A high-temperature resistant epoxy resin adhesive and its preparation method

Abstract

The present invention relates to a high temperature resistant epoxy resin adhesive and a preparation method thereof, belonging to the technical field of adhesives. The adhesive comprises, by weight, 100 parts of a matrix epoxy resin, 15-22 parts of an anti-thermal debonding aid, 45-55 parts of a latent curing agent, 1.5-2 parts of a leveling agent, and 28-36 parts of an active diluent; the anti-thermal debonding aid is prepared by click addition of mercaptoethylamine and diallylamine to form a diamine modifier, which is then prepolymerized by BPDA and ODA, and then copolymerized with the diamine modifier as a bridging material and the prepolymer to form a modified matrix, and finally epoxy groups are introduced into the side chains of the copolymer by epichlorohydrin to prepare the anti-thermal debonding aid; the anti-thermal debonding aid has good compatibility and dispersibility with the matrix epoxy resin, and is uniformly interlaced and staggered in the adhesive layer to form a high temperature resistant interwoven network, which has a fixing effect on the adhesive layer, reduces the bonding failure caused by deformation of the adhesive layer at high temperature, and thus improves the high temperature resistance of the adhesive layer.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives, and in particular, relates to a high temperature resistant epoxy resin adhesive and a preparation method thereof. Background Art

[0002] Epoxy resin adhesives are formulated with epoxy resin matrix, curing agent, etc., and can generate a three-dimensional network cross-linked structure after curing. Epoxy resin adhesives have excellent bonding properties, mechanical properties, water resistance, corrosion resistance, and also have the advantages of uniform stress distribution at the bonding site, simple construction process, and low energy consumption. They can be used to bond honeycomb sandwich structures, composite metal structures, etc., and have a wide range of applications. In the aerospace field, they can be used to assemble fuselages, wings, etc. In the field of automotive machinery, they can be used for car doors, assembly of car engine hoods, etc.; however, the traditional epoxy resin has insufficient high temperature resistance, which greatly limits the application of epoxy adhesives.

[0003] There are two main technical means for solving the problem of insufficient heat resistance of epoxy adhesives in the prior art. First, by chemical synthesis technology, high-temperature resistant segments such as phenolic and silicone are introduced to prepare phenolic-epoxy resins and silicone-epoxy resins, which can improve the heat resistance of adhesives to a certain extent. However, the production process is complicated, and the amount of the adhesive matrix is ​​large, resulting in high costs. Second, by blending technology, a certain amount of high-temperature resistant materials are compounded into traditional epoxy resins to improve the overall heat resistance, such as inorganic fillers such as silica and alumina, and organic polymer materials such as polyimide. Compared with synthetic special epoxy resin adhesives, the process is simple, the production is efficient, and the cost is relatively low. However, the dispersion of these externally added high-temperature resistant materials and the matrix epoxy resin is insufficient, and they are prone to segregation at high temperatures, which has limited improvement on the high-temperature bonding performance of the adhesive. Summary of the invention

[0004] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a high temperature resistant epoxy resin adhesive and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high temperature resistant epoxy resin adhesive comprises, by weight, 100 parts of base epoxy resin, 15-22 parts of anti-thermal debonding auxiliary agent, 45-55 parts of latent curing agent, 1.5-2 parts of leveling agent and 28-36 parts of active diluent.

[0007] The anti-heat debonding aid is prepared by the following method:

[0008] Step A1: Diallylamine, benzoin dimethyl ether and acetone were mixed, the air in the reaction system was replaced with nitrogen, the water bath temperature was controlled at 45-55°C, stirring was applied at 90-120 rpm and 150-200 W / m2 UV irradiation, slowly adding mercaptoethylamine to react for 6-8 hours, and after the reaction is completed, removing acetone by rotary evaporation to obtain a diamine modifier;

[0009] Furthermore, the dosage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone is 10mmol:25-30mmol:10-15mg:8-14mL, and mercaptoethylamine and diallylamine undergo click addition reaction under the promotion of benzoin dimethyl ether and the initiation of ultraviolet radiation to produce a compound with double-terminal amino groups.

[0010] Step A2: BPDA, ODA and dimethylacetamide are mixed, the air in the reaction system is replaced with nitrogen, and the mixture is stirred at 40-60 rpm at room temperature for 8-10 hours, then a diamine modifier and aluminum chloride are added and mixed, the temperature is raised to 60-75° C., the stirring rate is increased to 60-90 rpm, and the reaction is continued for 2.5-3.5 hours. After the reaction is completed, n-butylamine is added and mixed, and water is added and the dimethylacetamide is removed by vacuum rotary evaporation to obtain a modified matrix;

[0011] Furthermore, the dosage ratio of BPDA, ODA, diamine modifier, aluminum chloride and dimethylacetamide is 0.1 mol: 65-80 mmol: 15-25 mmol: 1.2-1.6 g: 100-140 mL, BPDA and ODA preferentially react to form a polyamic acid prepolymer, and then under the catalysis of aluminum chloride, the diamine modifier is copolymerized with the prepolymer as a bridging material, and finally quenched and capped by n-butylamine to prepare a small molecular weight polyamic acid with a diamine modifier block.

[0012] Step A3: Mix the modified substrate, sodium hydride and dimethyl sulfoxide, raise the temperature to 70-80°C, apply 120-180rpm, slowly add epichlorohydrin to react for 3-4h, and remove dimethyl sulfoxide by vacuum rotary evaporation after the reaction to obtain an anti-thermal debonding agent;

[0013] Furthermore, the dosage ratio of the modified substrate, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:6-9mL:0.5-0.7g:130-170mL, the sulfur-nitrogen structure of the diamine modifier segment of the modified substrate molecule forms a chelating effect, sodium hydride is enriched at the diamine modifier segment, the reaction of epichlorohydrin with its secondary amine group is promoted in situ, and epoxy groups are introduced into the side chains of the modified substrate.

[0014] Preferably, the matrix epoxy resin is one or more of E51 epoxy resin, TDE-85 epoxy resin and AG-80 epoxy resin.

[0015] Preferably, the latent curing agent is selected from 4,4'-diaminodiphenyl sulfone.

[0016] Preferably, the reactive diluent is selected from ethylene glycol diglycidyl ether.

[0017] A method for preparing a high temperature resistant epoxy resin adhesive comprises the following steps: premixing an anti-heat debonding aid, a latent curing agent, a leveling agent and an active diluent, and then uniformly adding a matrix epoxy resin and mixing the mixture under stirring to obtain the high temperature resistant epoxy resin adhesive.

[0018] Beneficial effects of the present invention:

[0019] The invention discloses an anti-heat-debonding aid, which has good compatibility with an existing high-temperature epoxy resin, and the compounded adhesive has excellent high-temperature resistance and can provide stable bonding ability within the range of 300°C; the anti-heat-debonding aid is prepared by click addition of mercaptoethylamine and diallylamine to form a compound with double-terminal amino groups, namely a diamine modifier, and then BPDA and ODA are reacted to form a polyamic acid prepolymer, and then the diamine modifier is used as a bridging material and copolymerized with the prepolymer under the catalysis of aluminum trichloride to prepare a small molecular weight polyamic acid with a diamine modifier block, namely a modified matrix, and the sulfur-nitrogen structure of the diamine modifier chain segment of the modified matrix molecule forms a chelating effect, sodium hydride is enriched at the diamine modifier chain segment, epichlorohydrin and its secondary amine group are promoted to react in situ, and epoxy groups are introduced into the side chains of the modified matrix. , that is, an anti-thermal debonding aid is made; the epoxy structure of the side chain of the anti-thermal debonding aid molecule forms a modification effect, has good compatibility and dispersibility with the epoxy resin matrix, and is evenly dispersed in the epoxy resin during the preparation process. After the bonding is cured, the sulfur-nitrogen structure of the anti-thermal debonding aid forms a chelate with the metal bonded substrate. At the same time, the epoxy structure of the side chain is co-crosslinked with the matrix epoxy resin, giving the adhesive layer an adhesive force in addition to cohesive force, thereby improving the bonding strength of the adhesive; under high temperature conditions, the matrix epoxy resin is preferentially softened or even thermally decomposed, resulting in a decrease in bonding strength, while the main chain of the anti-thermal debonding aid is mainly composed of polyimide segments with high thermal stability, which are evenly interspersed and staggered in the adhesive layer to form a high-temperature resistant interwoven network, which plays a fixing role on the adhesive layer, reducing the bonding failure caused by the deformation of the adhesive layer at high temperature, thereby improving the high-temperature resistance of the adhesive layer. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1, preparation of high temperature resistant epoxy resin adhesive, the specific implementation process is as follows:

[0022] (1) Synthesis of anti-thermal debonding agent

[0023] Step A1: Mix diallylamine, benzoin dimethyl ether and acetone, replace the air in the reaction system with nitrogen, control the water bath temperature at 55°C, apply 120 rpm stirring and 200 W / m 2 Under ultraviolet irradiation, slowly add mercaptoethylamine, control the addition time to be 2h, continue the constant temperature irradiation reaction after the addition, control the total reaction time of mercaptoethylamine addition to be 6h, wherein the dosage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone is 10mmol:30mmol:15mg:14mL, and after the reaction is completed, remove the acetone by rotary evaporation to obtain diamine modification.

[0024] Step A2: BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride), ODA (4,4'-diaminodiphenyl ether) and dimethylacetamide were mixed, the air in the reaction system was replaced with nitrogen, and the mixture was stirred at 60 rpm at room temperature for 8 hours. Then, a diamine modifier and aluminum trichloride were added and mixed, the temperature was raised to 75°C, and the stirring rate was increased to 90 rpm to continue the reaction for 2.5 hours. The amount ratio of BPDA, ODA, diamine modifier, aluminum trichloride and dimethylacetamide was 0.1 mol: 80 mmol: 15 mmol: 1.6 g: 140 mL. After the reaction was completed, 5 wt% of n-butylamine was added to the reaction substrate and mixed, and water was repeatedly added to remove dimethylacetamide by vacuum rotary evaporation to obtain a modified matrix.

[0025] Step A3: Take the modified substrate, sodium hydride and dimethyl sulfoxide, mix them, heat to 80°C, apply 180rpm, slowly add epichlorohydrin, control the addition time to be 1h, continue to stir the reaction at a constant temperature after addition, and control the total addition reaction time of epichlorohydrin to be 3h, wherein the amount ratio of the modified substrate, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:6mL:0.7g:170mL. After the reaction is completed, the dimethyl sulfoxide is removed by vacuum rotary evaporation to obtain an anti-thermal debonding agent.

[0026] (2) Preparation of adhesive

[0027] Ingredients: The raw materials are measured in parts by weight: 100 parts of base epoxy resin, which is a mixture of E51 epoxy resin and AG-80 epoxy resin in a ratio of 3:1 during the implementation process; 15 parts of anti-thermal debonding agent, which is homemade in this embodiment; 45 parts of latent curing agent, which is an industrial-grade 4,4'-diaminodiphenyl sulfone during the implementation process; 1.5 parts of leveling agent, which is an organic silicon leveling agent BYK-346 during the implementation process; 28 parts of active diluent, which is an industrial-grade ethylene glycol diglycidyl ether during the implementation process.

[0028] Glue preparation: Add the anti-thermal debonding agent, latent curing agent, leveling agent and active diluent into the stirrer, stir at 180 rpm for 10 min, then reduce the stirring rate to 40 rpm, add the base epoxy resin at a uniform speed and mix for 1 h to obtain a high temperature resistant epoxy resin adhesive.

[0029] Example 2, preparing a high temperature resistant epoxy resin adhesive, the specific implementation process is as follows:

[0030] (1) Synthesis of anti-thermal debonding agent

[0031] Step A1: Mix diallylamine, benzoin dimethyl ether and acetone, replace the air in the reaction system with nitrogen, control the temperature of the water bath to 45°C, apply 90 rpm stirring and 150 W / m 2 Under ultraviolet irradiation, slowly add mercaptoethylamine, control the addition time to be 3h, continue the constant temperature irradiation reaction after the addition, control the total reaction time of mercaptoethylamine addition to be 8h, wherein the dosage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone is 10mmol:25mmol:10mg:8mL, and after the reaction is completed, remove the acetone by rotary evaporation to obtain diamine modification.

[0032] Step A2: BPDA, ODA and dimethylacetamide are mixed, the air in the reaction system is replaced with nitrogen, and the reaction is stirred at 40 rpm at room temperature for 10 hours, then a diamine modifier and aluminum chloride are added and mixed, the temperature is raised to 60°C, and the stirring rate is increased to 60 rpm to continue the reaction for 3.5 hours, wherein the amount ratio of BPDA, ODA, diamine modifier, aluminum chloride and dimethylacetamide is 0.1 mol: 65 mmol: 25 mmol: 1.2 g: 100 mL, and after the reaction is completed, 5 wt% of n-butylamine is added to the reaction substrate and mixed, and then water is repeatedly added and reduced pressure rotary evaporation is performed to remove dimethylacetamide to obtain a modified matrix.

[0033] Step A3: Take the modified matrix, sodium hydride and dimethyl sulfoxide, mix them, heat to 70°C, apply 120rpm, slowly add epichlorohydrin, control the addition time to be 1.5h, continue to stir the reaction at a constant temperature after addition, and control the total addition reaction time of epichlorohydrin to be 4h, wherein the amount ratio of the modified matrix, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:9mL:0.5g:130mL. After the reaction is completed, the dimethyl sulfoxide is removed by vacuum rotary evaporation to obtain an anti-thermal debonding agent.

[0034] (2) Preparation of adhesive

[0035] Ingredients: The raw materials are measured by weight: 100 parts of base epoxy resin, which is a mixture of E51 epoxy resin and TDE-85 epoxy resin in a ratio of 3:1; 22 parts of anti-thermal debonding agent, which is homemade in this embodiment; 55 parts of latent curing agent, which is an industrial-grade 4,4'-diaminodiphenyl sulfone; 2 parts of leveling agent, which is an organosilicon leveling agent BYK-346; 36 parts of active diluent, which is an industrial-grade ethylene glycol diglycidyl ether.

[0036] Glue preparation: Add the anti-thermal debonding agent, latent curing agent, leveling agent and active diluent into the stirrer, stir at 180 rpm for 10 min, then reduce the stirring rate to 40 rpm, add the base epoxy resin at a uniform speed and mix for 1 h to obtain a high temperature resistant epoxy resin adhesive.

[0037] Example 3, preparation of high temperature resistant epoxy resin adhesive, the specific implementation process is as follows:

[0038] (1) Synthesis of anti-thermal debonding agent

[0039] Step A1: Mix diallylamine, benzoin dimethyl ether and acetone, replace the air in the reaction system with nitrogen, control the water bath temperature at 50°C, apply 90 rpm stirring and 180 W / m 2 Under ultraviolet irradiation, slowly add mercaptoethylamine, control the addition time to be 2.5h, continue the constant temperature irradiation reaction after the addition, control the total reaction time of mercaptoethylamine addition to be 7h, wherein the dosage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone is 10mmol:28mmol:13mg:12mL, and after the reaction, remove the acetone by rotary evaporation to obtain diamine modification.

[0040] Step A2: BPDA, ODA and dimethylacetamide are mixed, the air in the reaction system is replaced with nitrogen, and the reaction is stirred at 40 rpm at room temperature for 9 hours, then a diamine modifier and aluminum chloride are added and mixed, the temperature is raised to 65°C, and the stirring rate is increased to 90 rpm to continue the reaction for 3 hours, wherein the amount ratio of BPDA, ODA, diamine modifier, aluminum chloride and dimethylacetamide is 0.1 mol: 70 mmol: 20 mmol: 1.4 g: 120 mL, and after the reaction is completed, 5 wt% of n-butylamine is added to the reaction substrate and mixed, and then water is repeatedly added and the dimethylacetamide is removed by reduced pressure rotary evaporation to obtain a modified matrix.

[0041] Step A3: Take the modified matrix, sodium hydride and dimethyl sulfoxide, mix them, heat to 75°C, apply 120rpm, slowly add epichlorohydrin, control the addition time to be 1.2h, continue to stir the reaction at a constant temperature after addition, and control the total addition reaction time of epichlorohydrin to be 3.5h, wherein the amount ratio of the modified matrix, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:7mL:0.6g:150mL. After the reaction is completed, the dimethyl sulfoxide is removed by vacuum rotary evaporation to obtain an anti-thermal debonding agent.

[0042] (2) Preparation of adhesive

[0043] Ingredients: The raw materials are measured in parts by weight: 100 parts of base epoxy resin, which is a mixture of E51 epoxy resin, AG-80 epoxy resin and TDE-85 epoxy resin in the ratio of 2:1:1 during the implementation process; 18 parts of anti-thermal debonding agent, which is homemade in this embodiment; 48 parts of latent curing agent, which is an industrial-grade 4,4'-diaminodiphenyl sulfone during the implementation process; 1.8 parts of leveling agent, which is an organosilicon leveling agent BYK-346 during the implementation process; 30 parts of active diluent, which is an industrial-grade ethylene glycol diglycidyl ether during the implementation process.

[0044] Glue preparation: Add the anti-thermal debonding agent, latent curing agent, leveling agent and active diluent into the stirrer, stir at 180 rpm for 10 min, then reduce the stirring rate to 40 rpm, add the base epoxy resin at a uniform speed and mix for 1 h to obtain a high temperature resistant epoxy resin adhesive.

[0045] Example 4, preparation of high temperature resistant epoxy resin adhesive, the specific implementation process is as follows:

[0046] (1) Synthesis of anti-thermal debonding agent

[0047] Step A1: Mix diallylamine, benzoin dimethyl ether and acetone, replace the air in the reaction system with nitrogen, control the water bath temperature at 52°C, apply 120 rpm stirring and 180 W / m 2 Under ultraviolet irradiation, mercaptoethylamine was slowly added, and the addition time was controlled to be 2.2h. After the addition, the constant temperature irradiation reaction was continued, and the total reaction time of mercaptoethylamine was controlled to be 7.5h. Among them, the dosage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone was 10mmol:25mmol:15mg:12mL. After the reaction, the acetone was removed by rotary evaporation to obtain diamine modification.

[0048] Step A2: BPDA, ODA and dimethylacetamide are mixed, the air in the reaction system is replaced with nitrogen, and the reaction is stirred at 60 rpm at room temperature for 8.5 hours, then a diamine modifier and aluminum chloride are added and mixed, the temperature is raised to 65°C, and the stirring rate is increased to 90 rpm to continue the reaction for 3.5 hours, wherein the amount ratio of BPDA, ODA, diamine modifier, aluminum chloride and dimethylacetamide is 0.1 mol: 75 mmol: 22 mmol: 1.5 g: 120 mL, and after the reaction is completed, 5 wt% of n-butylamine is added to the reaction substrate and mixed, and then water is repeatedly added and the dimethylacetamide is removed by reduced pressure rotary evaporation to obtain a modified matrix.

[0049] Step A3: Take the modified matrix, sodium hydride and dimethyl sulfoxide, mix them, heat to 75°C, apply 180rpm, slowly add epichlorohydrin, control the addition time to be 1.5h, continue to stir the reaction at a constant temperature after addition, and control the total addition reaction time of epichlorohydrin to be 3.5h, wherein the amount ratio of the modified matrix, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:8mL:0.6g:160mL. After the reaction is completed, the dimethyl sulfoxide is removed by vacuum rotary evaporation to obtain an anti-thermal debonding agent.

[0050] (2) Preparation of adhesive

[0051] Ingredients: The raw materials are measured in parts by weight: 100 parts of base epoxy resin, which is a mixture of E51 epoxy resin, AG-80 epoxy resin and TDE-85 epoxy resin in the ratio of 2:1:1 during the implementation process; 20 parts of anti-thermal debonding agent, which is homemade in this embodiment; 50 parts of latent curing agent, which is an industrial-grade 4,4'-diaminodiphenyl sulfone during the implementation process; 1.7 parts of leveling agent, which is an organosilicon leveling agent BYK-346 during the implementation process; 32 parts of active diluent, which is an industrial-grade ethylene glycol diglycidyl ether during the implementation process.

[0052] Glue preparation: Add the anti-thermal debonding agent, latent curing agent, leveling agent and active diluent into the stirrer, stir at 180 rpm for 10 min, then reduce the stirring rate to 40 rpm, add the base epoxy resin at a uniform speed and mix for 1 h to obtain a high temperature resistant epoxy resin adhesive.

[0053] Comparative Example

[0054] This comparative example refers to Example 4, except that the anti-thermal debonding agent is replaced with a polyimide solution of model PAA-2, and the rest of the implementation process is exactly the same.

[0055] In order to detect the high temperature resistant bonding performance of the above adhesives, the tensile shear strength test was carried out in accordance with the GB / T 7124-2008 standard. Specifically, 7075 aviation aluminum alloy sheets were used as bonding objects and processed into sheets with specifications of 50×15×3mm. The bonding surface was first polished crosswise with 100-grit sandpaper, and then immersed in a chromic acid solution for 30 minutes. After cleaning and drying, the above prepared adhesive was scraped onto the surface. The thickness of the adhesive layer was about 30μm, and the overlapping surface was controlled to be 15×15mm. It was sent to a hot press with a controlled pressure of 0.3MPa. The curing process was: 120℃ curing for 1h + 180℃ curing for 3h. After cooling to room temperature, it was placed in an oven and then kept at 60℃ for 6h to destress. The bonding specimens were subjected to tensile shear tests. The test temperatures were 25℃, 150℃, 220℃, 280℃ and 300℃, respectively, and the loading rate was 3mm / min. The specific test results are shown in the following table:

[0056]

[0057] It can be seen from the test results in the above table that the tensile shear strength of the epoxy resin adhesive in the test increases slightly in the range of room temperature to 150°C, which may be related to the sufficient curing of the epoxy resin. Compared with the comparative example, the initial tensile shear strength of the embodiment is higher than that of the comparative example, and stable and effective bonding performance can be provided in the range of 280°C, and it still has a certain bonding strength at 300°C, while the comparative example can only stably bond within 220°C, and the bonding performance deteriorates sharply in the range of 220-280°C. At 280°C, the tensile shear strength remains only 2.59MPa, which does not meet the bonding stability.

[0058] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0059] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A high temperature resistant epoxy resin adhesive, characterized in that: The composition comprises, by weight: 100 parts of base epoxy resin, 15-22 parts of anti-thermal debonding agent, 45-55 parts of latent curing agent, 1.5-2 parts of leveling agent and 28-36 parts of active diluent; The anti-heat debonding aid is prepared by the following method: Step A1: Mix diallylamine, benzoin dimethyl ether and acetone, replace the air in the reaction system with nitrogen, control the water bath temperature at 45-55°C, apply 150-200W / m 2 UV irradiation, stirring and slowly adding mercaptoethylamine to react for 6-8 hours, after the reaction is completed, acetone is removed by rotary evaporation to obtain a diamine modifier; Step A2: BPDA, ODA and dimethylacetamide are mixed, the air in the reaction system is replaced with nitrogen, and the mixture is stirred at room temperature for 8-10 hours, and then a diamine modifier and aluminum chloride are added and mixed, and the mixture is heated to 60-75°C, and the mixture is stirred and reacted for 2.5-3.5 hours. After the reaction is completed, n-butylamine is added and mixed, and water is added and the dimethylacetamide is removed by vacuum rotary evaporation to obtain a modified matrix; Step A3: The modified substrate, sodium hydride and dimethyl sulfoxide are mixed, the temperature is raised to 70-80° C., epichlorohydrin is slowly added with stirring to react for 3-4 hours, and the dimethyl sulfoxide is removed by vacuum rotary evaporation after the reaction to obtain an anti-thermal debonding agent.

2. A high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The usage ratio of diallylamine, mercaptoethylamine, benzoin dimethyl ether and acetone is 10mmol:25-30mmol:10-15mg:8-14mL.

3. A high temperature resistant epoxy resin adhesive according to claim 2, characterized in that: The usage ratio of BPDA, ODA, diamine modifier, aluminum chloride and dimethylacetamide is 0.1 mol: 65-80 mmol: 15-25 mmol: 1.2-1.6 g: 100-140 mL.

4. A high temperature resistant epoxy resin adhesive according to claim 3, characterized in that: The usage ratio of the modified matrix, epichlorohydrin, sodium hydride and dimethyl sulfoxide is 50g:6-9mL:0.5-0.7g:130-170mL.

5. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The matrix epoxy resin is one or more of E51 epoxy resin, TDE-85 epoxy resin and AG-80 epoxy resin.

6. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The latent curing agent is 4,4'-diaminodiphenyl sulfone.

7. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The active diluent is ethylene glycol diglycidyl ether.

8. A method for preparing a high temperature resistant epoxy resin adhesive according to any one of claims 1 to 7, characterized in that: The anti-heat-debonding aid, latent curing agent, leveling agent and reactive diluent are premixed, and then added into the base epoxy resin at a uniform speed under stirring to obtain a high temperature resistant epoxy resin adhesive.

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