A methyl epoxy resin cured product, its preparation method and application; a methyl epoxy resin cured film, its preparation method and application.

Abstract

This invention provides a cured methyl epoxy resin product, its preparation method, and its application; and a cured methyl epoxy resin film, its preparation method, and its application, relating to the field of epoxy resin technology. This invention uses methyl epichlorohydrin and bisphenol A as initial raw materials. Due to the presence of the β-methyl group in methyl epichlorohydrin, fewer side reactions occur, resulting in a methyl epoxy resin with high purity and low total chlorine content. The methyl epoxy resin prepared by this invention contains methyl groups, which enhances the chemical solvent resistance and hydrophobic properties of the cured methyl epoxy resin. The epoxy groups in the methyl epoxy resin react with the curing agent to form a cross-linked network, and the curing efficiency and degree of curing are improved by adding a curing accelerator. This enhances the impact resistance, tensile strength, and flexural strength of the cured product. Simultaneously, the presence of methyl groups in the methyl epoxy resin reduces the cross-linking density, decreases the regularity of the three-dimensional network structure, reduces brittleness, and enhances toughness, resulting in excellent overall mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, specifically to a methyl epoxy resin cured product and its preparation method and application, and a methyl epoxy resin cured film and its preparation method and application. Background Technology

[0002] Epoxy resins are widely used in coatings, construction, composite materials, and the electronics industry due to their excellent mechanical properties, chemical resistance, adhesive properties, and electrical insulation properties. Bisphenol A diglycidyl ether, prepared by the reaction of bisphenol A (BPA) and epichlorohydrin (ECH), accounts for approximately 90% of the world's epoxy resins and is an important general-purpose epoxy resin. However, the chemical solvent resistance of cured epoxy resins still needs further improvement. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a methyl epoxy resin cured product, its preparation method and application, and a methyl epoxy resin cured film, its preparation method and application. The methyl epoxy resin cured product and the methyl epoxy resin cured film provided by this invention exhibit excellent resistance to chemical solvents.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing a methyl epoxy resin cured product, comprising the following steps:

[0006] Bisphenol A, methyl epichlorohydrin, and an etherification catalyst are mixed and subjected to an etherification reaction to obtain bisphenol A methyl chloro ether alcohol; the molar ratio of bisphenol A to methyl epichlorohydrin is 1:4 to 15.

[0007] The bisphenol A methyl chloro ether alcohol, a strong alkaline solution and an organic solvent are mixed and subjected to an epoxidation reaction to obtain a methyl epoxy resin.

[0008] The methyl epoxy resin, curing agent, and curing accelerator are mixed and cured to obtain a cured methyl epoxy resin.

[0009] Preferably, the etherification catalyst comprises one or more of boron trifluoride diethyl ether complex, tin tetrachloride, zinc perchlorate, and quaternary ammonium salt; the mass of the etherification catalyst is 0.5-6% of the mass of bisphenol A;

[0010] The etherification reaction is carried out at a temperature of 50–110°C for a time of 0.5–4 hours.

[0011] Preferably, the strong alkali in the strong alkaline solution includes an alkali metal hydroxide; the mass concentration of the strong alkaline solution is 10-50%; and the molar ratio of bisphenol A to the strong alkali is 1:1.8-2.2.

[0012] The organic solvent includes one or more of toluene, cyclohexane, dichloroethane, and chloroform;

[0013] The epoxidation reaction is carried out at a temperature of 45–80°C for a time of 1–6.5 h.

[0014] Preferably, the curing accelerator includes one or more of 2-methylimidazole, 2-ethylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol; the mass ratio of the methyl epoxy resin to the curing accelerator is 1:0.01 to 0.08.

[0015] The curing agent includes one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, isophorone diamine, and polyetheramine; the mass ratio of the methyl epoxy resin to the curing agent is 1:0.2 to 0.45.

[0016] Preferably, the curing temperature is 70–230°C and the holding time is 3.5–10 h.

[0017] The present invention also provides a methyl epoxy resin cured product obtained by the preparation method described above, wherein the methyl epoxy resin in the methyl epoxy resin cured product has the structure shown in Formula I:

[0018]

[0019] Where n is between 0 and 0.8.

[0020] This invention also provides a method for preparing a methyl epoxy resin cured film, comprising the following steps:

[0021] Methyl epoxy resin was prepared according to the preparation method described in the above technical solution;

[0022] The methyl epoxy resin, curing agent, curing accelerator and organic solvent are mixed, coated onto the substrate surface and cured to obtain a methyl epoxy resin cured film on the substrate surface.

[0023] Preferably, the curing accelerator includes one or more of 2-methylimidazole, 2-ethylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol; the mass ratio of the methyl epoxy resin to the curing accelerator is 1:0.01 to 0.08.

[0024] The curing agent includes one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, isophorone diamine, and polyetheramine; the mass ratio of the methyl epoxy resin to the curing agent is 1:0.2 to 0.45.

[0025] The organic solvent includes one or more of acetone, chloroform, and N,N-dimethylformamide;

[0026] The curing temperature is 70–230°C, and the holding time is 3.5–10 hours.

[0027] The present invention also provides a methyl epoxy resin cured film prepared by the preparation method described above, wherein the methyl epoxy resin in the methyl epoxy resin cured film has the structure shown in Formula I:

[0028]

[0029] Where n is between 0 and 0.8.

[0030] The present invention also provides the application of the methyl epoxy resin cured product or the methyl epoxy resin cured film described in the above technical solutions in adhesives, coatings, building materials or electronics industries.

[0031] This invention uses methyl epichlorohydrin and bisphenol A as initial raw materials, and carries out an etherification reaction in the presence of an etherification catalyst, followed by an epoxidation reaction in the presence of a strong alkaline solution to prepare methyl epoxy resin. Due to the presence of the β-methyl group in methyl epichlorohydrin, fewer side reactions occur during the etherification and epoxidation reactions, resulting in high purity of the prepared methyl epoxy resin. Furthermore, methyl epichlorohydrin has lower toxicity and volatility than epichlorohydrin, making the reaction process safer and more environmentally friendly. This invention improves the reaction rate and selectivity of the target product by adding an etherification catalyst, resulting in a low total chlorine content in the prepared methyl epoxy resin. The presence of methyl groups in the structure of the methyl epoxy resin prepared by this invention enhances the chemical solvent resistance and hydrophobic properties of the cured methyl epoxy resin and the cured methyl epoxy resin film (collectively referred to as the cured material). The epoxy groups in methyl epoxy resin react with the curing agent to form a cross-linked network, and the curing efficiency and degree of curing are improved by adding a curing accelerator. Simultaneously, the presence of methyl groups in the methyl epoxy resin reduces the cross-linking density and the regularity of the three-dimensional network structure, resulting in decreased brittleness and enhanced impact resistance, tensile strength, and flexural strength. The overall mechanical properties of the cured material are excellent. The methyl epoxy resin cured product and methyl epoxy resin cured film prepared by this invention possess excellent chemical solvent resistance, comprehensive mechanical properties, and hydrophobic properties, showing great application potential in adhesives, coatings, construction, composite materials, and the electronics industry.

[0032] Moreover, the preparation method of the methyl epoxy resin cured product and the methyl epoxy resin cured film provided by the present invention is simple in process, easy to operate, safe and environmentally friendly, and suitable for industrial production. Detailed Implementation

[0033] This invention provides a method for preparing a methyl epoxy resin cured product, comprising the following steps:

[0034] Bisphenol A, methyl epichlorohydrin, and an etherification catalyst are mixed and subjected to an etherification reaction to obtain bisphenol A methyl chloro ether alcohol; the molar ratio of bisphenol A to methyl epichlorohydrin is 1:4 to 15.

[0035] The bisphenol A methyl chloro ether alcohol, a strong alkaline solution and an organic solvent are mixed and subjected to an epoxidation reaction to obtain a methyl epoxy resin.

[0036] The methyl epoxy resin, curing agent, and curing accelerator are mixed and cured to obtain a cured methyl epoxy resin.

[0037] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0038] This invention involves mixing bisphenol A, methyl epichlorohydrin, and an etherification catalyst to perform an etherification reaction, thereby obtaining bisphenol A methyl chloro ether alcohol.

[0039] In this invention, the molar ratio of bisphenol A to methyl epichlorohydrin is 1:4 to 15, and in specific embodiments it can be 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15. Due to the presence of the β-methyl group in methyl epichlorohydrin, the preparation of methyl epoxy resin using it as a raw material results in fewer side reactions and higher purity of the methyl epoxy resin. Moreover, methyl epichlorohydrin has lower toxicity and volatility than epichlorohydrin, making the reaction process safer and more environmentally friendly.

[0040] In this invention, the etherification catalyst preferably comprises one or more of boron trifluoride diethyl ether complex, tin tetrachloride, zinc perchlorate, and quaternary ammonium salts, more preferably a mixed catalyst of boron trifluoride diethyl ether and quaternary ammonium salts, or boron trifluoride diethyl ether or quaternary ammonium salts; the quaternary ammonium salt preferably comprises one or more of benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and tetrabutylammonium bromide; the mass ratio of boron trifluoride diethyl ether to quaternary ammonium salt in the mixed catalyst is preferably 1:0.3 to 0.7, and in specific embodiments it can be 1:0.3, 1:0.4, 1:0.5, 1:0.6, or 1:0.7. In this invention, the mass of the etherification catalyst is 0.5% to 6% of the mass of bisphenol A, and in specific embodiments it can be 0.5%, 1%, 2%, 3%, 4%, 5%, or 6%. By adding an etherification catalyst and controlling the amount of etherification catalyst, this invention can improve the reaction rate and the selectivity of the target product, and reduce the total chlorine content in methyl epoxy resin.

[0041] In this invention, the mixing preferably includes: mixing bisphenol A and methyl epichlorohydrin until dissolved, heating and then adding an etherification catalyst for mixing; the temperature of the system after heating is preferably 50-70°C, and in a specific embodiment it can be 65°C.

[0042] In this invention, the temperature of the etherification reaction is preferably 50-110°C, and in specific embodiments it can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or 110°C; the time of the etherification reaction is preferably 0.5-4h, and in specific embodiments it can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h.

[0043] Following the etherification reaction, the present invention preferably further includes: recovering the methyl epichlorohydrin from the reaction solution obtained by the etherification reaction to obtain bisphenol A methyl chloro ether alcohol. In the present invention, the recovery preferably includes distillation, the distillation temperature preferably being 80–145°C, and in specific embodiments, it can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 145°C; the vacuum degree of the distillation is preferably -0.06 to -0.1 MPa, and in specific embodiments, it can be -0.06 MPa, -0.07 MPa, -0.08 MPa, -0.09 MPa, or -0.1 MPa. The methyl epichlorohydrin recovered by the present invention can be reused.

[0044] After obtaining bisphenol A methyl chloroether alcohol, the present invention mixes the bisphenol A methyl chloroether alcohol, a strong alkaline solution and an organic solvent, and performs an epoxidation reaction to obtain methyl epoxy resin.

[0045] In this invention, the strong alkali in the strong alkali solution preferably includes an alkali metal hydroxide, and in a specific embodiment, it can be at least one of NaOH and KOH; the mass concentration of the strong alkali solution is preferably 10-50%, and in a specific embodiment, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0046] In this invention, the molar ratio of bisphenol A to the strong alkali in the strong alkali solution is preferably 1:1.8 to 2.2, and in specific embodiments it can be 1:1.8, 1:1.9, 1:2, 1:2.1 or 1:2.2.

[0047] In this invention, the organic solvent preferably includes one or more of toluene, cyclohexane, dichloroethane, and chloroform. In this invention, the molar ratio of bisphenol A to the volume of the organic solvent is preferably 1 mol: 150-350 g, and in specific embodiments it can be 1:150 g, 1 mol: 180 g, 1 mol: 200 g, 1 mol: 220 g, 1 mol: 250 g, 1 mol: 280 g, 1 mol: 300 g, 1 mol: 320 g, or 1 mol: 350 g. In this invention, the organic solvent serves to dilute the viscosity of the chloroether alcohol.

[0048] In this invention, the mixing preferably includes: mixing bisphenol A methyl chloroether alcohol and an organic solvent and then mixing with a strong alkali solution; the temperature of the system when the strong alkali solution is added is preferably 45-60°C, and in specific embodiments it can be 45°C, 50°C, 55°C or 60°C.

[0049] In this invention, the temperature of the epoxidation reaction is preferably 45-80°C, and in specific embodiments it can be 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C; the time of the epoxidation reaction is preferably 1-6.5 hours, and in specific embodiments it can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, or 6.5 hours.

[0050] After completing the epoxidation reaction, the present invention preferably further includes: cooling the reaction system obtained from the epoxidation reaction to room temperature, filtering, separating the alkaline water, washing the obtained organic phase with water until neutral, and removing the solvent by vacuum distillation to obtain methyl epoxy resin (liquid). In the present invention, the temperature of the vacuum distillation is preferably 65-150°C, and in specific embodiments it can be 65°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C; the vacuum degree of the vacuum distillation is preferably -0.05 to -0.10 MPa, and in specific embodiments it can be -0.05 MPa, -0.06 MPa, -0.07 MPa, -0.08 MPa, -0.09 MPa or -0.1 MPa.

[0051] The methyl epoxy resin prepared by this invention has high purity and low total chlorine content. The preparation process is simple, environmentally friendly and safe, and easy for industrial production.

[0052] After obtaining the methyl epoxy resin, the present invention mixes the methyl epoxy resin, curing agent and curing accelerator, and cures them to obtain a cured methyl epoxy resin.

[0053] In this invention, the curing accelerator preferably includes one or more of 2-methylimidazole, 2-ethylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol. In this invention, the mass ratio of the methyl epoxy resin to the curing accelerator is preferably 1:0.01 to 0.08, and in specific embodiments it can be 1:0.01, 1:0.02, 1:0.03, 1:0.0, 1:0.0, 1:0.05, 1:0.06, 1:0.07, or 1:0.08. By adding a curing accelerator, this invention can improve curing efficiency and degree of curing, and enhance the impact resistance, tensile strength, flexural strength, and chemical resistance of the cured methyl epoxy resin.

[0054] In this invention, the curing agent preferably includes one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, isophorone diamine, and polyetheramine. In this invention, the mass ratio of the methyl epoxy resin to the curing agent is preferably 1:0.2 to 0.45, and in specific embodiments it can be 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, or 1:0.45.

[0055] The present invention does not have any special limitations on the mixing, as long as the raw materials are mixed evenly.

[0056] After mixing, the present invention preferably further includes: removing air bubbles from the mixture obtained by mixing, and then performing subsequent curing. In the present invention, the removal of air bubbles preferably includes vacuum removal; the vacuum degree of the vacuum removal is preferably -0.09 to -0.1 MPa; the time of vacuum removal is preferably 10 to 40 minutes, and in specific embodiments it can be 10 minutes, 20 minutes, 30 minutes or 40 minutes.

[0057] In this invention, the curing temperature is preferably 70–230°C, and the holding time is preferably 3.5–10 hours. In this invention, the curing is preferably programmed curing, which preferably includes sequentially performing a first curing, a second curing, a third curing, and a fourth curing. The temperature of the first curing is preferably 70–120°C, and in specific embodiments, it can be 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C. The holding time of the first curing is preferably 0.5–1.5 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, or 1.5 hours. The temperature of the second curing is preferably 125–145°C, and in specific embodiments, it can be 120°C, 125°C, 130°C, 135°C, 140°C, or 145°C. The holding time of the second curing is preferably… The curing time is preferably 0.5–2 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, 1.5 hours, or 2 hours. The third curing temperature is preferably 150–170°C, and in specific embodiments, it can be 150°C, 155°C, 160°C, 165°C, or 170°C. The holding time for the third curing is preferably 2–5 hours, and in specific embodiments, it can be 2 hours or 3 hours. The fourth curing temperature is preferably 175–230°C, and in specific embodiments, it can be 170°C, 175°C, 180°C, 185°C, 190°C, or 195°C. The holding time for the fourth curing is preferably 0.5–1.5 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, or 1.5 hours. In this invention, the curing is preferably carried out in a mold. This invention does not have any special limitations on the mold; any mold well known to those skilled in the art can be used.

[0058] After the curing is completed, the present invention preferably further includes: cooling the cured product to room temperature and then demolding it to obtain a methyl epoxy resin cured product.

[0059] The present invention also provides a methyl epoxy resin cured product obtained by the preparation method described above, wherein the methyl epoxy resin in the methyl epoxy resin cured product has the structure shown in Formula I:

[0060]

[0061] Wherein, n is 0 to 0.8, and in specific embodiments it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8.

[0062] Compared to existing epoxy resins, the methyl epoxy resin cured products provided by this invention have significantly improved mechanical properties such as impact resistance and tensile strength, enhanced chemical solvent resistance, and significantly reduced water absorption, making them more promising for applications in adhesives, coatings, construction, composite materials, and the electronics industry.

[0063] This invention also provides a method for preparing a methyl epoxy resin cured film, comprising the following steps:

[0064] Methyl epoxy resin was prepared according to the preparation method described in the above technical solution;

[0065] The methyl epoxy resin, curing agent, curing accelerator and organic solvent are mixed, coated onto the substrate surface and cured to obtain a methyl epoxy resin cured film on the substrate surface.

[0066] In this invention, the curing accelerator preferably includes one or more of 2-methylimidazole, 2-ethylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol. In this invention, the mass ratio of the methyl epoxy resin to the curing accelerator is preferably 1:0.01 to 0.08, and in specific embodiments it can be 1:0.01, 1:0.02, 1:0.03, 1:0.0, 1:0.0, 1:0.05, 1:0.06, 1:0.07, or 1:0.08. By adding a curing accelerator, this invention can improve curing efficiency and degree of curing, further enhancing the impact resistance, tensile strength, flexural strength, and chemical resistance of the cured methyl epoxy resin film.

[0067] In this invention, the curing agent preferably includes one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, isophorone diamine, and polyetheramine. In this invention, the mass ratio of the methyl epoxy resin to the curing agent is preferably 1:0.2 to 0.45, and in specific embodiments it can be 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, or 1:0.45.

[0068] In this invention, the organic solvent preferably includes one or more of acetone, chloroform, and N,N-dimethylformamide. In this invention, the mass ratio of the methyl epoxy resin to the organic solvent is preferably 1:0.2 to 0.4, and in specific embodiments it can be 1:0.2, 1:0.3, or 1:0.4.

[0069] The present invention does not have any special limitations on the mixing, as long as the raw materials are mixed evenly.

[0070] In this invention, the coating preferably includes spraying.

[0071] In this invention, the curing temperature is preferably 70–230°C, and the holding time is preferably 3.5–10 hours. In this invention, the curing is preferably programmed curing, which preferably includes sequentially performing a first curing, a second curing, a third curing, and a fourth curing. The temperature of the first curing is preferably 70–120°C, and in specific embodiments, it can be 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C. The holding time of the first curing is preferably 0.5–1.5 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, or 1.5 hours. The temperature of the second curing is preferably 125–145°C, and in specific embodiments, it can be 120°C, 125°C, 130°C, 135°C, 140°C, or 145°C. The holding time of the second curing is preferably… The curing time is preferably 0.5–2 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, 1.5 hours, or 2 hours. The third curing temperature is preferably 150–170°C, and in specific embodiments, it can be 150°C, 155°C, 160°C, 165°C, or 170°C. The holding time for the third curing is preferably 2–5 hours, and in specific embodiments, it can be 2 hours or 3 hours. The fourth curing temperature is preferably 175–230°C, and in specific embodiments, it can be 170°C, 175°C, 180°C, 185°C, 190°C, or 195°C. The holding time for the fourth curing is preferably 0.5–1.5 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, or 1.5 hours. In this invention, the curing is preferably carried out in a mold. This invention does not have any special limitations on the mold; any mold well known to those skilled in the art can be used.

[0072] After the curing is completed, the present invention preferably further includes: cooling the cured product to room temperature and then demolding it to obtain a methyl epoxy resin cured product.

[0073] The present invention also provides a methyl epoxy resin cured film prepared by the preparation method described above, wherein the methyl epoxy resin in the cured methyl epoxy resin has the structure shown in Formula I:

[0074]

[0075] Wherein, n is 0 to 0.8, and in specific embodiments it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8.

[0076] Compared to existing epoxy resins, the methyl epoxy resin cured film provided by this invention has significantly improved mechanical properties such as impact resistance and tensile strength, enhanced chemical solvent resistance, and significantly reduced water absorption, making it more promising for applications in adhesives, coatings, construction, composite materials, and the electronics industry.

[0077] This invention also provides the application of the methyl epoxy resin cured film or the methyl epoxy resin cured product described in the above-described technical solutions in adhesives, coatings, composite materials, building materials, or the electronics industry. In this invention, the electronics industry preferably includes electronic components or microelectronic packaging materials.

[0078] The methyl epoxy resin used in this invention contains methyl groups in its structure, which enhances the chemical solvent resistance and hydrophobic properties of the cured methyl epoxy resin and the cured methyl epoxy resin film (collectively referred to as the cured material). The epoxy groups in the methyl epoxy resin react with the curing agent to form a cross-linked network, and the curing efficiency and degree of curing are improved by adding a curing accelerator. Simultaneously, the presence of methyl groups in the methyl epoxy resin reduces the cross-linking density and the regularity of the three-dimensional network structure, resulting in decreased brittleness and enhanced impact resistance, tensile strength, and flexural strength. The cured material exhibits excellent overall mechanical properties. The methyl epoxy resin cured product and the methyl epoxy resin cured film prepared by this invention possess excellent chemical solvent resistance, comprehensive mechanical properties, and hydrophobic properties, showing great application potential in adhesives, coatings, construction, composite materials, and the electronics industry.

[0079] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, provides a methyl epoxy resin cured product, its preparation method and application, and a methyl epoxy resin cured film, its preparation method and application. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0080] Example 1

[0081] The preparation method of methyl epoxy resin is as follows: bisphenol A and methyl epichlorohydrin are added and stirred until dissolved and evenly dispersed. After heating to 65℃, boron trifluoride diethyl ether is added and mixed evenly. The temperature is raised to 90℃ and kept at that temperature for 3 hours. Methyl epichlorohydrin is recovered by vacuum distillation at 130℃ and a vacuum degree of -0.098 MPa to obtain bisphenol A methyl chloro ether alcohol. Toluene is added, and 20 wt% strong alkali solution is added dropwise at 50℃. The temperature is raised to 60℃ and kept at that temperature for 4 hours. After the reaction is completed, the mixture is allowed to stand and cool, filtered, and the alkali water is separated. The obtained organic phase is washed with water until neutral. The solvent is removed by vacuum distillation at 120℃ and a vacuum degree of -0.098 MPa to obtain liquid methyl epoxy resin with an epoxy value of 0.50 mol / 100 g and a total chlorine content of 800 ppm. The molar ratio of bisphenol A, methyl epichlorohydrin and sodium hydroxide is 1:10:2, the mass of boron trifluoride ether is 2% of the mass of bisphenol A, and the ratio of bisphenol A to toluene is 1 mol: 200 g.

[0082] The preparation of the methyl epoxy resin cured product is as follows: methyl epoxy resin, diaminodiphenyl sulfone, and 2-methylimidazole are mixed evenly at a mass ratio of 100:27:5. The mixture is then degassed by vacuuming and transferred into a mold. The mixture is cured at 110℃ for 1 hour, at 130℃ for 1 hour, at 165℃ for 3 hours, and at 185℃ for 1 hour (the curing program is recorded as: 110℃×1h+130℃×1h+165℃×3h+185℃×1h). After cooling to room temperature, the product is demolded to obtain the methyl epoxy resin cured product.

[0083] Example 2

[0084] The preparation method of methyl epoxy resin is as follows: bisphenol A and methyl epichlorohydrin are added and stirred until dissolved and evenly dispersed. Benzyltrimethylammonium chloride is added when the temperature is raised to 65℃ and mixed evenly. The temperature is raised to 90℃ and held for 3 hours. Methyl epichlorohydrin is recovered by vacuum distillation at 130℃ and a vacuum degree of -0.098 MPa to obtain bisphenol A methyl chloro ether alcohol. Toluene is added, and 20 wt% strong alkali solution is added dropwise at 50℃. The temperature is raised to 60℃ and the reaction is held for 4 hours. After the reaction is completed, the mixture is allowed to stand and cool, filtered, and the alkali water is separated. The obtained organic phase is washed with water until neutral. The solvent is removed by vacuum distillation at 120℃ and a vacuum degree of -0.098 MPa to obtain liquid methyl epoxy resin with an epoxy value of 0.46 mol / 100 g and a total chlorine content of 950 ppm. The molar ratio of bisphenol A, methyl epichlorohydrin and sodium hydroxide is 1:10:2, the mass of benzyltrimethylammonium chloride is 2.5% of the mass of bisphenol A, and the ratio of bisphenol A to toluene is 1 mol: 200 g.

[0085] The preparation of the methyl epoxy resin cured product is as follows: methyl epoxy resin, diaminodiphenyl sulfone, and 2-methylimidazole are mixed evenly at a mass ratio of 100:27:5, the air bubbles are removed by vacuuming, the mixture is transferred into a mold, and cured under a programmed curing condition of 110℃×1h+130℃×1h+165℃×3h+185℃×1h. After cooling to room temperature, the product is demolded to obtain the methyl epoxy resin cured product.

[0086] Example 3

[0087] The preparation method of methyl epoxy resin is as follows: bisphenol A and methyl epichlorohydrin are added and stirred until dissolved and evenly dispersed. When the temperature is raised to 65℃, boron trifluoride ether and benzyltrimethylammonium chloride are added and mixed evenly. The temperature is raised to 90℃ and kept at that temperature for 3 hours. Methyl epichlorohydrin is recovered by vacuum distillation at 130℃ and a vacuum degree of -0.098 MPa to obtain bisphenol A methyl chloro ether alcohol. Toluene is added, and 20 wt% strong alkali solution is added dropwise at 50℃. The temperature is raised to 60℃ and kept at that temperature for 4 hours. After the reaction is completed, the mixture is allowed to stand and cool, filtered, and the alkali water is separated. The obtained organic phase is washed with water until neutral. The solvent is removed by vacuum distillation at 120℃ and a vacuum degree of -0.098 MPa to obtain liquid methyl epoxy resin with an epoxy value of 0.52 mol / 100g and a total chlorine content of 650 ppm. The molar ratio of bisphenol A, methyl epichlorohydrin and sodium hydroxide is 1:10:2, the mass of boron trifluoride ether is 2% of the mass of bisphenol A, the mass of benzyltrimethylammonium chloride is 1% of the mass of bisphenol A, and the ratio of bisphenol A to toluene is 1 mol: 200 g.

[0088] The preparation of the methyl epoxy resin cured product is as follows: methyl epoxy resin, diaminodiphenyl sulfone, and 2-methylimidazole are mixed evenly at a mass ratio of 100:27:5. The mixture is then degassed under vacuum and transferred into a mold. It is cured under a programmed curing condition of 110℃×1h+130℃×1h+165℃×3h+185℃×1h, cooled to room temperature, and demolded to obtain the methyl epoxy resin cured product.

[0089] Comparative Example 1

[0090] The methyl epoxy resin prepared in Example 3 and diaminodiphenyl sulfone were mixed evenly at a mass ratio of 100:27. The mixture was degassed by vacuuming and transferred into a mold. It was then cured under a programmed curing condition of 140℃×1h+160℃×2h+185℃×4h+200℃×1h. After cooling to room temperature, the mixture was demolded to obtain the cured methyl epoxy resin.

[0091] Comparative Example 2

[0092] Bisphenol A epoxy resin (E51), diaminodiphenyl sulfone, and 2-methylimidazole were mixed uniformly at a mass ratio of 100:31:5. The mixture was degassed under vacuum and transferred into a mold. It was cured under a programmed curing condition of 110℃×1h+130℃×1h+165℃×3h+185℃×1h. After cooling to room temperature, the product was demolded to obtain a cured methyl epoxy resin. Similarly, in Comparative Example 2 and Examples 1-3, the molar ratio of epoxy resin to diaminodiphenyl sulfone was the same, 2:1.

[0093] Test Example 1

[0094] The performance test results of the epoxy resin cured products prepared in Examples 1-3 and Comparative Examples 1-2 are shown in Table 1. The impact strength test method was GB / T 1843-2008 Determination of Impact Strength of Plastic Cantilever Beams. The flexural properties (flexural strength and flexural modulus) test method was GB / T 9341-2008 Determination of Flexural Properties of Plastics. The tensile properties (tensile strength, tensile modulus, and elongation at break) test method was GB / T1040.2-2022 Determination of Tensile Properties of Plastics. The water absorption test method was GB / T 1034-2008 Determination of Water Absorption of Plastics.

[0095] Table 1. Test results of mechanical properties of epoxy resin cured products

[0096]

[0097] As shown in Table 1, the methyl epoxy resin provided by this invention can significantly improve the mechanical properties and impact strength of the cured methyl epoxy resin, wherein the impact strength of the cured methyl epoxy resin can reach 38.41 kJ / m. 2 It exhibits a tensile strength of up to 77.36 MPa, a flexural strength of up to 121.10 MPa, a flexural modulus of up to 3.31 GPa, a tensile modulus of up to 1.43 GPa, an elongation at break of up to 4.55%, and a water absorption rate as low as 1.77%, demonstrating excellent comprehensive mechanical properties and hydrophobicity. Furthermore, the introduction of a curing accelerator improves the curing efficiency and degree of curing of the methyl epoxy resin, resulting in even superior overall performance.

[0098] Example 4

[0099] The methyl epoxy resin prepared in Example 3, diaminodiphenyl sulfone, and 2-methylimidazole were added to a beaker at a mass ratio of 100:27:5, and acetone was added. The mixture was stirred until homogeneous to obtain a homogeneous mixture. The mixture was uniformly sprayed onto a tinplate sheet and cured under a programmed curing condition of 110℃×1h+130℃×1h+165℃×3h+185℃×1h to obtain a methyl epoxy resin cured film. The mass ratio of methyl epoxy resin to acetone was 1:0.3.

[0100] Comparative Example 3

[0101] Bisphenol A epoxy resin (E51), diaminodiphenyl sulfone, and 2-methylimidazole were added to a beaker at a mass ratio of 100:31:5, along with acetone. The mixture was stirred until homogeneous and maintained at a low viscosity. The mixture was then uniformly sprayed onto a tinplate sheet and cured under a programmed curing condition of 110℃×1h+130℃×2h+165℃×3h+185℃×1h to obtain a bisphenol A epoxy resin cured film. The mass ratio of methyl epoxy resin to acetone was 1:0.3. In Comparative Example 3 and Example 4, the molar ratio of epoxy resin to diaminodiphenyl sulfone was the same, 2:1.

[0102] Test Example 2

[0103] The performance test results of the epoxy resin cured films prepared in Example 4 and Comparative Example 3 are shown in Table 2. The hardness test method was a hand-drawing method using a Chinese pencil. The pencil hardness levels, from lowest to highest, were 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H. The solvent resistance test method was GB / T 23989-2009, "Determination of Solvent Resistance of Coatings by Wiping".

[0104] Table 2. Test results of chemical solvent resistance of epoxy resin cured film

[0105] Cured film hardness Acetone wiping count THF wiping resistance Toluene-resistant wiping cycles Example 4 5～6H 141 times 122 times 100 times Comparative Example 3 3H 82 times 89 times 76 times

[0106] As shown in Table 2, the methyl epoxy resin cured film provided by the present invention has good resistance to chemical solvents.

[0107] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing a cured product of a methylcyclohexane-epoxide, characterized by, The method comprises the following steps: mixing bisphenol A, methyl epichlorohydrin and etherification catalyst to perform etherification reaction to obtain bisphenol A methyl chloro ether alcohol; the molar ratio of bisphenol A to methyl epichlorohydrin is 1:4-15; the etherification catalyst is a mixed catalyst of boron trifluoride diethyl ether and quaternary ammonium salt or boron trifluoride diethyl ether; the mass of the etherification catalyst is 2-6% of the mass of bisphenol A; the temperature of the etherification reaction is 60-110℃; mixing the bisphenol A methyl chloro ether alcohol, strong alkali solution and organic solvent to perform epoxidation reaction to obtain methyl epoxy resin; the temperature of the epoxidation reaction is 55-80℃; mixing the methyl epoxy resin, curing agent and curing accelerator to perform curing to obtain methyl epoxy resin cured product; the methyl epoxy resin in the methyl epoxy resin cured product has the structure shown in formula I: Formula I; wherein n is 0-0.

8.

2. The production method according to claim 1, characterized by, the time of the etherification reaction is 0.5-4h.

3. The preparation method according to claim 1, characterized in that, the strong alkali in the strong alkali solution comprises alkali metal hydroxide; the mass concentration of the strong alkali solution is 10-50%; the molar ratio of bisphenol A to strong alkali is 1:1.8-2.2; the organic solvent comprises one or more of toluene, cyclohexane, dichloroethane and chloroform; the time of the epoxidation reaction is 1-6.5h.

4. The method of claim 1, wherein, the curing accelerator comprises one or more of 2-methyl imidazole, 2-ethyl imidazole and 2,4,6-tris(dimethylaminomethyl) phenol; the mass ratio of the methyl epoxy resin to the curing accelerator is 1:0.01-0.08; the curing agent comprises one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylene triamine, isophorone diamine and polyether amine; the mass ratio of the methyl epoxy resin to the curing agent is 1:0.2-0.

45.

5. The production method according to claim 1 or 4, characterized by, the curing temperature is 70-230℃, and the holding time is 3.5-10h.

6. The methyl epoxy resin cured product prepared by the preparation method in any one of claims 1-5, wherein the methyl epoxy resin in the methyl epoxy resin cured product has the structure shown in formula I: Formula I; wherein n is 0-0.

8.

7. A method for producing a cured film of a methylcyclohexane-epoxide resin, characterized by, The method comprises the following steps: The methyl epoxy resin is prepared by the preparation method in any one of claims 1-3; mixing the methyl epoxy resin, curing agent, curing accelerator and organic solvent, coating on the surface of the substrate and curing to obtain methyl epoxy resin cured film on the surface of the substrate.

8. The production method according to claim 7, characterized by, the curing accelerator comprises one or more of 2-methyl imidazole, 2-ethyl imidazole and 2,4,6-tris(dimethylaminomethyl) phenol; the mass ratio of the methyl epoxy resin to the curing accelerator is 1:0.01-0.08; the curing agent comprises one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylene triamine, isophorone diamine and polyether amine; the mass ratio of the methyl epoxy resin to the curing agent is 1:0.2-0.45; the organic solvent comprises one or more of acetone, chloroform and N,N-dimethylformamide; the curing temperature is 70-230℃, and the holding time is 3.5-10h.

9. A cured film of a methyl epoxy resin prepared by the method of claim 7 or 8, the methyl epoxy resin in the cured film having the structure of Formula I: ###0001### Formula I wherein n is 0 to 0.

8. Formula I; wherein, 10. Use of the cured product of the methyl epoxy resin of claim 6 or the cured film of the methyl epoxy resin of claim 9 in adhesives, coatings, construction materials, or the electronics industry. ​

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