High-performance epoxy resin and preparation method therefor

Abstract

The present invention relates to a high-performance epoxy resin and a preparation method therefor. The preparation method comprises: dissolving cyclohexyl-3-alkenyl-1-diethyl ether and methylphenyldichlorosilane in a solvent, carrying out stirring for dissolution and then adding an inorganic peroxide catalyst, and carrying out heating, a reflux reaction, cooling, washing with water, and drying to obtain a first solid intermediate product; dissolving 3-furoic acid and maleic anhydride in a solvent, carrying out stirring for dissolution and then adding an alkaline catalyst, carrying out first heating, a first reflux reaction, first cooling, washing with water, and drying, adding an acidic catalyst, and carrying out second heating, a second reflux reaction, second cooling, washing with water, and drying to obtain a second solid intermediate product; and dissolving the first solid intermediate product and the second solid intermediate product in a solvent, carrying out stirring for dissolution, and then carrying out heating, a reflux reaction, cooling, and drying to obtain a high-performance epoxy resin. The present invention solves the problem of resins having low molecular regularity, non-concentrated molecular weight distribution, high molecular activity, poor thermal stability after curing, and a low self-healing rate.

Description

A high-performance epoxy resin and its preparation method Technical Field

[0001] The present invention relates to the technical field of resins, in particular to a high-performance epoxy resin and a preparation method thereof. Background Art

[0002] Self-healing polymers are widely used in various fields, including ultra-high voltage power transmission, new energy equipment, and aerospace vehicles, due to their significant potential to improve material reliability and service life. Long-term exposure to mechanical, electrical, and thermal stresses gradually develops fatigue defects within the material, such as "mechanical cracks" and "electrical trees." Fatigue defects typically begin with a degradation of material properties, then evolve into internal pores and cracks, ultimately leading to catastrophic equipment failure. This type of internal damage is difficult to detect externally until it causes a severe, catastrophic failure.

[0003] Currently, most self-healing methods are mainly aimed at exposed damage, such as shear damage and surface cracks, while there is less research on the repair of invisible damage inside the material. External self-healing methods, such as those based on the use of microcapsules and fiber-reinforced composites, have the disadvantages of limited healing time and complex preparation. In addition, methods commonly used for soft or thermoplastic materials usually lose their mechanical and electrical stability during the healing process. In order to meet the growing demand for self-healing properties of materials, there is an urgent need to design and use new self-healing materials. The introduction of special groups into epoxy resins can reversibly switch between the glassy state and high elasticity. The coexistence of reversible and permanent cross-linking sites in the resin can prepare new self-healing materials. Therefore, the preparation of self-healing materials by modifying epoxy resins by introducing special groups has very broad prospects.

[0004] In their article (Effect of Nano-SiO2 on the Performance of Self-Healing Materials Filled with Epoxy Resin Microcapsules), Zhang Lunliang et al. proposed that the mechanical properties, repair rate and surface morphology of epoxy resins could be improved by adding inorganic nanoparticles (nano-SiO2). When the nano-silicon oxide content was 10%, the mechanical properties of the epoxy resin were optimal, and the repair rate reached 94.6%. In their article (Preparation and Performance Study of Self-Healing Epoxy Resin Based on Quadruple Hydrogen Bonds), Jing Ying et al. pointed out that the greater the cross-linking density of the epoxy resin, the stronger the hardness / tensile strength. The lower the cross-linking degree, the lower the glass transition temperature Tg, and the better the self-healing efficiency. Therefore, the present invention considers introducing Si-O groups into the epoxy structure to develop different types of high-performance epoxy resins. These high-performance epoxy resins are superior to traditional epoxies in terms of mechanics, thermal stability, self-healing, etc., and can meet the requirements of high-performance epoxy resins with higher cross-linking density, higher glass transition temperature Tg, and better self-healing efficiency.

[0005] Therefore, in view of the above problems, the present invention is in urgent need of providing a high-performance epoxy resin and a preparation method thereof.

[0006] Summary of the Invention

[0007] The present invention aims to provide a high-performance epoxy resin and a method for preparing the same, which aims to solve the technical problems in the prior art of obtaining resins with low molecular regularity, non-centralized molecular weight distribution, high molecular activity, poor thermal stability of the cured epoxy resin, low self-healing rate, and unstable preparation methods.

[0008] The present invention provides a method for preparing a high-performance epoxy resin, characterized by comprising the following steps:

[0009] s1: dissolving cyclohexyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane in a solvent, stirring to dissolve, adding an inorganic peroxide catalyst, heating, performing a reflux reaction, cooling, washing with water, and drying to obtain a first solid intermediate product;

[0010] s2: dissolving 3-furoic acid and maleic anhydride in a solvent, stirring and dissolving, adding a basic catalyst, heating for a first time, performing a first reflux reaction, cooling for a first time, washing with water, drying, adding an acidic catalyst, heating for a second time, performing a second reflux reaction, cooling for a second time, washing with water, and drying to obtain a second solid intermediate product;

[0011] s3: dissolving the first solid intermediate product and the second solid intermediate product in a solvent, stirring and dissolving, heating, performing a reflux reaction, cooling, and drying to obtain a high-performance epoxy resin.

[0012] Preferably, in step s1, by mass:

[0013] 60-75 parts of cycloethyl-3-enyl-1-ethyl ether, 35-45 parts of methylphenyldichlorosilane, and 0.6-0.8 parts of inorganic peroxide catalyst.

[0014] Preferably, in step s1, nitrogen is introduced into the reaction system, the heating temperature is 57-65°C, the reflux reaction time is 24-36h, and the temperature is lowered to 30-35°C.

[0015] Preferably, the inorganic peroxide catalyst is at least one of hydrogen peroxide, sodium peroxide, calcium peroxide and magnesium peroxide.

[0016] Preferably, in step s2, by mass:

[0017] 70-85 parts of 3-furoic acid, 80-110 parts of maleic anhydride, 4-8 parts of basic catalyst, and 0.2-0.4 parts of acidic catalyst.

[0018] Preferably, in step s2, the alkaline catalyst is at least one of sodium carbonate, sodium carbonate or calcium carbonate, and the acidic catalyst is at least one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid;

[0019] The first heating temperature is 65-75°C, the first reflux reaction time is 12-24h, and the first cooling temperature is 30-35°C;

[0020] The second heating temperature is 60-85°C, the second reflux reaction time is 12-24h, and the second cooling is to 30-35°C.

[0021] Preferably, in step s3, the heating temperature is 95-130°C, the reflux reaction time is 12-24h, and the temperature is lowered to 30-35°C.

[0022] Preferably, the solvent is at least one of acetone, diethyl ether or tetrahydrofuran.

[0023] Preferably, the reaction is carried out in a reactor.

[0024] The present invention also provides a high-performance epoxy resin obtained by the preparation method of any one of the high-performance epoxy resins described above.

[0025] The high-performance epoxy resin and preparation method provided by the present invention have the following improvements compared with the prior art:

[0026] 1. The present invention provides a high-performance epoxy resin and a preparation method thereof. The Si-O contained in the first solid intermediate product is very stable, which can make the epoxy resin have acid resistance, alkali resistance and high temperature resistance. Methylphenyldichlorosilane contains multi-arm highly reactive Si-Cl bonds, which are easy to chemically replace to obtain silicon-modified epoxy resin. The molecular design flexibility is high and it is very suitable for the preparation of silicon-modified epoxy resin. The hydroxyl group in cycloethyl-3-alkenyl-1-ethyl ether can undergo a substitution reaction with the multi-arm highly reactive Si-Cl bonds in methylphenyldichlorosilane to generate a stable multi-substituted silicon-containing compound. 3-Furoic acid and maleic anhydride contain carbon-carbon double bonds. Under certain conditions, the carbon-carbon double bonds are opened and the two undergo an addition reaction. The resulting product has two functional groups, anhydride and carboxyl, and other groups or molecules can be introduced to further improve the design flexibility of the molecule. The synthesized product has good heat resistance and excellent flame retardancy. The mechanical properties of the modified epoxy resin obtained after curing are greatly improved.

[0027] 2. In the preparation process of the high-performance epoxy resin provided by the present invention, the reaction is roughly divided into three stages, and the reactants in each stage are different. In step s1, nitrogen is introduced to keep the reaction system in an oxygen-free and water-free state. The highly reactive Si-Cl bond of methylphenyldichlorosilane is catalytically activated, and a hydrolysis-like reaction occurs. The hydroxyl groups in the reaction system can participate in the reaction to form Si-O bonds. Methylphenyldichlorosilane and cycloethyl-3-enyl-1-ethyl ether continue to react to produce a carbon-carbon double bond product, and then an inorganic peroxide is added to further oxidize the double bond into an epoxy functional group, successfully preparing a bifunctional epoxy resin. resin; sodium carbonate is added in step s2 to make the reaction system weakly alkaline, preventing the carboxylic acid in 3-furoic acid from participating in the reaction; dilute hydrochloric acid is added to neutralize the sodium carbonate and generate carboxyl groups in the product, providing reactive groups for the next reaction; step s3 is a ring-opening reaction of carboxyl groups, acid anhydride and epoxy groups to generate an epoxy network structure. The reaction will spontaneously move in the ring-opening direction after heating, and no additional catalyst is required. The four monomers are added in the order provided in the method name and mixed separately, which is conducive to contact reaction between different reactants during the reaction, improves the regularity of the molecular structure of the epoxy resin, and is conducive to the stability of the quality of the modified epoxy resin.

[0028] 3. In the preparation process of the high-performance epoxy resin provided by the present invention, the core of self-repair is acid anhydride and carboxyl group. In step s2, excess maleic anhydride is added to improve the utilization rate of 3-furoic acid, thereby generating more six-membered rings. The three reaction stages require first stirring the solvent and the raw materials evenly, and then adding the catalyst, in order to ensure sufficient contact between the different reactants and improve the molecular regularity of the product. In step s1, excess cycloethyl-3-alkenyl-1-ethyl ether is added to improve the utilization rate of methylphenyldichlorosilane, which can generate more binary substituted silicon-modified epoxy resin, improve the molecular regularity of the resin, reduce the resin activity, and improve the thermal stability of the resin.

[0029] 4. The preparation process provided by the present invention is divided into three stages, and each stage performs reflux reaction in a different solvent, which can improve the conversion rate of each reaction step. The reflux time of step s1 is longer than that of step s2 and step s3, which can improve the conversion rate of silane. On the other hand, the catalytic rate of inorganic peroxide is slow, and the extension of reaction time ensures that silane is converted into silicon-containing epoxy resin; the selection of inorganic peroxide as the catalyst in step s1 can ensure the catalytic efficiency; step s2 needs to improve the catalytic efficiency, and the commonly used strong acid dilute hydrochloric acid is selected to better improve the economic benefits of the preparation process.

[0030] 5. The high-performance epoxy resin and preparation method provided by the present invention have high molecular regularity and low molecular activity. The cured resin has strong heat resistance, excellent self-repairing properties, and stable mechanical properties. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0032] The present invention provides a method for preparing a high-performance epoxy resin, characterized by comprising the following steps:

[0033] S1: Dissolve cyclohexyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane in a solvent, stir and dissolve, then add an inorganic peroxide catalyst, heat, perform reflux reaction, cool, wash with water, and dry to obtain a first solid intermediate product. The reaction formula is as follows:

[0034] S2: Dissolve 3-furoic acid and maleic anhydride in a solvent, stir and dissolve, then add a basic catalyst, heat for the first time, perform a first reflux reaction, cool for the first time, wash with water, dry, add an acidic catalyst, heat for the second time, perform a second reflux reaction, cool for the second time, wash with water, and dry to obtain a second solid intermediate product, the reaction formula is as follows:

[0035] S3: Dissolve the first solid intermediate product and the second solid intermediate product in a solvent, stir and dissolve, heat, perform reflux reaction, cool, and dry to obtain a high-performance epoxy resin. The reaction formula is as follows:

[0036] Specifically, in step s1, by mass:

[0037] 60-75 parts of cycloethyl-3-enyl-1-ethyl ether, 35-45 parts of methylphenyldichlorosilane, and 0.6-0.8 parts of inorganic peroxide catalyst.

[0038] Specifically, in step s1, nitrogen is introduced into the reaction system, the heating temperature is 57-65°C, the reflux reaction time is 24-36h, and the temperature is lowered to 30-35°C.

[0039] Specifically, the inorganic peroxide catalyst is at least one of hydrogen peroxide, sodium peroxide, calcium peroxide and magnesium peroxide.

[0040] Specifically, in step s2, by mass:

[0041] 70-85 parts of 3-furoic acid, 80-110 parts of maleic anhydride, 4-8 parts of basic catalyst, and 0.2-0.4 parts of acidic catalyst.

[0042] Specifically, in step s2, the alkaline catalyst is at least one of sodium carbonate, sodium carbonate or calcium carbonate, and the acidic catalyst is at least one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid;

[0043] The first heating temperature is 65-75°C, the first reflux reaction time is 12-24h, and the first cooling temperature is 30-35°C;

[0044] The second heating temperature is 60-85°C, the second reflux reaction time is 12-24h, and the second cooling is to 30-35°C.

[0045] Specifically, in step s3, the heating temperature is 95-130°C, the reflux reaction time is 12-24h, and the temperature is lowered to 30-35°C.

[0046] Specifically, the solvent is at least one of acetone, ether or tetrahydrofuran.

[0047] Specifically, the reaction is carried out in a reactor.

[0048] The present invention also provides a high-performance epoxy resin obtained by the preparation method of any one of the high-performance epoxy resins described above.

[0049] Example 1

[0050] Preparation of Sample 1:

[0051] Weigh 70 parts of cyclohexyl-3-enyl-1-ethyl ether, 35 parts of methylphenyldichlorosilane, 0.6 parts of hydrogen peroxide, 70 parts of 3-furoic acid, 90 parts of maleic anhydride, 8 parts of sodium carbonate and 0.4 parts of dilute hydrochloric acid;

[0052] The specific steps include:

[0053] (1) adding acetone, cyclohexyl-3-enyl-1-ethyl ether, and methylphenyldichlorosilane, stirring thoroughly to dissolve, adding hydrogen peroxide, heating to 60° C. until the solution boils, refluxing for 24 hours, cooling to 30° C., washing with water, and drying to obtain a first solid intermediate product;

[0054] (2) adding ether, maleic anhydride and 3-furoic acid, stirring and dissolving, adding sodium carbonate, heating to 70°C and boiling the solution, reflux reaction for 12 hours, cooling to 30°C, washing with water, drying, adding dilute hydrochloric acid, heating to 75°C and boiling the solution, reflux reaction for 12 hours, cooling to 30°C, washing with water, and drying to obtain a second solid intermediate product;

[0055] (3) The first solid intermediate product and the second solid intermediate product were added to tetrahydrofuran, stirred and dissolved, heated to 120° C. until the solution boiled, refluxed for 12 h, cooled to 30° C., and vacuum dried to obtain a high-performance epoxy resin.

[0056] The high-performance epoxy resin prepared in Example 1 has the following properties: glass transition temperature of 173.3° C., tensile strength of 68.7 MPa at 150° C., flexural strength of 124.6 MPa at 150° C., and self-healing rate of 98.9%.

[0057] Example 2

[0058] Preparation of Sample 2:

[0059] The preparation method of sample 2 is the same as that of sample 1, except that 3 parts of sodium carbonate are weighed.

[0060] The obtained properties are shown in Table 1. By comparing sample 1 with sample 2, it is found that the glass transition temperature of sample 1 is higher than that of sample 2. The 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of sample 2.

[0061] Example 3

[0062] Preparation of Sample 3:

[0063] The preparation method of sample 3 is the same as that of sample 1, with the only difference being:

[0064] Weigh 60 parts of cyclohexyl-3-enyl-1-ethyl ether, 45 parts of methylphenyldichlorosilane, 75 parts of 3-furoic acid, and 80 parts of maleic anhydride;

[0065] In step (1), acetone, cyclohexyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane are added and stirred thoroughly to dissolve, and then hydrogen peroxide is added. The solution is heated to 57° C. and boiled. After reflux reaction for 28 hours, the solution is cooled to 35° C., washed with water, and dried to obtain a first solid intermediate product.

[0066] In step (2), ether, maleic anhydride and 3-furoic acid were added and stirred to dissolve, sodium carbonate was added, and the solution was heated to 65° C. and boiled, and refluxed for 18 h. After the reflux reaction was completed, the solution was cooled to 35° C., washed with water, and dried;

[0067] In step (3), the first solid intermediate product and the second solid intermediate product are added to tetrahydrofuran, stirred and dissolved, refluxed for 18 hours, cooled to 35° C., and vacuum dried to obtain a high-performance epoxy resin.

[0068] The obtained properties are shown in Table 1. By comparing sample 1 with sample 3, it is found that the glass transition temperature of sample 1 is higher than that of sample 3, and the 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of sample 3.

[0069] Example 4

[0070] Preparation of Sample 4:

[0071] The preparation method of sample 4 is the same as that of sample 1, with the only difference being:

[0072] Weigh 75 parts of cyclohexyl-3-enyl-1-ethyl ether, 40 parts of methylphenyldichlorosilane, 80 parts of 3-furoic acid, and 100 parts of maleic anhydride;

[0073] In step (1), acetone, cyclohexyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane are added and stirred thoroughly to dissolve, and then hydrogen peroxide is added. The solution is heated to 65° C. and boiled. After reflux reaction for 36 hours, the solution is cooled to 34° C., washed with water, and dried to obtain a first solid intermediate product.

[0074] In step (2), ether, maleic anhydride and 3-furoic acid were added and stirred to dissolve, sodium carbonate was added, and the solution was heated to 75°C and boiled, and refluxed for 24 hours. After the reflux reaction was completed, the temperature was lowered to 33°C;

[0075] In step (3), the first solid intermediate product and the second solid intermediate product are added to tetrahydrofuran, stirred and dissolved, heated to 110° C. to boil the solution, refluxed for 24 hours, cooled to 33° C., and vacuum dried to obtain a high-performance epoxy resin.

[0076] The obtained properties are shown in Table 1. By comparing sample 1 with sample 4, it is found that the glass transition temperature of sample 1 is higher than that of sample 4, and the 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of sample 4.

[0077] Example 5

[0078] Preparation of Sample 5:

[0079] The preparation method of sample 5 is the same as that of sample 1, with the only difference being:

[0080] Weigh 72 parts of cyclohexyl-3-enyl-1-ethyl ether, 38 parts of methylphenyldichlorosilane, 85 parts of 3-furoic acid, and 110 parts of maleic anhydride;

[0081] In step (1), acetone, cyclohexyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane are added and stirred thoroughly to dissolve, and then hydrogen peroxide is added. The solution is heated to 63° C. and boiled. After reflux reaction for 30 hours, the solution is cooled to 32° C., washed with water, and dried to obtain a first solid intermediate product.

[0082] In step (2), ether, maleic anhydride and 3-furoic acid were added and stirred to dissolve, sodium carbonate was added, and the solution was heated to 68° C. and boiled, and refluxed for 20 h. After the reflux reaction was completed, the temperature was lowered to 32° C.;

[0083] In step (3), the first solid intermediate product and the second solid intermediate product are added to tetrahydrofuran, stirred and dissolved, heated to 110° C. to boil the solution, refluxed for 20 hours, cooled to 32° C., and vacuum dried to obtain a high-performance epoxy resin.

[0084] The obtained properties are shown in Table 1. By comparing sample 1 with sample 5, it is found that the glass transition temperature of sample 1 is higher than that of sample 5, and the 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of sample 5.

[0085] Comparative Example 1

[0086] Preparation of Sample 6:

[0087] Sample 6 was prepared in the same manner as Sample 1, with the only difference being that no sodium carbonate was added;

[0088] In step (2), ether, maleic anhydride and 3-furoic acid were added and stirred to dissolve, 0.2 parts of dilute hydrochloric acid was added, and the solution was heated to 70°C and boiled, and refluxed for 12 hours. After the reflux reaction was completed, the solution was cooled to 30°C, washed with water, and dried. 0.2 parts of dilute hydrochloric acid was added again, and the solution was heated to 75°C and boiled. After refluxed for 12 hours, the solution was cooled to 30°C, washed with water, and dried to obtain a second solid intermediate product.

[0089] Preparation of Sample 7:

[0090] Sample 7 was prepared in the same manner as Sample 1, with the only difference being that no dilute hydrochloric acid was added;

[0091] In step (2), ether, maleic anhydride and 3-furoic acid were added and stirred to dissolve, 4 parts of sodium carbonate were added, and the solution was heated to 70°C and boiled, and refluxed for 12 hours. After the reflux reaction was completed, the temperature was lowered to 30°C, washed with water, and dried. 4 parts of sodium carbonate were added again, and the solution was heated to 75°C and boiled, and refluxed for 12 hours, and then cooled to 30°C, washed with water, and dried to obtain a second solid intermediate product.

[0092] Preparation of Sample 8:

[0093] Sample 8 was prepared in the same manner as Sample 1, except that sodium carbonate and dilute hydrochloric acid were not added;

[0094] In step (2), ether, maleic anhydride and 3-furoic acid are added, stirred and dissolved, heated to 70° C. until the solution boils, and refluxed for 12 h. After the reflux reaction is completed, the mixture is cooled to 30° C., washed with water, and dried to obtain a second solid intermediate product.

[0095] The obtained properties are shown in Table 1. By comparing sample 1 with samples 6, 7, and 8, it is found that the glass transition temperature of sample 1 is higher than that of samples 6, 7, and 8. The 150°C tensile strength, 150°C flexural strength, and self-repair rate of sample 1 are all better than those of samples 6, 7, and 8.

[0096] During the reaction of 3-furoic acid and maleic anhydride, the addition of sodium carbonate (a basic catalyst, weakly alkaline) protects the carboxylic acid group, promoting a directional reaction between the anhydride and the double bond without reacting with the carboxylic acid. Dilute hydrochloric acid (an acid catalyst, weakly acidic) is then added to neutralize the carbonic acid group, generating the carboxyl group in the product.

[0097] In sample 6, no sodium carbonate was added, but only dilute hydrochloric acid was added. The carboxyl groups in 3-furoic acid reacted with each other to produce anhydride and water, and the self-healing ability of the final product was not ideal.

[0098] In sample 7, no dilute hydrochloric acid was added, only sodium carbonate was added, and salt, water and carbon dioxide were generated in part of the product. Step (1) only reacted with the anhydride in step (2). The molecular mechanical properties and environmental resistance of the final product did not reach the best state, and the self-repair effect was affected.

[0099] No catalyst (sodium carbonate and dilute hydrochloric acid) was added to sample 8, and the active hydrogen atoms and epoxy groups would undergo addition reactions, resulting in non-unique products, low self-healing ability and instability.

[0100] Comparative Example 2

[0101] Preparation of Sample 9:

[0102] The only difference between Sample 9 and Sample 1 is that no 3-furoic acid, maleic anhydride, sodium carbonate, and dilute hydrochloric acid were added;

[0103] Acetone, cycloethyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane were added and stirred thoroughly to dissolve, and then hydrogen peroxide was added. The solution was heated to 57°C and boiled. After reflux reaction for 28 hours, the temperature was lowered to 35°C, washed with water, and dried to obtain epoxy resin.

[0104] Preparation of Sample 10:

[0105] The only difference between sample 10 and sample 1 is that cyclohexyl-3-enyl-1-ethyl ether, methylphenyldichlorosilane and hydrogen peroxide were not added;

[0106] Add ether, maleic anhydride and 3-furoic acid, stir and dissolve, add sodium carbonate, heat to 70°C until the solution boils, reflux for 12 hours, cool to 30°C after the reflux reaction is completed, wash with water, and dry, then add dilute hydrochloric acid, heat to 75°C until the solution boils, reflux for 12 hours, cool to 30°C, wash with water, and dry to obtain epoxy resin.

[0107] The obtained properties are shown in Table 1. By comparing sample 1 with samples 9 and 10, it is found that the glass transition temperature of sample 1 is higher than that of samples 9 and 10. The 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of samples 9 and 10.

[0108] Sample 9 has a stable Si-O bond, mainly because epoxy resin has acid resistance, alkali resistance, high temperature resistance, and excellent mechanical properties. Although the epoxy group has high reactivity, it does not undergo a synthetic reaction with the second fixed intermediate product obtained in step (2) of Example 1. It is very stable and not easy to react.

[0109] Sample 10 has two functional groups, anhydride and carboxyl, and has high flexibility in molecular design. Although it has self-healing ability, the product's mechanical properties and environmental stability are average.

[0110] Comparative Example 3

[0111] Preparation of Sample 11:

[0112] The only difference between sample 11 and sample 1 is:

[0113] A one-step heating and insulation reaction was carried out, acetone, methylphenyldichlorosilane and cycloethyl-3-enyl-1-ethyl ether were added and stirred to dissolve, hydrogen peroxide, sodium carbonate, dilute hydrochloric acid, tetrahydrofuran, maleic anhydride and 3-furoic acid were added, and the mixture was fully stirred to dissolve, and the solution was heated to 110°C until boiling, refluxed for 48 hours, and then cooled to 30°C, washed with water, and dried to obtain an epoxy resin.

[0114] The obtained properties are shown in Table 1. By comparing sample 1 with sample 11, it is found that the glass transition temperature of sample 1 is higher than that of sample 11, and the 150°C tensile strength, 150°C flexural strength and self-repair rate of sample 1 are all better than those of sample 11.

[0115] Comparative Example 4

[0116] Preparation of Sample 12:

[0117] The preparation method of sample 12 is the same as that of sample 1, except that cyclohexyl-3-enyl-1-ethyl ether is not added.

[0118] Preparation of Sample 13:

[0119] Sample 13 was prepared in the same manner as Sample 1, except that no maleic anhydride was added.

[0120] Preparation of Sample 14:

[0121] The preparation method of sample 14 is the same as that of sample 1, except that no methylphenyldichlorosilane is added.

[0122] The obtained properties are shown in Table 1. By comparing Sample 1 with Samples 12, 13, and 14, it is found that the glass transition temperature of Sample 1 is higher than that of Samples 12, 13, and 14. The 150°C tensile strength, 150°C flexural strength, and self-healing rate of Sample 1 are all better than those of Samples 12, 13, and 14. Specifically, no epoxy groups were introduced into Sample 12, no carboxyl groups were introduced into Sample 13, and Si-O bonds were introduced into Sample 14.

[0123] Comparative Example 5

[0124] Sample 15 is E-51 epoxy resin produced by Jining Zhongjian Information Technology Co., Ltd.

[0125] Test Method

[0126] After curing, the high-performance epoxy resins prepared in the above examples and the epoxy resins obtained in the comparative examples were tested for glass transition temperature, self-repair rate, tensile properties at 150°C, and impact strength at 150°C. The test results are shown in Table 1 below:

[0127] Table 1 Test results

[0128] As can be seen from Table 1, the present invention screens the selection and ratio of each component and improves the preparation method. The high-performance epoxy resin prepared by the preparation method of the present invention is compared with the epoxy resin obtained by the current conventional preparation method and the ordinary epoxy resin on the market. The glass transition temperature, tensile strength and impact strength of the high-performance epoxy resin in the embodiment are higher than the epoxy resin obtained in the comparative example; the self-healing rate of the high-performance epoxy resin in the embodiment is higher than that of the epoxy resin obtained in the comparative example; the high-performance epoxy resin has high molecular regularity and low molecular activity, and the cured resin has strong heat resistance, excellent self-healing performance, and stable mechanical properties.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a high-performance epoxy resin, characterized in that: The steps include: S1: dissolving cycloethyl-3-enyl-1-ethyl ether and methylphenyldichlorosilane in a solvent, adding an inorganic peroxide catalyst after stirring and dissolving, heating, performing a reflux reaction, cooling, washing with water, and drying to obtain a first solid intermediate product; S2: dissolving 3-furoic acid and maleic anhydride in a solvent, adding a basic catalyst after stirring and dissolving, heating for the first time, performing a first reflux reaction, cooling for the first time, washing with water, drying, adding an acidic catalyst, heating for the second time, performing a second reflux reaction, cooling for the second time, washing with water, and drying to obtain a second solid intermediate product; S3: dissolving the first solid intermediate product and the second solid intermediate product in a solvent, stirring and dissolving, heating, performing a reflux reaction, cooling, and drying to obtain a high-performance epoxy resin.

2. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: In step S1, by mass: 60-75 parts of cycloethyl-3-enyl-1-ethyl ether, 35-45 parts of methylphenyldichlorosilane, and 0.6-0.8 parts of inorganic peroxide catalyst.

3. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: In step S1, nitrogen is introduced into the reaction system, the heating temperature is 57-65°C, the reflux reaction time is 24-36h, and the temperature is lowered to 30-35°C.

4. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: The inorganic peroxide catalyst is at least one of hydrogen peroxide, sodium peroxide, calcium peroxide and magnesium peroxide.

5. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: In step S2, by mass fraction: 70-85 parts of 3-furoic acid, 80-110 parts of maleic anhydride, 4-8 parts of alkaline catalyst, and 0.2-0.4 parts of acidic catalyst.

6. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: In step S2, the alkaline catalyst is at least one of sodium carbonate, sodium carbonate or calcium carbonate, and the acidic catalyst is at least one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; The first heating temperature is 65-75°C, the first reflux reaction time is 12-24h, and the first cooling is to 30-35°C; The second heating temperature is 60-85°C, the second reflux reaction time is 12-24h, and the second cooling is to 30-35°C.

7. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: In step S3, the heating temperature is 95-130°C, the reflux reaction time is 12-24h, and the temperature is lowered to 30-35°C.

8. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: The solvent is at least one of acetone, ether or tetrahydrofuran.

9. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: The reaction is carried out in a reactor.

10. A high-performance epoxy resin obtained based on the preparation method of the high-performance epoxy resin according to any one of claims 1 to 9.

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