A comb-shaped polyarylene ether nitrile modified epoxy resin adhesive and a preparation method thereof

Abstract

The application discloses a comb-type polyarylether nitrile modified epoxy resin adhesive and a preparation method thereof, relates to the field of epoxy resin adhesives, and aims to solve the problem that the existing polyarylether nitrile as a toughening modifier introduced into an epoxy resin system has a relatively large viscosity and is not conducive to painting construction. The comb-type polyarylether nitrile modified epoxy resin adhesive comprises a component A and a component B, the component A comprises the following components: an epoxy resin, a modified heterocyclic resin, a comb-type polyarylether nitrile, thermosetting PI fiber powder, a coupling agent, an epoxy phosphate and a thixotropic agent; and the component B comprises the following components: an aromatic amine curing agent, a polyamide curing agent, an accelerator and a grafting agent. The method comprises the following steps: uniformly stirring the component A and the component B to obtain the comb-type polyarylether nitrile modified epoxy resin adhesive. In the application, the comb-type polyarylether nitrile powder is used as a toughening modifier of the epoxy resin, the viscosity of the epoxy resin adhesive itself is not changed much by introducing the powder, the epoxy resin adhesive is conducive to painting construction when used, and the epoxy resin adhesive can be used for filling, repairing and bonding holes, grooves and gaps of workpieces made of various materials.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin adhesives, and more particularly to a comb-type polyarylene ether nitrile modified epoxy resin adhesive and its preparation method. Background Technology

[0002] Epoxy resins possess excellent adhesive properties, mechanical properties, and chemical stability. They also offer good processability and low cost, making them widely used as adhesive materials in various fields. However, epoxy resins also have drawbacks such as brittleness and poor impact resistance. Therefore, when used as adhesive materials, they often require toughening modification.

[0003] There are many methods for toughening and modifying epoxy resins. Commonly used modifiers include thermoplastic resins, thermosetting resins, macromolecular rubbers, core-shell nanoparticles, inorganic nanoparticles, and inorganic fiber powders. Among them, polyarylene ether nitrile (PAHN) is a novel high-performance thermoplastic resin, and there are numerous research reports on its use in modifying epoxy resins. However, most researchers have used solvent methods or hot-melt methods to introduce PAHN into the epoxy resin system. Solvent methods are highly toxic and not safe or environmentally friendly, while hot-melt methods require high temperatures to achieve uniform mixing, resulting in poor processability. Furthermore, these methods significantly increase the viscosity of the epoxy resin adhesive, making application difficult and resulting in adhesives with strong interfacial selectivity and a narrow range of applications. In addition, some studies have shown that blending aromatic amine curing agents, polyamide curing agents, polyether amine curing agents, aliphatic amine curing agents, imidazole curing agents, and thiol curing agents in various combinations can improve the overall performance of epoxy resin adhesives. However, most of these blends are added separately as multiple components, which complicates practical application. Summary of the Invention

[0004] The present invention aims to solve the problem that existing polyarylene ether nitrile (PAHN) used as toughening modifiers in epoxy resin systems have high viscosity, which is not conducive to application. The invention provides a comb-type PAHN-modified epoxy resin adhesive and its preparation method.

[0005] The comb-type polyarylene ether nitrile modified epoxy resin adhesive of the present invention comprises component A and component B. Component A comprises, by weight parts: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate, and 1-5 parts thixotropic agent. Component B comprises, by weight parts: 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent.

[0006] The comb-shaped polyarylene ether nitrile structure is as follows:

[0007] ,

[0008] The comb-type polyarylether nitrile has a mesh size of 120–180 mesh and a glass transition temperature of 127°C.

[0009] Furthermore, the epoxy resin is one or a mixture of several of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90, and hydantoin epoxy.

[0010] Furthermore, the modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130°C for 4 hours.

[0011] Furthermore, the thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425°C.

[0012] Furthermore, the coupling agent is γ-mercaptopropylmethyldimethoxysilane, bis-[γ-(triethoxysilane)propyl]tetrasulfide, or bis-[γ-(triethoxysilane)propyl]disulfide.

[0013] Furthermore, the epoxy phosphate ester is CM-801 or 4901.

[0014] Furthermore, the thixotropic agent is fumed silica R972, A300, A380 or R202.

[0015] Furthermore, the aromatic amine curing agent is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amino... One or a mixture of several of the following: phenoxybenzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, and 4,4'-bis(3-aminophenoxy)benzophenone.

[0016] Furthermore, the polyamide curing agent is one or a mixture of several of polyamide resins 651, 650, V115, V125, V140, 200, and 300.

[0017] Furthermore, the promoter is obtained by mixing an imidazole derivative with triphenylphosphine at a mass ratio of 1:1.

[0018] The imidazole derivatives therein are 1-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium or 1-(2-cyanoethyl)-2-undecylimidazolium.

[0019] Furthermore, the grafting agent is selected from polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, 1,4-cyclohexanediethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether, or diethylene glycol diglycidyl ether.

[0020] The above-mentioned method for preparing comb-type polyarylene ether nitrile modified epoxy resin adhesive is carried out according to the following steps:

[0021] I. Weigh out the following components by weight: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate ester, 1-5 parts thixotropic agent, 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent.

[0022] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly at room temperature, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, grind and disperse to obtain component A.

[0023] 3. Stir the aromatic amine curing agent, polyamide curing agent, accelerator and grafting agent in a reaction vessel at 80-100℃ for 4-8 hours, cool to room temperature for later use, and obtain component B;

[0024] 4. Mix component A obtained in step 2 and component B obtained in step 3 at room temperature to obtain comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0025] The beneficial effects of this invention are:

[0026] This invention uses comb-shaped polyarylene ether nitrile powder as a toughening modifier for epoxy resin. It eliminates the need for traditional solvent-based or high-temperature hot-melt methods, allowing for uniform grinding and dispersion at room temperature. The preparation process is very simple, safe, and environmentally friendly. Furthermore, this method of introduction minimizes the viscosity change of the epoxy resin adhesive itself, making it highly suitable for application as a paste-like adhesive. It can be used for filling, repairing, and structural bonding of holes, grooves, and gaps in various metals, composites, and specialty plastics.

[0027] Due to the unique molecular structure of comb-type polyarylether nitrile, its glass transition temperature is only 127℃. During the heating and curing process, comb-type polyarylether nitrile exhibits the state of a rubber elastomer. Its synergistic effect with thermosetting PI fiber powder can significantly improve the toughness and high-temperature aging resistance of epoxy resin adhesives.

[0028] The modified heterocyclic resin used in this invention is liquid at room temperature, which has very little impact on the workability of epoxy resin adhesives. Through multiple polymerization reactions between the double bonds of bismaleimide, vinyl double bonds, and alkynyl groups in its molecules and the epoxy groups and amino groups in the resin matrix, the non-uniformity of the crosslinked network structure gives the modified epoxy resin adhesive good toughness, as well as excellent high-temperature anti-aging and media resistance.

[0029] The curing system of this invention uses aromatic amine curing agent, polyamide curing agent and accelerator at the same time. It uses a low viscosity grafting agent with epoxy groups to organically bridge them together. After being placed at room temperature for 1 year, it does not separate into layers or crystals, and has excellent storage stability. It does not need to be added one by one when used, which is convenient and quick.

[0030] The comb-type polyarylene ether nitrile modified epoxy resin adhesive prepared in this invention exhibits a shear strength of 30–38 MPa at room temperature when bonding aluminum alloys. After aging at 200℃ for 1000 hours, the shear strength at room temperature is 22–31 MPa. After immersion in artificial seawater for 30 days, the shear strength at room temperature is 28–34 MPa. The shear strength at room temperature when bonding carbon steel is 26–37 MPa, and the shear strength at room temperature when bonding nylon composite materials can reach 19–26 MPa. It is evident that the comb-type polyarylene ether nitrile modified epoxy resin adhesive of this invention demonstrates good resistance to various media, excellent high-temperature aging resistance, and good bonding effects on interfaces of various materials, with a wide range of applications and broad practical value. Attached Figure Description

[0031] Figure 1 The infrared spectrum of comb-type polyarylether nitrile;

[0032] Figure 2 This is the infrared spectrum of thermosetting PI fiber powder. Detailed Implementation

[0033] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

[0034] Specific Implementation Method 1: The comb-type polyarylene ether nitrile modified epoxy resin adhesive of this embodiment includes component A and component B. Component A, by weight, includes: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate, and 1-5 parts thixotropic agent. Component B, by weight, includes: 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent.

[0035] The comb-shaped polyarylene ether nitrile structure is as follows:

[0036] ,

[0037] The comb-type polyarylether nitrile has a mesh size of 120–180 mesh and a glass transition temperature of 127°C. Its infrared spectrum is shown in the attached figure. Figure 1 As shown.

[0038] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the epoxy resin is one or a mixture of several of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90, and hydantoin epoxy. Everything else is the same as in Specific Implementation Method One.

[0039] Specific Embodiment Three: This embodiment differs from Specific Embodiment One or Two in that the modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene, and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130°C for 4 hours. Everything else is the same as in Specific Embodiment One or Two.

[0040] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃. Its infrared spectrum is shown in the attached figure. Figure 2 As shown. Everything else is the same as in any of the specific embodiments one to three.

[0041] Specific Embodiment Five: This embodiment differs from Specific Embodiments One to Four in that the coupling agent is γ-mercaptopropylmethyldimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide, or bis-[γ-(triethoxysilyl)propyl]disulfide. Everything else is the same as in Specific Embodiments One to Four.

[0042] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the epoxy phosphate ester is CM-801 or 4901. Everything else is the same as in Specific Implementation Methods One to Five.

[0043] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the thixotropic agent is fumed silica R972, A300, A380, or R202. Everything else is the same as in Specific Implementation Methods One to Six.

[0044] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the aromatic amine curing agent is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)... One or a mixture of several of the following: benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, and 4,4'-bis(3-aminophenoxy)benzophenone. Other aspects are the same as in any one of embodiments one to seven.

[0045] Specific Embodiment Nine: This embodiment differs from Specific Embodiments One to Eight in that the polyamide curing agent is one or a mixture of several of polyamide resins 651, 650, V115, V125, V140, 200, and 300. Everything else is the same as in Specific Embodiments One to Eight.

[0046] Specific Embodiment Ten: This embodiment differs from Specific Embodiments One to Nine in that the accelerator is obtained by mixing an imidazole derivative and triphenylphosphine in a mass ratio of 1:1. Everything else is the same as in Specific Embodiments One to Nine.

[0047] Specific Embodiment Eleven: This embodiment differs from Specific Embodiment Ten in that the imidazole derivative is 1-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, or 1-(2-cyanoethyl)-2-undecylimidazolium. Everything else is the same as in Specific Embodiment Ten.

[0048] Specific Embodiment Twelve: This embodiment differs from Specific Embodiments One to Eleven in that the grafting agent is polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, 1,4-cyclohexanediethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether, or diethylene glycol diglycidyl ether. Everything else is the same as in Specific Embodiments One to Eleven.

[0049] Specific Implementation Method Thirteen: The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this implementation method is carried out according to the following steps:

[0050] I. Weigh out the following components by weight: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate ester, 1-5 parts thixotropic agent, 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent.

[0051] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly at room temperature, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, grind and disperse to obtain component A.

[0052] 3. Stir the aromatic amine curing agent, polyamide curing agent, accelerator and grafting agent in a reaction vessel at 80-100℃ for 4-8 hours, cool to room temperature for later use, and obtain component B;

[0053] 4. Mix component A obtained in step 2 and component B obtained in step 3 at room temperature to obtain comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0054] The embodiments of the present invention will be described in detail below. The following embodiments are implemented based on the technical solution of the present invention, and detailed implementation schemes and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0055] Example 1:

[0056] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0057] 1. Weigh out 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 22 parts of comb-type polyarylene ether nitrile, 6 parts of thermosetting PI fiber powder, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate ester and 1 part of thixotropic agent according to the following mass proportions.

[0058] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0059] 3. Weigh out 15 parts of aromatic amine curing agent, 28 parts of polyamide curing agent, 0.6 parts of accelerator and 0.8 parts of grafting agent according to the following weight proportions;

[0060] IV. Stir all the raw materials weighed in step III in a reaction vessel at 80°C for 7 hours. When the appearance is uniform and no solid substances are precipitated, cool to room temperature for later use to obtain component B.

[0061] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0062] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4.

[0063] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130℃ for 4 hours.

[0064] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0065] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0066] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate ester is CM-801, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is 1,3-bis(3-aminophenoxy)benzene, and the polyamide curing agent is polyamide resin V140. The accelerator is prepared by conventional physical mixing of 2-methylimidazolium and triphenylphosphine at a mass ratio of 1:1. The grafting agent is resorcinol diglycidyl ether.

[0067] Example 2:

[0068] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0069] 1. Weigh out 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 28 parts of comb-type polyarylene ether nitrile, 6 parts of thermosetting PI fiber powder, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate ester and 1 part of thixotropic agent according to the following mass proportions.

[0070] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0071] 3. Weigh out 15 parts of aromatic amine curing agent, 28 parts of polyamide curing agent, 0.6 parts of accelerator and 0.8 parts of grafting agent according to the following weight proportions;

[0072] IV. Stir all the raw materials weighed in step III in a reaction vessel at 80°C for 7 hours. When the appearance is uniform and no solid substances are precipitated, cool to room temperature for later use to obtain component B.

[0073] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0074] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4.

[0075] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130℃ for 4 hours.

[0076] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0077] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0078] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate ester is CM-801, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is 1,3-bis(3-aminophenoxy)benzene, the polyamide curing agent is polyamide resin V140, and the accelerator is 2-methylimidazole and triphenylphosphine at a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is resorcinol diglycidyl ether.

[0079] Example 3:

[0080] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0081] 1. Weigh out 45 parts of epoxy resin, 14 parts of modified heterocyclic resin, 22 parts of comb-type polyarylene ether nitrile, 8 parts of thermosetting PI fiber powder, 1.2 parts of coupling agent, 1.6 parts of epoxy phosphate ester and 2.8 parts of thixotropic agent according to the following weight proportions;

[0082] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0083] 3. Weigh out 18 parts of aromatic amine curing agent, 36 parts of polyamide curing agent, 0.8 parts of accelerator and 1.2 parts of grafting agent according to the following weight proportions;

[0084] 4. Stir all the raw materials weighed in step 3 in a reaction vessel at 95°C for 4.5 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0085] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0086] The epoxy resin is a mixture of E-44 and AG-80 in a mass ratio of 1:2.

[0087] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130℃ for 4 hours.

[0088] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0089] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0090] The coupling agent is bis-[γ-(triethoxysilyl)propyl]disulfide, the epoxy phosphate ester is CM-801, the thixotropic agent is fumed silica A380, the aromatic amine curing agent is 2,2'-bis(4-(3-aminophenoxy)phenyl)propane, the polyamide curing agent is polyamide resin 200, and the accelerator is prepared by conventional physical mixing of 1-cyanoethyl-2-ethyl-4-methylimidazolium and triphenylphosphine at a mass ratio of 1:1. The grafting agent is polypropylene glycol diglycidyl ether.

[0091] Example 4:

[0092] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0093] 1. Weigh out 52 parts of epoxy resin, 17 parts of modified heterocyclic resin, 10 parts of comb-type polyarylene ether nitrile, 3 parts of thermosetting PI fiber powder, 0.3 parts of coupling agent, 0.7 parts of epoxy phosphate ester and 4.5 parts of thixotropic agent according to the following weight proportions;

[0094] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0095] 3. Weigh out 20 parts of aromatic amine curing agent, 22 parts of polyamide curing agent, 0.4 parts of accelerator and 0.7 parts of grafting agent according to the following weight proportions;

[0096] IV. Stir all the raw materials weighed in step III in a reaction vessel at 98°C for 8 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0097] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0098] The epoxy resin is AG-70. The modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene, and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130°C for 4 hours.

[0099] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0100] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0101] The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate ester is 4901, the thixotropic agent is fumed silica A300, the aromatic amine curing agent is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, the polyamide curing agent is polyamide resin 650, and the accelerator is 2-ethyl-4-methylimidazolium and triphenylphosphine at a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is 1,4-cyclohexanediethanol diglycidyl ether.

[0102] Example 5:

[0103] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0104] 1. Weigh out 60 parts of epoxy resin, 10 parts of modified heterocyclic resin, 25 parts of comb-type polyarylene ether nitrile, 7 parts of thermosetting PI fiber powder, 1.0 part of coupling agent, 1.5 parts of epoxy phosphate ester and 3.3 parts of thixotropic agent according to the following weight proportions;

[0105] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0106] 3. Weigh out 21 parts of aromatic amine curing agent, 30 parts of polyamide curing agent, 0.5 parts of accelerator and 1.0 part of grafting agent according to the following weight proportions;

[0107] IV. Stir all the raw materials weighed in step III in a reaction vessel at 90°C for 6 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0108] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0109] The epoxy resin is a mixture of E-44, E-51 and TDE-85 in a mass ratio of 1:1:1.

[0110] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130℃ for 4 hours.

[0111] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0112] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0113] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate ester is CM-801, the thixotropic agent is fumed silica R972, the aromatic amine curing agent is a mixture of 3,4'-diaminodiphenyl ether and 1,4-bis(2-trifluoromethyl-4-aminophenoxy) in a 2:1 mass ratio, the polyamide curing agent is a mixture of polyamide resin V115 and polyamide resin 651 in a 1:1 mass ratio, and the accelerator is 2-heptadecylimidazolium and triphenylphosphine in a 1:1 mass ratio. This mixture was prepared by conventional physical mixing. The grafting agent is neopentyl glycol diglycidyl ether.

[0114] Example 6:

[0115] The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive in this embodiment is carried out according to the following steps:

[0116] 1. Weigh out 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of comb-type polyarylene ether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate ester and 3 parts of thixotropic agent by weight.

[0117] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0118] 3. Weigh out 16 parts of aromatic amine curing agent, 35 parts of polyamide curing agent, 0.8 parts of accelerator and 1.4 parts of grafting agent according to the following weight proportions;

[0119] IV. Stir all the raw materials weighed in step III in a reaction vessel at 90°C for 6 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0120] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0121] The epoxy resin is a mixture of E-51 and hydantoin epoxy in a mass ratio of 5:1, and the modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0122] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0123] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

[0124] The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate ester is 4901, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is a mixture of 4,4'-diaminodiphenylmethane and 4,4'-bis(3-aminophenoxy)diphenyl sulfone in a mass ratio of 3:2, the polyamide curing agent is a mixture of polyamide resin 200 and polyamide resin 300 in a mass ratio of 5:2, and the accelerator is 1-benzyl-2-methylimidazolium and triphenylphosphine in a mass ratio of 1:1. All components are prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0125] Comparative Example 1:

[0126] The preparation method of this comparative modified epoxy resin adhesive is carried out according to the following steps:

[0127] 1. Weigh out 55 parts epoxy resin, 8 parts modified heterocyclic resin, 6 parts thermosetting PI fiber powder, 0.5 parts coupling agent, 1.1 parts epoxy phosphate ester and 1 part thixotropic agent by weight.

[0128] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0129] 3. Weigh out 15 parts of aromatic amine curing agent, 28 parts of polyamide curing agent, 0.6 parts of accelerator and 0.8 parts of grafting agent according to the following weight proportions;

[0130] IV. Stir all the raw materials weighed in step III in a reaction vessel at 80°C for 7 hours. When the appearance is uniform and no solid substances are precipitated, cool to room temperature for later use to obtain component B.

[0131] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain a modified epoxy resin adhesive.

[0132] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4. The modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline in a mass ratio of 2:1:1 at 130℃ for 4 hours. The thermosetting PI fiber powder has a mesh size of 100 mesh and a glass transition temperature of 425℃. The coupling agent is γ-mercaptopropylmethyldimethoxysilane. The epoxy phosphate ester is CM-801. The thixotropic agent is fumed silica R202. The aromatic amine curing agent is 1,3-bis(3-aminophenoxy)benzene. The polyamide curing agent is polyamide resin V140. The accelerator is 2-methylimidazolium and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is resorcinol diglycidyl ether.

[0133] Comparative Example 2:

[0134] The preparation method of this comparative modified epoxy resin adhesive is carried out according to the following steps:

[0135] 1. Weigh out 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 28 parts of comb-type polyarylene ether nitrile, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate ester and 1 part of thixotropic agent according to the following weight proportions;

[0136] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add comb-type polyarylether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0137] 3. Weigh out 15 parts of aromatic amine curing agent, 28 parts of polyamide curing agent, 0.6 parts of accelerator and 0.8 parts of grafting agent according to the following weight proportions;

[0138] IV. Stir all the raw materials weighed in step III in a reaction vessel at 80°C for 7 hours. When the appearance is uniform and no solid substances are precipitated, cool to room temperature for later use to obtain component B.

[0139] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain a modified epoxy resin adhesive.

[0140] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4, and the modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0141] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0142] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate ester is CM-801, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is 1,3-bis(3-aminophenoxy)benzene, and the polyamide curing agent is polyamide resin V140. The accelerator is prepared by conventional physical mixing of 2-methylimidazolium and triphenylphosphine at a mass ratio of 1:1. The grafting agent is resorcinol diglycidyl ether.

[0143] Comparative Example 3:

[0144] The preparation method of this comparative modified epoxy resin adhesive is carried out according to the following steps:

[0145] 1. Weigh out 48 parts of epoxy resin, 24 parts of comb-type polyarylene ether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate ester and 3 parts of thixotropic agent according to the following weight proportions;

[0146] 2. Mix the epoxy resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0147] 3. Weigh out 16 parts of aromatic amine curing agent, 35 parts of polyamide curing agent, 0.8 parts of accelerator and 1.4 parts of grafting agent according to the following weight proportions;

[0148] IV. Stir all the raw materials weighed in step III in a reaction vessel at 90°C for 6 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0149] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature until homogeneous to obtain a modified epoxy resin adhesive.

[0150] The epoxy resin is a mixture of E-51 and hydantoin epoxy in a mass ratio of 5:1.

[0151] The structural formula of comb-type polyarylether nitrile is: It has a mesh size of 150 and a glass transition temperature of 127℃.

[0152] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃. The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate ester is 4901, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is a mixture of 4,4'-diaminodiphenylmethane and 4,4'-bis(3-aminophenoxy)diphenyl sulfone in a 3:2 mass ratio, and the polyamide curing agent is a mixture of polyamide resin 200 and polyamide resin 300 in a 5:2 mass ratio. The accelerator is 1-benzyl-2-methylimidazolium and triphenylphosphine in a 1:1 mass ratio, prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0153] Comparative Example 4:

[0154] The preparation method of this comparative example phenolphthalein-type polyarylene ether nitrile modified epoxy resin adhesive is carried out according to the following steps:

[0155] 1. Weigh out 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of phenolphthalein-type polyarylene ether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate ester and 3 parts of thixotropic agent according to the following mass proportions.

[0156] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly in a disperser at room temperature using conventional methods, then add thermosetting PI fiber powder, phenolphthalein type polyarylene ether nitrile and thixotropic agent, and grind and disperse three times using a three-roll mill to obtain component A.

[0157] 3. Weigh out 16 parts of aromatic amine curing agent, 35 parts of polyamide curing agent, 0.8 parts of accelerator and 1.4 parts of grafting agent according to the following weight proportions;

[0158] IV. Stir all the raw materials weighed in step III in a reaction vessel at 90°C for 6 hours until the appearance is uniform and no solid substances precipitate out. Cool to room temperature for later use to obtain component B.

[0159] 5. Manually stir the components A obtained in step 2 and B obtained in step 4 at room temperature until homogeneous to obtain a phenolphthalein-type polyarylene ether nitrile modified epoxy resin adhesive.

[0160] The epoxy resin is a mixture of E-51 and hydantoin epoxy in a mass ratio of 5:1, and the modified heterocyclic resin is prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0161] Phenolphthalein-type polyarylether nitrile is a commercially available industrial product with the following structural formula: It has a mesh size of 150 and a glass transition temperature of 260℃.

[0162] The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃. The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate ester is 4901, the thixotropic agent is fumed silica R202, the aromatic amine curing agent is a mixture of 4,4'-diaminodiphenylmethane and 4,4'-bis(3-aminophenoxy)diphenyl sulfone in a 3:2 mass ratio, and the polyamide curing agent is a mixture of polyamide resin 200 and polyamide resin 300 in a 5:2 mass ratio. The accelerator is 1-benzyl-2-methylimidazolium and triphenylphosphine in a 1:1 mass ratio, prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0163] Comparative Example 5:

[0164] This comparative example uses the exact same raw materials and formulation as Example 6. A polyarylene ether nitrile modified epoxy resin adhesive is prepared by a traditional hot melt method, wherein component A is prepared according to the following steps:

[0165] Step 1: Weigh out 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of comb-type polyarylene ether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate ester and 3 parts of thixotropic agent according to the following mass proportions.

[0166] Step 2: Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in Step 1, and stir evenly in a disperser at room temperature using conventional methods. Then add comb-type polyarylene ether nitrile and melt at 150°C for 3 hours until it becomes uniform and transparent. While it is still hot, add thermosetting PI fiber powder and thixotropic agent, and stir evenly to obtain component A.

[0167] The preparation process of component B in this comparative example is exactly the same as that in Example 6.

[0168] Comparative experiments revealed that when component A prepared in Comparative Example 5 was cooled to room temperature, it was in a semi-solid resin state and could not be manually stirred evenly with component B at room temperature, nor could it be applied. Therefore, no test results were obtained for its adhesive performance.

[0169] In this comparative example, when comb-type polyarylene ether nitrile was used as a toughening modifier for epoxy resin, the problem of high viscosity, which was not conducive to application, could not be solved by using the hot-melt method. Only by adding it to the system in powder form (the mesh size of the comb-type polyarylene ether nitrile powder was 150 mesh) could the viscosity of the epoxy resin adhesive itself be kept relatively stable, which was very beneficial for application.

[0170] The modified epoxy resin adhesives prepared in Examples 1-6 and Comparative Examples 1-4 were used to bond aluminum alloy, carbon steel, and nylon composite materials, respectively. The aluminum alloy surface was sanded with 80-grit sandpaper before use, and then surface-treated according to HB / Z197-1991 standard. The carbon steel and nylon composite materials were sanded with 80-grit sandpaper only before use. The adhesive curing procedure was to first hold at 70℃ for 2 hours and then at 150℃ for 3 hours. The room temperature shear strength was tested according to GB / T 7124-2008, and the test results are shown in Table 1, in MPa.

[0171] Table 1

[0172]

[0173] As shown in Table 1, the shear strength of the comb-type polyarylene ether nitrile modified epoxy resin adhesive prepared in this invention for bonding aluminum alloys at room temperature is 30–38 MPa. After aging at 200℃ for 1000 h, the shear strength of the bonded aluminum alloy at room temperature is 22–31 MPa. After immersion in artificial seawater for 30 days, the shear strength of the bonded aluminum alloy at room temperature is 28–34 MPa. The shear strength for bonding carbon steel at room temperature is 26–37 MPa, and the shear strength for bonding nylon composite materials at room temperature can reach 19–26 MPa. Therefore, the comb-type polyarylene ether nitrile modified epoxy resin adhesive prepared in this invention exhibits good resistance to media, excellent high-temperature aging resistance, and good bonding effect on interfaces of various materials, with a wide range of applications and broad practical value.

[0174] Compared to Example 2, Comparative Example 1 lacked comb-type polyarylene ether nitrile, while Comparative Example 2 lacked thermosetting PI fiber powder. Neither could exert the synergistic effect of the two, and the toughness and high-temperature aging resistance of the prepared modified epoxy resin adhesive were relatively poor. Specifically, the shear strength at 25°C when bonding aluminum alloy and the shear strength at 25°C after aging at 200°C for 1000 hours were significantly lower than those in Example 2.

[0175] Compared to Example 6, Comparative Example 3 lacked modified heterocyclic resin. The modified epoxy resin adhesive prepared in this example showed a significant decrease in shear strength at 25°C after aging at 200°C for 1000 hours and after immersion in artificial seawater for 30 days. This indicates that the adhesive has poor high-temperature aging resistance and media resistance.

[0176] Compared to Example 6, in Comparative Example 4, the comb-type polyarylene ether nitrile was replaced with phenolphthalein-type polyarylene ether nitrile. Since its glass transition temperature is as high as 260°C, the phenolphthalein-type polyarylene ether nitrile inside the prepared modified epoxy resin adhesive still exhibits a rigid state similar to that of inorganic fillers during the heating and curing process, and cannot play a synergistic role with the thermosetting PI fiber powder. Therefore, the bonding strength of the prepared modified epoxy resin adhesive is significantly lower.

Claims

1. A comb-type polyarylether nitrile modified epoxy resin adhesive, characterized in that, The comb-type polyarylene ether nitrile modified epoxy resin adhesive comprises component A and component B. Component A, by weight, comprises: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate, and 1-5 parts thixotropic agent. Component B, by weight, comprises: 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent. The structural formula of the comb-type polyarylene ether nitrile is: ， The mesh size of the comb-type polyarylether nitrile is 120-180 mesh, and the glass transition temperature is 127℃; The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-ethyleneaniline at a mass ratio of 2:1:1 at 130°C for 4 hours. The preparation method of component A is as follows: epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate are mixed and stirred evenly at room temperature. Then, thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent are added, and the mixture is ground and dispersed to obtain component A.

2. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The epoxy resin is one or a mixture of several of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90, and Hein Epoxy.

3. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The thermosetting PI fiber powder has a mesh size of 100 and a glass transition temperature of 425℃.

4. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The aromatic amine curing agent is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, etc. One or a mixture of several of the following: 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, and 4,4'-bis(3-aminophenoxy)benzophenone.

5. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The polyamide curing agent is one or a mixture of several of the following: polyamide resin 651, polyamide resin 650, polyamide resin V115, polyamide resin V125, polyamide resin V140, polyamide resin 200, and polyamide resin 300.

6. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The accelerator is obtained by mixing an imidazole derivative with triphenylphosphine at a mass ratio of 1:

1.

7. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 6, characterized in that, The imidazole derivative is 1-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium or 1-(2-cyanoethyl)-2-undecylimidazolium.

8. The comb-type polyarylene ether nitrile modified epoxy resin adhesive according to claim 1, characterized in that, The grafting agent is polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, 1,4-cyclohexanediethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether, or diethylene glycol diglycidyl ether.

9. The preparation method of the comb-type polyarylene ether nitrile modified epoxy resin adhesive as described in claim 1, characterized in that... The preparation method is carried out according to the following steps: I. Weigh out the following components by weight: 40-65 parts epoxy resin, 6-20 parts modified heterocyclic resin, 8-30 parts comb-type polyarylene ether nitrile, 2-10 parts thermosetting PI fiber powder, 0.2-1.5 parts coupling agent, 0.5-2 parts epoxy phosphate ester, 1-5 parts thixotropic agent, 15-25 parts aromatic amine curing agent, 20-40 parts polyamide curing agent, 0.3-1.0 parts accelerator, and 0.6-1.5 parts grafting agent.

2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate ester weighed in step 1, stir evenly at room temperature, then add thermosetting PI fiber powder, comb-type polyarylene ether nitrile and thixotropic agent, grind and disperse to obtain component A.

3. Stir the aromatic amine curing agent, polyamide curing agent, accelerator and grafting agent in a reaction vessel at 80-100℃ for 4-8 hours, cool to room temperature for later use, and obtain component B; 4. Mix component A obtained in step 2 and component B obtained in step 3 at room temperature to obtain comb-type polyarylene ether nitrile modified epoxy resin adhesive.

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