Comb-type polyarylene ether nitrile modified epoxy resin adhesive and preparation method thereof

Abstract

The invention discloses a comb-type polyarylene ether nitrile modified epoxy resin adhesive and a preparation method thereof, relates to the field of epoxy resin adhesives, and aims to solve the problems that existing polyarylene ether nitrile serving as a toughening modifier is introduced into an epoxy resin system, the viscosity is high, and smearing construction is not facilitated. The comb-type polyarylene ether nitrile modified epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises epoxy resin, modified heterocyclic resin, comb-type polyarylene ether nitrile, thermosetting PI fiber powder, a coupling agent, epoxy phosphate and a thixotropic agent; the component B comprises an aromatic amine curing agent, a polyamide curing agent, an accelerant and a grafting agent. The method comprises the following steps: uniformly stirring the component A and the component B to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive. According to the invention, the comb-type polyarylene ether nitrile powder is used as a toughening modifier of epoxy resin, and the viscosity of the epoxy resin adhesive is not greatly changed by introducing the powder, so that the epoxy resin adhesive is beneficial to smearing construction when being used, and can be used for filling, repairing and bonding holes, grooves and gaps on workpieces made of various materials.

Description

Technical Field

[0001] The invention relates to the field of epoxy resin adhesives, and in particular to a comb-type polyarylether nitrile modified epoxy resin adhesive and a preparation method thereof. Background Art

[0002] Epoxy resin has excellent bonding properties, mechanical properties and chemical stability, as well as good processability and low cost. As an adhesive material, it has been widely used in different fields. However, epoxy resin also has disadvantages such as hardness and brittleness and poor impact resistance. Therefore, when used as an adhesive material, it often needs to be toughened and modified.

[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, poly(arylether nitrile) is a new type of high-performance thermoplastic resin, and there are also a lot of research reports on the modification of epoxy resins. However, most scholars use solvent method or hot melt method to introduce poly(arylether nitrile) into epoxy resin system. The solvent method is highly toxic and not safe and environmentally friendly. The hot melt method needs to be heated to a high temperature to mix evenly, and the processability is poor. At the same time, this method causes the viscosity of the epoxy resin adhesive itself to increase significantly, which is not conducive to coating construction. The prepared adhesive has strong selectivity for the interface of the bonded material and has a very narrow scope of application. In addition, there are also studies that show that the comprehensive performance of epoxy resin adhesives can be improved by blending aromatic amine curing agents, polyamide curing agents, polyether amine curing agents, fatty amine curing agents, imidazole curing agents, thiol curing agents, etc. in various combinations. However, most of them are added separately in the form of multiple components, which brings troubles to the actual operation. Summary of the invention

[0004] The invention aims to solve the problem that the existing polyarylether nitrile is introduced into the epoxy resin system as a toughening modifier, the viscosity is relatively large, and it is not conducive to coating construction. A comb-shaped polyarylether nitrile modified epoxy resin adhesive and a preparation method thereof are provided.

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

[0006] The comb-type polyarylethernitrile structural formula is:

[0007]

[0008] The mesh number of the comb-shaped polyarylethernitrile is 120 to 180 meshes, and the glass transition temperature is 127°C.

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

[0010] Furthermore, the modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline 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 meshes and a glass transition temperature of 425°C.

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

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

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

[0015] Further, 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, phenoxy)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, 4,4'-bis(3-aminophenoxy)benzophenone or a mixture of any of the above.

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

[0017] Furthermore, the accelerator is obtained by mixing an imidazole derivative and triphenylphosphine in a mass ratio of 1:1.

[0018] The imidazole derivative is 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-(2-cyanoethyl)-2-undecylimidazole.

[0019] Furthermore, 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-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether.

[0020] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive is carried out according to the following steps:

[0021] 1. Weigh 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb-type polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate, 1-5 parts of thixotropic agent, 15-25 parts of aromatic amine curing agent, 20-40 parts of polyamide curing agent, 0.3-1.0 parts of accelerator and 0.6-1.5 parts of grafting agent according to mass proportion;

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

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

[0024] 4. Stir the component A obtained in step 2 and the component B obtained in step 3 evenly at room temperature to obtain a comb-shaped polyarylether nitrile modified epoxy resin adhesive.

[0025] The beneficial effects of the present invention are:

[0026] The present invention uses comb-shaped polyarylether nitrile powder as a toughening modifier for epoxy resin, and does not require the introduction of a traditional solvent method or a high-temperature hot melt method. It can be evenly ground and dispersed at room temperature, and the preparation process is very simple, safe and environmentally friendly. At the same time, this introduction method of the present invention makes the viscosity of the epoxy resin adhesive itself change little, and when used as a paste adhesive, it is very conducive to coating construction, and can be used to fill, repair and structurally bond holes, grooves, and gaps on various metals, composite materials, and special plastic parts.

[0027] Due to the particularity of the molecular structure of comb-type polyarylethernitrile, its glass transition temperature is only 127°C. During the heating and curing process, the comb-type polyarylethernitrile presents the state of a rubber elastomer. The synergistic effect with the thermosetting PI fiber powder can significantly improve the toughness and high-temperature aging resistance of the epoxy resin adhesive.

[0028] The modified heterocyclic resin used in the present invention is liquid at room temperature and has very little effect on the construction processability of the epoxy resin adhesive. Multiple polymerization reactions occur through the double bonds of bismaleimide, vinyl double bonds, and alkynyl groups in its molecules with epoxy groups, amino groups, etc. in the resin matrix. The heterogeneity of the cross-linked network structure makes the modified epoxy resin adhesive have good toughness, and also has excellent high-temperature anti-aging and medium resistance.

[0029] The curing system of the present invention simultaneously adopts an aromatic amine curing agent, a polyamide curing agent and an accelerator, and adopts a low-viscosity grafting agent with an epoxy group to organically bridge them together. After being placed at room temperature for one year, there is no stratification and no crystal precipitation, and the storage stability is very good. It does not need to be added one by one during use, which is convenient and quick.

[0030] The comb-shaped polyarylether nitrile modified epoxy resin adhesive prepared by the present invention has a shear strength of 30 to 38 MPa at room temperature for bonding aluminum alloy. After high-temperature aging at 200°C for 1000 hours, the shear strength of the bonding aluminum alloy at room temperature is 22 to 31 MPa. After soaking in artificial seawater for 30 days, the shear strength of the bonding aluminum alloy at room temperature is 28 to 34 MPa. The shear strength of bonding carbon steel at room temperature is 26 to 37 MPa, and the shear strength of bonding nylon composite materials at room temperature can reach 19 to 26 MPa. It can be seen that the comb-shaped polyarylether nitrile modified epoxy resin adhesive in the present invention has good medium resistance and excellent high-temperature anti-aging performance, has good bonding effect on various material interfaces, has a wide bonding application surface, and has a wide range of practical value.

[0031] Instruction Manual

[0032] Figure 1 This is the infrared spectrum of comb-type poly(arylene ether nitrile);

[0033] Figure 2 This is the infrared spectrum of thermosetting PI fiber powder. DETAILED DESCRIPTION

[0034] The technical solution of the present invention is not limited to the specific implementation modes listed below, but also includes any combination of the specific implementation modes.

[0035] Specific implementation method 1: The comb-type polyarylether nitrile modified epoxy resin adhesive of this implementation method includes component A and component B, wherein the component A includes, by mass, 40 to 65 parts of epoxy resin, 6 to 20 parts of modified heterocyclic resin, 8 to 30 parts of comb-type polyarylether nitrile, 2 to 10 parts of thermosetting PI fiber powder, 0.2 to 1.5 parts of coupling agent, 0.5 to 2 parts of epoxy phosphate and 1 to 5 parts of thixotropic agent; the component B includes, by mass, 15 to 25 parts of aromatic amine curing agent, 20 to 40 parts of polyamide curing agent, 0.3 to 1.0 parts of accelerator and 0.6 to 1.5 parts of grafting agent;

[0036] The comb-type polyarylethernitrile structural formula is:

[0037]

[0038] The mesh number of the comb-shaped poly(arylether nitrile) is 120-180 mesh, the glass transition temperature is 127°C, and its infrared spectrum is as shown in the attached figure. Figure 1 shown.

[0039] Specific embodiment 2: This embodiment is different from specific embodiment 1 in that the epoxy resin is one or a mixture of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90, hydantoin epoxy. Others are the same as specific embodiment 1.

[0040] Specific embodiment 3: This embodiment is different from specific embodiment 1 or 2 in that the modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline at a mass ratio of 2:1:1 at 130°C for 4 hours. Others are the same as specific embodiment 1 or 2.

[0041] Specific embodiment 4: This embodiment is different from the specific embodiments 1 to 3 in that: the mesh number of the thermosetting PI fiber powder is 100 mesh, the glass transition temperature is 425°C, and its infrared spectrum is as shown in the attached Figure 2 The rest is the same as that of the first to third embodiments.

[0042] Specific embodiment 5: This embodiment is different from specific embodiments 1 to 4 in that the coupling agent is γ-mercaptopropylmethyldimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide or bis-[γ-(triethoxysilyl)propyl]disulfide. Others are the same as specific embodiments 1 to 4.

[0043] Specific embodiment 6: This embodiment is different from specific embodiments 1 to 5 in that the epoxy phosphate is CM-801 or 4901. The rest is the same as specific embodiments 1 to 5.

[0044] Specific embodiment 7: This embodiment is different from specific embodiments 1 to 6 in that the thixotropic agent is fumed silica R972, A300, A380 or R202. The rest is the same as specific embodiments 1 to 6.

[0045] Specific embodiment eight: This embodiment is different from any one of the specific embodiments 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) )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, 4,4'-bis(3-aminophenoxy)benzophenone or a mixture of several thereof. Others are the same as those in any one of the first to seventh embodiments.

[0046] Specific embodiment 9: This embodiment is different from specific embodiments 1 to 8 in that the polyamide curing agent is one or a mixture of polyamide resin 651, polyamide resin 650, polyamide resin V115, polyamide resin V125, polyamide resin V140, polyamide resin 200, and polyamide resin 300. Other aspects are the same as specific embodiments 1 to 8.

[0047] Specific embodiment 10: This embodiment is different from specific embodiments 1 to 9 in that the accelerator is obtained by mixing an imidazole derivative and triphenylphosphine in a mass ratio of 1:1. The rest is the same as specific embodiments 1 to 9.

[0048] Specific embodiment 11: This embodiment is different from specific embodiment 10 in that the imidazole derivative is 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-(2-cyanoethyl)-2-undecylimidazole. The rest is the same as specific embodiment 10.

[0049] Specific embodiment 12: This embodiment is different from specific embodiments 1 to 11 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-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether. Others are the same as specific embodiments 1 to 11.

[0050] Specific implementation method 13: The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive in this implementation method is carried out according to the following steps:

[0051] 1. Weigh 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb-type polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate, 1-5 parts of thixotropic agent, 15-25 parts of aromatic amine curing agent, 20-40 parts of polyamide curing agent, 0.3-1.0 parts of accelerator and 0.6-1.5 parts of grafting agent according to mass proportion;

[0052] 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1, stir evenly at room temperature, then add thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent, grind and disperse, and obtain component A;

[0053] 3. Stir the aromatic amine curing agent, polyamide curing agent, accelerator and grafting agent in a reaction kettle at 80-100° C. for 4-8 hours, cool to room temperature for standby use, and obtain component B;

[0054] 4. Stir the component A obtained in step 2 and the component B obtained in step 3 evenly at room temperature to obtain a comb-shaped polyarylether nitrile modified epoxy resin adhesive.

[0055] The embodiments of the present invention are described in detail below. The following embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation schemes and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.

[0056] Embodiment 1:

[0057] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0058] 1. Weigh 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 22 parts of comb-type polyarylether nitrile, 6 parts of thermosetting PI fiber powder, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate and 1 part of thixotropic agent according to mass proportion;

[0059] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0060] 3. Weigh 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 by mass;

[0061] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 80° C. for 7 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0062] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0063] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4.

[0064] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0065] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0066] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0067] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate 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 2-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is resorcinol diglycidyl ether.

[0068] Embodiment 2:

[0069] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0070] 1. Weigh 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 28 parts of comb-type polyarylether nitrile, 6 parts of thermosetting PI fiber powder, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate and 1 part of thixotropic agent according to mass proportion;

[0071] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0072] 3. Weigh 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 by mass;

[0073] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 80° C. for 7 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0074] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0075] The epoxy resin is a mixture of F-44 and E-51 in a mass ratio of 1:4.

[0076] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0077] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0078] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0079] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate 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 in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is resorcinol diglycidyl ether.

[0080] Embodiment 3:

[0081] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0082] 1. Weigh 45 parts of epoxy resin, 14 parts of modified heterocyclic resin, 22 parts of comb-type polyarylethernitrile, 8 parts of thermosetting PI fiber powder, 1.2 parts of coupling agent, 1.6 parts of epoxy phosphate and 2.8 parts of thixotropic agent according to mass proportion;

[0083] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0084] 3. Weigh 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 by mass;

[0085] 4. Stir all the raw materials weighed in step 3 in a reactor at 95° C. for 4.5 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0086] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0087] The epoxy resin is a mixture of E-44 and AG-80 in a mass ratio of 1:2.

[0088] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0089] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0090] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0091] The coupling agent is bis-[γ-(triethoxysilyl)propyl] disulfide, the epoxy phosphate 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 1-cyanoethyl-2-ethyl-4-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is polypropylene glycol diglycidyl ether.

[0092] Embodiment 4:

[0093] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0094] 1. Weigh 52 parts of epoxy resin, 17 parts of modified heterocyclic resin, 10 parts of comb-type polyarylethernitrile, 3 parts of thermosetting PI fiber powder, 0.3 parts of coupling agent, 0.7 parts of epoxy phosphate and 4.5 parts of thixotropic agent according to mass proportion;

[0095] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0096] 3. Weigh 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 by mass;

[0097] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 98° C. for 8 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0098] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0099] The epoxy resin is AG-70. The modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline at a mass ratio of 2:1:1 at 130°C for 4 hours.

[0100] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0101] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0102] The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate 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-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is 1,4-cyclohexanedimethanol diglycidyl ether.

[0103] Embodiment 5:

[0104] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0105] 1. Weigh 60 parts of epoxy resin, 10 parts of modified heterocyclic resin, 25 parts of comb-type polyarylethernitrile, 7 parts of thermosetting PI fiber powder, 1.0 parts of coupling agent, 1.5 parts of epoxy phosphate and 3.3 parts of thixotropic agent according to mass proportion;

[0106] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0107] 3. Weigh 21 parts of aromatic amine curing agent, 30 parts of polyamide curing agent, 0.5 parts of accelerator and 1.0 parts of grafting agent by mass;

[0108] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 90° C. for 6 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0109] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0110] The epoxy resin is a mixture of E-44, E-51 and TDE-85 in a mass ratio of 1:1:1.

[0111] The modified heterocyclic resin was prepared by prepolymerization of 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0112] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0113] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0114] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate 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 mass ratio of 2:1, the polyamide curing agent is a mixture of polyamide resin V115 and polyamide resin 651 in a mass ratio of 1:1, and the accelerator is 2-heptadecylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is neopentyl glycol diglycidyl ether.

[0115] Embodiment 6:

[0116] The preparation method of the comb-shaped polyarylether nitrile modified epoxy resin adhesive of this embodiment is carried out according to the following steps:

[0117] 1. Weigh 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of comb-type polyarylethernitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate and 3 parts of thixotropic agent according to mass proportion;

[0118] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0119] 3. Weigh 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 by mass;

[0120] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 90° C. for 6 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0121] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain the comb-type polyarylene ether nitrile modified epoxy resin adhesive.

[0122] 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 prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0123] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0124] The mesh number of thermosetting PI fiber is 100 mesh and the glass transition temperature is 425℃.

[0125] The coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, the epoxy phosphate 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-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0126] Comparative Example 1:

[0127] The preparation method of the modified epoxy resin adhesive of this comparative example is carried out according to the following steps:

[0128] 1. Weigh 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 6 parts of thermosetting PI fiber powder, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate and 1 part of thixotropic agent according to mass proportion;

[0129] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder and thixotropic agent are added, and grind and dispersed three times using a three-roll grinder to obtain component A;

[0130] 3. Weigh 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 by mass;

[0131] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 80° C. for 7 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0132] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain a modified epoxy resin adhesive.

[0133] Among them, 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 prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours, the thermosetting PI fiber powder has a mesh number of 100 mesh and a glass transition temperature of 425°C, the coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate 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-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing, and the grafting agent is resorcinol diglycidyl ether.

[0134] Comparative Example 2:

[0135] The preparation method of the modified epoxy resin adhesive of this comparative example is carried out according to the following steps:

[0136] 1. Weigh 55 parts of epoxy resin, 8 parts of modified heterocyclic resin, 28 parts of comb-type polyarylether nitrile, 0.5 parts of coupling agent, 1.1 parts of epoxy phosphate and 1 part of thixotropic agent according to mass proportion;

[0137] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, stirred uniformly in a conventional manner at room temperature using a disperser, and then the comb-shaped polyarylether nitrile and thixotropic agent are added, and ground and dispersed three times using a three-roll mill to obtain component A;

[0138] 3. Weigh 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 by mass;

[0139] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 80° C. for 7 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0140] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain a modified epoxy resin adhesive.

[0141] 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 prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0142] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0143] The coupling agent is γ-mercaptopropylmethyldimethoxysilane, the epoxy phosphate 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 2-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is resorcinol diglycidyl ether.

[0144] Comparative Example 3:

[0145] The preparation method of the modified epoxy resin adhesive of this comparative example is carried out according to the following steps:

[0146] 1. Weigh 48 parts of epoxy resin, 24 parts of comb-type polyarylether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate and 3 parts of thixotropic agent according to mass proportion;

[0147] 2. The epoxy resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent are added, and ground and dispersed three times using a three-roll grinder to obtain component A;

[0148] 3. Weigh 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 by mass;

[0149] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 90° C. for 6 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0150] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain a modified epoxy resin adhesive.

[0151] The epoxy resin is a mixture of E-51 and hydantoin epoxy in a mass ratio of 5:1.

[0152] The structural formula of comb-type polyarylether nitrile is: The mesh number is 150 mesh and the glass transition temperature is 127℃.

[0153] The thermosetting PI fiber powder has a mesh number of 100 and a glass transition temperature of 425°C. The coupling agent is bis-[γ-(triethoxysilyl)propyl] tetrasulfide, the epoxy phosphate 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, and the polyamide curing agent is a mixture of polyamide resin 200 and polyamide resin 300 in a mass ratio of 5:2. The accelerator is 1-benzyl-2-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0154] Comparative Example 4:

[0155] The preparation method of the phenolphthalein type polyarylether nitrile modified epoxy resin adhesive of this comparative example is carried out according to the following steps:

[0156] 1. Weigh 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of phenolphthalein type polyarylethernitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate and 3 parts of thixotropic agent according to mass proportion;

[0157] 2. The epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1 are mixed, and stirred uniformly in a conventional manner at room temperature using a disperser, and then thermosetting PI fiber powder, phenolphthalein type polyarylether nitrile and thixotropic agent are added, and grind and dispersed three times using a three-roll mill to obtain component A;

[0158] 3. Weigh 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 by mass;

[0159] 4. Stir all the raw materials weighed in step 3 in a reaction kettle at 90° C. for 6 h, wait until the appearance is uniform and no solid matter is precipitated, cool to room temperature for use, and obtain component B;

[0160] 5. Manually stir the component A obtained in step 2 and the component B obtained in step 4 at room temperature to obtain a phenolphthalein type polyarylether nitrile modified epoxy resin adhesive.

[0161] 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 prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline in a mass ratio of 2:1:1 at 130°C for 4 hours.

[0162] Phenolphthalein polyarylethernitrile is a commercially available industrial product with the structural formula: The mesh size is 150 mesh and the glass transition temperature is 260℃.

[0163] The thermosetting PI fiber powder has a mesh number of 100 meshes, a glass transition temperature of 425°C, a coupling agent of bis-[γ-(triethoxysilyl)propyl] tetrasulfide, an epoxy phosphate of 4901, a thixotropic agent of fumed silica R202, an aromatic amine curing agent of a mixture of 4,4'-diaminodiphenylmethane and 4,4'-bis(3-aminophenoxy)diphenyl sulfone in a mass ratio of 3:2, and a polyamide curing agent of a mixture of polyamide resin 200 and polyamide resin 300 in a mass ratio of 5:2. The accelerator is 1-benzyl-2-methylimidazole and triphenylphosphine in a mass ratio of 1:1, prepared by conventional physical mixing. The grafting agent is triethylene glycol diglycidyl ether.

[0164] Comparative Example 5:

[0165] This comparative example uses exactly the same raw materials and formulation as Example 6 to prepare a polyarylether nitrile modified epoxy resin adhesive by a conventional hot melt method, wherein component A is prepared according to the following steps:

[0166] Step 1: Weigh 48 parts of epoxy resin, 15 parts of modified heterocyclic resin, 24 parts of comb-type polyarylether nitrile, 5 parts of thermosetting PI fiber powder, 0.8 parts of coupling agent, 1.2 parts of epoxy phosphate and 3 parts of thixotropic agent by mass;

[0167] Step 2: Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1, stir evenly in a conventional manner at room temperature using a disperser, then add comb-type polyarylethernitrile and melt at 150°C for 3 hours until it becomes a uniform and transparent state, add thermosetting PI fiber powder and thixotropic agent while hot, stir evenly to obtain component A.

[0168] The preparation process of component B in this comparative example is exactly the same as that in Example 6.

[0169] Through comparative experiments, it was found 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 mixed evenly with component B at room temperature, let alone applied for construction. Therefore, no test results of its bonding performance were obtained.

[0170] In this comparative example, when comb-shaped polyarylethernitrile is used as a toughening modifier for epoxy resin, the hot melt method cannot solve the problem of high viscosity and inconvenience in coating construction. Only when it is added into the system in the form of powder (the mesh number of comb-shaped polyarylethernitrile powder is 150 mesh), the viscosity of the epoxy resin adhesive itself does not change much, which is very conducive to coating construction when used.

[0171] The modified epoxy resin adhesives prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were respectively bonded to aluminum alloy, carbon steel and nylon composite materials, wherein the aluminum alloy was polished with 80-mesh sandpaper before use, and then surface treated according to HB / Z197-1991 standard, and the carbon steel and nylon composite materials were only polished with 80-mesh sandpaper before use. The curing procedure of the adhesive was first 70°C for 2h and then 150°C for 3h. The room temperature shear strength was tested according to GB / T 7124-2008, and the test results are shown in Table 1, in MPa.

[0172] Table 1

[0173]

[0174] As can be seen from Table 1, the shear strength of the comb-shaped polyarylether nitrile modified epoxy resin adhesive bonded to aluminum alloy at room temperature is 30 to 38 MPa. After high-temperature aging at 200°C for 1000 hours, the shear strength of the bonded aluminum alloy at room temperature is 22 to 31 MPa. After soaking in artificial seawater for 30 days, the shear strength of the bonded aluminum alloy at room temperature is 28 to 34 MPa. The shear strength of bonding carbon steel at room temperature is 26 to 37 MPa, and the shear strength of bonding nylon composite materials at room temperature can reach 19 to 26 MPa. It can be seen that the comb-shaped polyarylether nitrile modified epoxy resin adhesive prepared by the present invention has good medium resistance, excellent high-temperature anti-aging performance, good bonding effect on various material interfaces, wide bonding application surface, and has a wide range of practical value.

[0175] Compared with Example 2, Comparative Example 1 lacks comb-type polyarylether nitrile, and Comparative Example 2 does not have thermosetting PI fiber powder, and the synergistic effect of the two cannot be exerted. The toughness and high-temperature aging resistance of the prepared modified epoxy resin adhesive are relatively poor, which is specifically reflected in the 25°C shear strength when bonding aluminum alloy and the 25°C shear strength after high-temperature aging at 200°C for 1000 hours, which are significantly lower than those in Example 2.

[0176] Compared with Example 6, Comparative Example 3 lacks the modified heterocyclic resin, and the prepared modified epoxy resin adhesive has significantly reduced shear strength at 25°C after high-temperature aging at 200°C for 1000 hours and immersion in artificial seawater for 30 days, indicating that the high-temperature aging resistance and media resistance of the adhesive are poor.

[0177] Compared with Example 6, the comb-type polyarylether nitrile in Comparative Example 4 is replaced by phenolphthalein-type polyarylether nitrile. Due to its glass transition temperature of up to 260°C, during the heating and curing process of the prepared modified epoxy resin adhesive, the phenolphthalein-type polyarylether nitrile inside still presents a rigid state similar to that of an inorganic filler, and cannot exert a synergistic effect with the thermosetting PI fiber powder. Therefore, the bonding strength of the prepared modified epoxy resin adhesive is significantly low.

Claims

1. A comb-type polyarylether nitrile modified epoxy resin adhesive, characterized in that: The comb-type polyarylether nitrile modified epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises, by weight: 40 to 65 parts of epoxy resin, 6 to 20 parts of modified heterocyclic resin, 8 to 30 parts of comb-type polyarylether nitrile, 2 to 10 parts of thermosetting PI fiber powder, 0.2 to 1.5 parts of coupling agent, 0.5 to 2 parts of epoxy phosphate and 1 to 5 parts of thixotropic agent; and the component B comprises, by weight: 15 to 25 parts of aromatic amine curing agent, 20 to 40 parts of polyamide curing agent, 0.3 to 1.0 parts of accelerator and 0.6 to 1.5 parts of grafting agent; The comb-type polyarylethernitrile structural formula is: The mesh number of the comb-shaped polyarylethernitrile is 120 to 180 meshes, and the glass transition temperature is 127°C.

2. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that: The epoxy resin is one of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90, and hydantoin epoxy, or a mixture of several of them.

3. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that: The modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1,3-phenylbismaleimide, 3-aminophenylacetylene and 4-vinylaniline at a mass ratio of 2:1:1 at 130° C. for 4 hours.

4. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that: The mesh number of the thermosetting PI fiber powder is 100 meshes, and the glass transition temperature is 425°C.

5. The comb-shaped polyarylether 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, 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, 4,4'-bis(3-aminophenoxy)benzophenone or a mixture of any of the above.

6. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that: The polyamide curing agent is one of polyamide resin 651, polyamide resin 650, polyamide resin V115, polyamide resin V125, polyamide resin V140, polyamide resin 200, and polyamide resin 300, or a mixture of the two or more thereof.

7. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that: The accelerator is obtained by mixing an imidazole derivative and triphenylphosphine in a mass ratio of 1:

1.

8. The comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 7, characterized in that: The imidazole derivative is 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-(2-cyanoethyl)-2-undecylimidazole.

9. The comb-shaped polyarylether 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-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether or diethylene glycol diglycidyl ether.

10. The method for preparing the comb-shaped polyarylether nitrile modified epoxy resin adhesive according to claim 1, characterized in that The preparation method is carried out according to the following steps:

1. Weigh 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb-type polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate, 1-5 parts of thixotropic agent, 15-25 parts of aromatic amine curing agent, 20-40 parts of polyamide curing agent, 0.3-1.0 parts of accelerator and 0.6-1.5 parts of grafting agent according to mass proportion; 2. Mix the epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate weighed in step 1, stir evenly at room temperature, then add thermosetting PI fiber powder, comb-type polyarylether nitrile and thixotropic agent, grind and disperse, and obtain component A; 3. Stir the aromatic amine curing agent, polyamide curing agent, accelerator and grafting agent in a reaction kettle at 80-100° C. for 4-8 hours, cool to room temperature for standby use, and obtain component B; 4. Stir the component A obtained in step 2 and the component B obtained in step 3 evenly at room temperature to obtain a comb-shaped polyarylether nitrile modified epoxy resin adhesive.

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