saponifiable chlorine < 50 ppm, and total chlorine < 600 ppm. like Figure 2 As shown, this GPC spectrum is the result of gel permeation chromatography of electronic-grade diallyl bisphenol A diglycidyl ether purified by molecular distillation. Its number-average molecular weight is 288, weight-average molecular weight is 292, and purity is 99.6%. 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 and no significant low molecular weight impurities or high molecular weight oligomer residues. 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.

[0022] Based on the above description, this invention employs a two-step process: diallyl bisphenol A and epichlorohydrin are first etherified at low temperature under catalytic conditions, and then epoxidized 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 applying depressurized reflux to remove water, a diallyl bisphenol A diglycidyl ether 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.

[0023] The monomer purity of diallyl bisphenol A diglycidyl ether was further improved through molecular distillation purification, which further reduced the hydrolyzable chlorine, total chlorine, and viscosity of the obtained diallyl bisphenol A diglycidyl ether. Moreover, the diallyl bisphenol A diglycidyl ether 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 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 raw material for flame retardant epoxy resin, etc.

[0024] 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 two-step method for preparing diallyl bisphenol A diglycidyl ether, characterized in that: Includes the following steps: Step 1: Place diallyl bisphenol A and epichlorohydrin in a four-necked flask, stir to dissolve, and then heat to the etherification ring-opening temperature, specifically 40℃~100℃. Add a catalyst to carry out the reaction. The etherification ring-opening time is 2~6 hours. The specific process route is as follows: 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. Establish a vacuum, reflux to separate the water, and continue to keep the temperature for reaction after the addition is complete. Step 3: After the heat treatment reaction is complete, recover ECH. After ECH recovery, add solvent to mix and dilute, heat to 70~100℃ for purification, add alkaline solution, react for 1~4 hours, then wash with water, separate, and remove solvent under reduced pressure to obtain diallyl bisphenol A diglycidyl ether with viscosity, epoxy equivalent, easily saponifiable chlorine, and total chlorine. Its structure is shown in the following formula: In the formula, n = 0, 1, 2, 3, 4, 5. Step 4: Preheat the obtained diallyl bisphenol A diglycidyl ether and perform molecular distillation to obtain electronic-grade diallyl bisphenol A diglycidyl ether, the structure of which is shown in the following formula: 。 2. The two-step method for preparing diallyl bisphenol A diglycidyl ether according to claim 1, characterized in that: In step one, the molar ratio of diallyl bisphenol A and epichlorohydrin is 1:(4~20).

3. The two-step method for preparing diallyl bisphenol A diglycidyl ether 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 mass of diallylbisphenol A.

4. The two-step method for preparing diallyl bisphenol A diglycidyl ether 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.

5. The two-step method for preparing diallyl bisphenol A diglycidyl ether according to claim 1, characterized in that: In step two, the reaction temperature is 40℃~90℃, the reaction time is 2~8h, the vacuum degree is -0.06MPa~-0.09MPa, the heat preservation reaction temperature is 60~90℃, and the heat preservation reaction time is 1~4h.

6. The two-step method for preparing diallyl bisphenol A diglycidyl ether according to claim 1, characterized in that: In step three, the temperature for recovering ECH is 110~135℃, and the solvent is one or more of toluene, xylene, methyl isobutyl ketone, isopropanol, and n-butanol.

7. The two-step method for preparing diallyl bisphenol A diglycidyl ether 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.

8. The two-step method for preparing diallyl bisphenol A diglycidyl ether according to claim 1, characterized in that: In step three, the vacuum degree for descaling the solvent is -0.1MPa to -0.05MPa, and the temperature for descaling the solvent is 125 to 150℃. The viscosity of diallyl bisphenol A diglycidyl ether is 1500~3500 mPa·s (25℃), the epoxy equivalent is 210~250 g / mol, the saponifiable chlorine is <300 ppm, and the total chlorine is <1400 ppm.

9. The two-step method for preparing diallyl bisphenol A diglycidyl ether according to claim 1, characterized in that: In step four, the molecular distillation temperature is 180℃~250℃, the viscosity of electronic grade diallyl bisphenol A diglycidyl ether is 1300~2500 mPa·s (25℃), the epoxy equivalent is 210~240 g / mol, the saponifiable chlorine is <100 ppm, and the total chlorine is <700 ppm.

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