Two-component flexible epoxy modified carbon-based waterproof glue for exposure and preparation method of two-component flexible epoxy modified carbon-based waterproof glue

Abstract

The invention relates to the technical field of building materials, in particular to two-component flexible epoxy modified carbon-based waterproof glue for exposure and a preparation method of the two-component flexible epoxy modified carbon-based waterproof glue. The epoxy modified carbon-based waterproof glue comprises a component A and a component B. 100 parts by weight of the component A comprises the following raw materials in parts by weight: 55-65 parts of epoxy resin, 8-10 parts of glycidyl ether, 1-3 parts of amino silane and the balance of functional filler; the component B is prepared from the following raw materials in parts by weight: 11.5 to 13.5 parts of a compound amine curing agent, 14.5 to 16.5 parts of modified polyether amine, 14 to 16 parts of epoxy resin, 4 to 6 parts of monoepoxy glycidyl ether, 6 to 8 parts of benzyl alcohol, 1 to 3 parts of a silane coupling agent and the balance of silica powder. The waterproof glue disclosed by the invention has very good permeability, can play a role in waterproofing and bonding reinforcement while permeating base material cracks, has excellent elongation at break, tensile strength, bonding strength and weather resistance, and is strong in applicability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, in particular to a two-component flexible epoxy modified carbon-based waterproof adhesive for external use and a preparation method thereof. BACKGROUND

[0002] Epoxy waterproof adhesive is a two-component reactive material formed by reaction and curing of epoxy resin as the main component with amine curing agent. Compared with polyurea waterproof adhesive, it has excellent construction performance and good bonding strength, and becomes the most commonly used waterproof adhesive product. It also has the following advantages: (1) the cured product has strong bonding strength; (2) the cured product has high film compactness, which can play a good waterproof barrier role to prevent water from penetrating into the base material and effectively protect the base material.

[0003] However, the chemical crosslinking density of epoxy resin after curing is high, and the molecular chain flexibility is low, which leads to high brittleness. When used for leakage repair or waterproof prevention in poor environments such as roofs, basements, tunnels, etc., the cured adhesive is prone to cracking and even shrinkage, which affects the waterproof sealing effect.

[0004] CN109705784A discloses an epoxy adhesive with high peeling strength, which is composed of A component and B component. The A component is prepared from raw materials in the following mass percentages: epoxy resin 30-60%, toughening agent 5-20%, diluent 3-20%, filler 20-50%, hydrophobic fumed silica 0.2-1%, silane coupling agent 1-3%, and blue paste 0.5-2%. The B component is prepared from raw materials in the following mass percentages: low molecular weight polyamide curing agent 30-60%, modified amine curing agent 30-60%, accelerator 1-3%, filler 5-20%, hydrophobic fumed silica 0.2-1%, and silane coupling agent 1-3%. However, the epoxy adhesive with high peeling strength disclosed in this invention has long operation time, long curing time, and long construction cycle. Moreover, the epoxy adhesive does not further improve the weather resistance, and the weather resistance is still room for improvement when used for outdoor waterproofing. SUMMARY

[0005] In view of the defects of the prior art, the present application discloses a two-component flexible epoxy modified carbon-based waterproof adhesive for external use and a preparation method thereof. The waterproof adhesive disclosed in the present application has good permeability, which not only plays a waterproof role when penetrating into the base material cracks, but also has excellent elongation at break, tensile strength, bonding strength, and weather resistance, and has strong applicability.

[0006] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0007] The first aspect of the present application provides a two-component flexible epoxy-modified carbon-based waterproof adhesive for external use, which comprises component A and component B, wherein, based on 100 parts by weight, component A comprises the following raw materials in parts by weight: 55-65 parts of epoxy resin, 8-10 parts of glycidyl ether, 1-3 parts of amino silane, and the balance is functional filler; component B comprises the following raw materials in parts by weight: 11.5-13.5 parts of composite amine curing agent, 14.5-16.5 parts of modified polyether amine, 14-16 parts of epoxy resin, 4-6 parts of mono-epoxy glycidyl ether, 6-8 parts of benzyl alcohol, 1-3 parts of silane coupling agent, and the balance is silicon powder.

[0008] In some embodiments of the present application, the epoxy resins are both E51 epoxy resins.

[0009] In some embodiments of the present application, the glycidyl ether is polypropylene glycol diglycidyl ether.

[0010] In some embodiments of the present application, the composite amine curing agent is a mixture of alicyclic amine curing agent and aliphatic amine curing agent.

[0011] In some embodiments of the present application, the mass ratio of the alicyclic amine curing agent and the aliphatic amine curing agent is 1:(1-3).

[0012] Preferably, the alicyclic amine curing agent is 1,3-cyclohexane diamine.

[0013] Preferably, the aliphatic amine curing agent is 1,5-diamino-2-methylpentane.

[0014] In some embodiments of the present application, the functional filler is prepared by the following steps:

[0015] The graphene is dispersed in a mixed solvent of water and ethanol, and then a fluorosilicon-modified acrylic resin is added. After stirring at 25-30℃ for 1-3h until fully mixed, the stirring is maintained, and the temperature is continuously increased to 100-105℃. The reaction is carried out for 2-3h, and then the precipitate is collected, washed and dried to obtain the functional filler.

[0016] In some embodiments of the present application, the mass ratio of the graphene and the fluorosilicon-modified acrylic resin is 1:(0.8-1).

[0017] The modified graphene prepared by the application is added into a waterproof glue system as a functional filler, and it is found that the weather resistance of the system after curing is greatly improved. The possible reason is that the fluorosilicon modified acrylic resin is combined together with the active hydroxyl groups on the edges of the graphene sheet layer and the defects in the sheet through chemical grafting, and the long-chain structure of the fluorosilicon modified acrylic resin forms a stable self-supporting structure between the graphene layers, avoiding the problem that the functional decline is caused by the aggregation of graphene when added into the system. Meanwhile, the existence of fluorine and silicon groups on the fluorosilicon modified acrylic resin avoids the adverse effect of the increase of the content of oxygen-containing functional groups caused by grafting modification on the thermal stability of the functional filler, so that the functional filler can be uniformly and stably dispersed in the system, absorb ultraviolet rays, scavenge free radicals, and then protect the glue polymer segment, while synergistically filling the voids generated in the curing process, hindering the invasion of small molecules, and significantly improving the weather resistance of the waterproof glue.

[0018] In some embodiments of the application, the preparation steps of the modified polyetheramine are as follows:

[0019] (1) 4-aminomethylpiperidine and 1,1'-carbonyldiimidazole are added into a solvent, and the temperature is raised to 80-85 DEG C for stirring reaction for 2-3 h. After cooling, filtration, washing and drying, an intermediate product is obtained;

[0020] (2) The intermediate product of step (1) and polyetheramine are mixed, and the temperature is raised to 40-50 DEG C for reaction for 13-15 h. After purification, washing and drying, the modified polyetheramine is obtained.

[0021] In some embodiments of the application, the mass ratio of 4-aminomethylpiperidine and 1,1'-carbonyldiimidazole in step (1) is 1: (2.8-3.4).

[0022] In some embodiments of the application, the mass ratio of the intermediate product and polyetheramine in step (2) is (0.03-0.06): 1.

[0023] In some embodiments of the application, the preparation steps of the polyetheramine in step (2) are as follows:

[0024] 1,2-propanediamine and 1,4-butanediol diglycidyl ether are added into anhydrous ethanol, inert gas is introduced, and the temperature is raised to 40-45 DEG C for reaction for 24-26 h. After rotary evaporation, precipitation and drying, the polyetheramine is obtained.

[0025] In some embodiments of the application, the mass ratio of 1,2-propanediamine and 1,4-butanediol diglycidyl ether is 1: (3.2-3.8).

[0026] In some embodiments of the application, the single epoxy glycidyl ether is C12-14 alkyl glycidyl ether (AGE).

[0027] In some embodiments of the present application, the aminosilane is gamma-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.

[0028] In some embodiments of the present application, the silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-glycidyloxypropyl trimethoxysilane.

[0029] The present application prepares a new type of modified polyether amine and composite amine type curing agent composition epoxy modified carbon-based waterproof adhesive curing system, unexpectedly found that the comprehensive performance of the adhesive has been significantly improved, the applicant speculates that when the curing promoting structure is introduced into the polyether amine during preparation, the rigid structure balances the flexibility of the long molecular chain polyether amine, which may have an adverse effect on the mechanical properties of the adhesive after curing, and improves the weather resistance of the adhesive; at the same time, the introduction of methyl and branched chain structure in the modified polyether amine further increases the water resistance of the adhesive, and the presence of active groups on the adhesive further improves the crosslinking density of the curing system, which helps to increase the waterproof bonding strength of the system.

[0030] The applicant also found that when the composite amine type curing agent and the modified polyether amine are in a specific ratio, not only the fracture toughness, tensile strength and bonding strength of the adhesive are significantly improved, but also the processing efficiency is guaranteed by adjusting the curing reaction rate, and multiple performance optimization is realized. The applicant speculates that under this condition, the modified polyether amine not only helps the aliphatic amine curing agent to increase the system strength, but also enhances the adhesion of the aliphatic amine curing agent and improves the curing rate, while reducing the adverse effects of ether bonds on the curing rate of the adhesive. It also reduces the negative impact of the curing promoting structure on the stability of the adhesive by increasing the steric hindrance of the molecular chain, and realizes the balanced improvement of multiple performance.

[0031] The present application also provides a preparation method of a two-component flexible epoxy modified carbon-based waterproof adhesive for external use, comprising the following steps:

[0032] S1: mixing the epoxy resin, glycidyl ether and aminosilane in component A, stirring at 70-80℃ for 3-4h, then adding functional fillers and stirring for 30-40min to obtain component A;

[0033] S2: mixing the composite amine type curing agent, modified polyether amine, epoxy resin, mono-epoxy glycidyl ether, benzyl alcohol and silane coupling agent in component B, stirring at 80-90℃ for 3-4h, then adding silicon powder and stirring for 30-40min to obtain component B;

[0034] When used, component A of step S1 and component B of step S2 are mixed.

[0035] Preferably, when used, component A of step S1 and component B of step S2 are mixed in a mass ratio of 1:1.

[0036] Compared with the prior art, the application has the following advantages:

[0037] (1) The waterproof glue disclosed by the application has good permeability, can penetrate into cracks of a base material to play a waterproof and bonding and reinforcing role, has excellent elongation at break, tensile strength, bonding strength and weather resistance, and has strong applicability.

[0038] (2) The modified graphene prepared in the application is added to the system as a functional filler, which can be uniformly and stably dispersed in the system, absorb ultraviolet rays, scavenge free radicals, and then protect the colloid polymer chain segment; on the other hand, it can also cooperate with the silicon powder to adjust the viscosity of the system, fill the voids generated in the curing process, hinder the invasion of small molecules, and significantly improve the weather resistance of the waterproof glue.

[0039] (3) The modified polyether amine is obtained by introducing a curing promotion structure into the polyether amine, which balances the flexibility of the long molecular chain polyether amine and avoids the adverse effects of the ether bond on the curing rate of the glue, realizing the multiple effects of toughening, excellent mechanical properties and improving the curing reaction rate to ensure the processing efficiency. DETAILED DESCRIPTION

[0040] The application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the application and are only used to illustrate the application, but not to limit the application. Meanwhile, all professional terms mentioned below have the same meaning as generally understood by those skilled in the art, and the professional terms used in this paper are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the application. Without deviating from the main idea or scope of the application, other combinations and various modifications within the concept of the application can be made.

[0041] Unless otherwise specified, the reagents used in the following can be easily obtained from commercial companies, wherein the preparation steps of the fluorosilicon modified acrylic resin used refer to "Wu Zhenxian, et al: Preparation and Research of Fluorosilicon Modified Acrylic Resin" WPA-5; the size of the graphene used is 20-30 μm.

[0042] Unless otherwise specified, the post-treatment steps such as "dispersion", "rotary evaporation", "precipitation", "drying", "centrifugation" and the like used in the following are the routine operations of those skilled in the art, which can be selected by the actual operation.

[0043] Preparation Example 1

[0044] The preparation steps of the functional filler are as follows:

[0045] 1 g of graphene was dispersed in 100 mL of a mixed solvent of water and ethanol mixed at a volume ratio of 1:1, and 1 g of fluorosilicon-modified acrylic resin was added. The mixture was stirred at 28°C for 2 h until well mixed, and then the temperature was increased to 102°C while stirring was maintained. The reaction was continued for 2.5 h, and the precipitate was collected by centrifugation, washed, and dried to obtain the functional filler.

[0046] Preparation Example 2

[0047] The preparation procedure of the functional filler was the same as in Preparation Example 1, except that the amount of the fluorosilicon-modified acrylic resin added was 1.2 g.

[0048] Preparation Example 3

[0049] The preparation procedure of the functional filler was the same as in Preparation Example 1, except that the fluorosilicon-modified acrylic resin was replaced by an equal amount of polyacrylic acid (Mn = 2400).

[0050] Preparation Example 4

[0051] The polyether amine was prepared as follows:

[0052] 1 g of 1,2-propanediamine and 3.6 g of 1,4-butanediol diglycidyl ether were added to 20 mL of anhydrous ethanol, and nitrogen gas was bubbled through the mixture. The temperature was increased to 42°C, and the reaction was continued for 25 h. The product was obtained by rotary evaporation, precipitation, and drying.

[0053] Preparation Example 5

[0054] The modified polyether amine was prepared as follows:

[0055] (1) 5 g of 4-aminomethylpiperidine and 15.5 g of 1,1'-carbonyldiimidazole were added to 300 mL of dimethyl sulfoxide, and the temperature was increased to 83°C. The reaction was continued for 2.5 h while stirring, and then the temperature was decreased to room temperature. The intermediate product was obtained by filtration, washing, and drying.

[0056] (2) 3.6 g of the intermediate product from step (1) and 80 g of the polyether amine were mixed, and the temperature was increased to 45°C. The reaction was continued for 14 h, and then the product was obtained by purification, washing, and drying.

[0057] The polyether amine used in this preparation example was obtained from Preparation Example 4.

[0058] Preparation Example 6

[0059] The preparation procedure of the modified polyether amine was the same as in Preparation Example 5, except that the amount of 1,1'-carbonyldiimidazole added in step (1) was 18 g.

[0060] Preparation Example 7

[0061] The preparation procedure of the modified polyether amine was the same as in Preparation Example 5, except that the amount of the intermediate product added in step (2) was 6.5 g.

[0062] Preparation Example 8

[0063] The preparation procedure of the modified polyether amine is the same as that of Preparation Example 5, except that the polyether amine used in step (2) in this preparation example is polyether amine D400.

[0064] Unless otherwise specified, the epoxy resin used in the following specific embodiments is E51 epoxy resin (purchased from Nanya Electronic Materials (Kunshan) Co., Ltd.), the glycidyl ether is polypropylene glycol diglycidyl ether (Mn = 640), the amino silane used in the A component is γ-aminopropyl triethoxysilane, the composite amine curing agent is a mixture of 1,3-cyclohexane diamine and 1,5-diamino-2-methyl pentane in a mass ratio of 1:2, the mono-epoxy glycidyl ether is C12-14 alkyl glycidyl ether (AGE), the silane coupling agent used in the B component is γ-glycidyl ether propyl trimethoxysilane, and the particle size of the silicon powder is 10-20 μm.

[0065] Example 1

[0066] A two-component flexible epoxy modified carbon-based waterproof adhesive for exterior use comprises an A component and a B component, wherein, based on 100 parts by weight, the A component comprises the following raw materials in parts by weight: 60 parts of epoxy resin, 9 parts of glycidyl ether, 2 parts of amino silane, and the balance of functional fillers; the B component comprises the following raw materials in parts by weight: 12.5 parts of composite amine curing agent, 15.5 parts of modified polyether amine, 15 parts of epoxy resin, 5 parts of mono-epoxy glycidyl ether, 7 parts of benzyl alcohol, 2 parts of silane coupling agent, and the balance of silicon powder.

[0067] The preparation method of the two-component flexible epoxy modified carbon-based waterproof adhesive for exterior use in this example comprises the following steps:

[0068] S1: The epoxy resin, glycidyl ether and amino silane in the A component are mixed, stirred at 75°C for 3.5 h, and then the functional fillers are added and stirred for 40 min, to obtain the A component;

[0069] S2: The composite amine curing agent, modified polyether amine, epoxy resin, mono-epoxy glycidyl ether, benzyl alcohol and silane coupling agent in the B component are mixed, stirred at 85°C for 3.5 h, and then the silicon powder is added and stirred for 35 min, to obtain the B component.

[0070] The functional fillers used in this example are obtained from Preparation Example 1, and the modified polyether amine is obtained from Preparation Example 5.

[0071] Example 2

[0072] A two-component flexible epoxy-modified carbon-based waterproof adhesive for external use comprises a component A and a component B. Component A comprises the following raw materials in parts by weight, based on 100 parts by weight: 55 parts of epoxy resin, 8 parts of glycidyl ether, 1 part of aminosilane, and the remainder being a functional filler; and component B comprises the following raw materials in parts by weight: 11.5 parts of a complex amine curing agent, 14.5 parts of a modified polyetheramine, 14 parts of an epoxy resin, 4 parts of monoepoxy glycidyl ether, 6 parts of benzyl alcohol, 1 part of a silane coupling agent, and the remainder being silicon micropowder.

[0073] The preparation method of the two-component flexible epoxy-modified carbon-based waterproof adhesive for external use in this embodiment comprises the following steps:

[0074] S1: Mix the epoxy resin, glycidyl ether and aminosilane in component A, stir at 80°C for 3 hours, then add the functional filler and stir for 30 minutes to obtain component A;

[0075] S2: Mix the complex amine curing agent, modified polyetheramine, epoxy resin, monoepoxy glycidyl ether, benzyl alcohol and silane coupling agent in component B, stir at 80°C for 4 hours, then add silicon micropowder and stir for 30 minutes to obtain component B.

[0076] The functional filler used in this example is obtained from Preparation Example 1, and the modified polyetheramine is obtained from Preparation Example 5.

[0077] Example 3

[0078] A two-component flexible epoxy-modified carbon-based waterproof adhesive for external use comprises a component A and a component B. Component A comprises the following raw materials in parts by weight, based on 100 parts by weight: 65 parts of epoxy resin, 10 parts of glycidyl ether, 3 parts of aminosilane, and the remainder being a functional filler; and component B comprises the following raw materials in parts by weight: 13.5 parts of a complex amine curing agent, 16.5 parts of a modified polyetheramine, 16 parts of an epoxy resin, 6 parts of monoepoxy glycidyl ether, 8 parts of benzyl alcohol, 3 parts of a silane coupling agent, and the remainder being silicon micropowder.

[0079] The preparation method of the two-component flexible epoxy-modified carbon-based waterproof adhesive for external use in this embodiment comprises the following steps:

[0080] S1: Mix the epoxy resin, glycidyl ether and aminosilane in component A, stir at 70°C for 4 hours, then add the functional filler and stir for 40 minutes to obtain component A;

[0081] S2: Mix the complex amine curing agent, modified polyetheramine, epoxy resin, monoepoxy glycidyl ether, benzyl alcohol and silane coupling agent in component B, stir at 90°C for 3 hours, then add silicon micropowder and stir for 40 minutes to obtain component B.

[0082] The functional filler used in this example is obtained from Preparation Example 1, and the modified polyether amine is obtained from Preparation Example 5.

[0083] Example 4

[0084] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the functional filler used is obtained from Preparation Example 2.

[0085] Example 5

[0086] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the modified polyether amine used is obtained from Preparation Example 6.

[0087] Example 6

[0088] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the modified polyether amine used is obtained from Preparation Example 7.

[0089] Example 7

[0090] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the modified polyether amine used is obtained from Preparation Example 8.

[0091] Example 8

[0092] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the functional filler used is obtained from Preparation Example 3.

[0093] Example 9

[0094] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the functional filler is replaced by graphene with the same particle size.

[0095] Comparative Example 1

[0096] A two-component flexible epoxy modified carbon-based waterproof adhesive for exposed use and a preparation method thereof, the specific implementation manner of which is the same as that of Example 1, except that the modified polyether amine is replaced by polyether amine D400.

[0097] Performance test

[0098] The A component and the B component of the exposed two-component flexible epoxy-modified carbon-based waterproof adhesive obtained in the above Examples 1-9 and Comparative Example 1 were mixed in a mass ratio of 1:1, and then performance tests were conducted in combination with the standards JC / T2217-2014 and TCWA204-2021, wherein it was known from the tests that the epoxy-modified carbon-based waterproof adhesive coating of the present application Examples 1-3 had high impermeable pressure, high bonding strength, good elongation at break and tensile strength, and still had a high performance retention rate after artificial climate aging test, met the requirements of related waterproof indicators for exposure, and the specific test results are shown in Table 1:

[0099] Table 1

[0100]

[0101]

[0102] It can be known from the comparison of Example 4 and Example 1 that the change of the ratio of fluorosilicon-modified acrylic resin to graphene may cause the chain segment to wind and agglomerate, affecting the compatibility of the functional filler, and the flexibility, bonding strength and weather resistance change to different degrees.

[0103] It can be known from the comparison of Example 5 and Example 6 with Example 1 that when the addition amount of 1,1'-carbonyl diimidazole and the intermediate product is changed, the stability of the modified polyetheramine participating in curing may be affected to different degrees, so that the weather resistance decreases greatly; Example 6 may also be adversely affected by steric hindrance, the movement of the molecular chain is hindered, and the elongation at break and the tensile strength decrease.

[0104] It can be known from the comparison of Example 7 and Example 1 that when polyetheramine D400 is used to replace the polyetheramine of Preparation Example 3 in the same amount, the bonding and stability of the cured glue may be affected, the bonding strength after humid interface and immersion treatment decreases greatly, and the weather resistance also decreases.

[0105] It can be known from the comparison of Example 8 and Example 1 that when polyacrylic acid is used to replace the fluorosilicon-modified acrylic resin for graphene modification in the same amount, the weather resistance of the cured glue is greatly affected.

[0106] It can be known from the comparison of Example 9 and Example 1 that when unmodified graphene is used as a functional filler, the functionality of the functional filler decreases due to the insufficient performance of graphene in the system.

[0107] It can be known from the comparison of Comparative Example 1 and Example 1 that when polyetheramine D400 is used to replace the modified polyetheramine in the same amount, the crosslinking degree of the glue may change greatly, and the comprehensive performance of the cured glue decreases to different degrees.

[0108] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art, without departing from the technical solution of the present application, can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, without departing from the technical solution of the present application, shall still fall within the scope of the technical solution of the present application.

Claims

1. A two-component flexible epoxy-modified carbon-based waterproof adhesive for external use, characterized in that: The epoxy-modified carbon-based waterproof adhesive comprises component A and component B, wherein, based on 100 parts by weight, component A comprises the following raw materials in parts by weight: 55-65 parts of epoxy resin, 8-10 parts of glycidyl ether, 1-3 parts of aminosilane, and the balance is functional filler; component B comprises the following raw materials in parts by weight: 11.5-13.5 parts of complex amine curing agent, 14.5-16.5 parts of modified polyether amine, 14-16 parts of epoxy resin, 4-6 parts of monoepoxy glycidyl ether, 6-8 parts of benzyl alcohol, 1-3 parts of silane coupling agent, and the balance is silicon micropowder.

2. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 1, characterized in that: The epoxy resins are all E51 epoxy resins.

3. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 1, characterized in that: The glycidyl ether is polypropylene glycol diglycidyl ether.

4. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 1, characterized in that: The composite amine curing agent is a mixture of an alicyclic amine curing agent and a fatty amine curing agent.

5. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 1, characterized in that: The preparation steps of the functional filler are as follows: Graphene is dispersed in a mixed solvent of water and ethanol, and then fluorosilicone-modified acrylic resin is added. The mixture is stirred at 25-30°C for 1-3 hours until fully mixed. The stirring is maintained and the temperature is continuously raised to 100-105°C. The mixture is reacted for 2-3 hours. The precipitate is collected, washed, and dried to obtain a functional filler.

6. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 5, characterized in that: The mass ratio of the graphene to the fluorosilicone modified acrylic resin is 1:(0.8-1).

7. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 1, characterized in that: The preparation steps of the modified polyetheramine are as follows: (1) Add 4-aminomethylpiperidine and 1,1'-carbonyldiimidazole to dimethyl sulfoxide, heat to 80-85°C, stir and react for 2-3 hours, cool, filter, wash and dry to obtain an intermediate product; (2) The intermediate product of step (1) and polyetheramine are mixed, the temperature is raised to 40-50° C. and the mixture is reacted for 13-15 hours, and the mixture is purified, washed and dried to obtain the modified polyetheramine.

8. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 7, characterized in that: The mass ratio of 4-aminomethylpiperidine to 1,1'-carbonyldiimidazole in step (1) is 1:(2.8-3.4).

9. The two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to claim 7, characterized in that: The mass ratio of the intermediate product to the polyetheramine in the step (2) is (0.03-0.06):

1.

10. A method for preparing the two-component flexible epoxy-modified carbon-based waterproof adhesive for external use according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: Mix the epoxy resin, glycidyl ether and aminosilane in component A, stir at 70-80°C for 3-4 hours, then add the functional filler and stir for 30-40 minutes to obtain component A; S2: Mix the complex amine curing agent, modified polyetheramine, epoxy resin, monoepoxy glycidyl ether, benzyl alcohol and silane coupling agent in component B, stir at 80-90°C for 3-4 hours, then add silicon micropowder and stir for 30-40 minutes to obtain component B; When in use, component A of step S1 and component B of step S2 are mixed and used.

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