Preparation method of epoxy adhesive for concrete tower of wind generating set

Abstract

The invention discloses a preparation method of an epoxy adhesive for a concrete tower of a wind generating set, and relates to the technical field of epoxy adhesives. The heat-resistant aromatic heterocyclic modified epoxy resin is used as a main base material, so that the hydrophobicity and the thermal stability are enhanced, and the damp-heat aging resistance and the mechanical property are improved. Surface alloy coating rubber particles are adopted as auxiliary materials, and alloy is melted to wrap the rubber particles by prolonging the spraying distance. The rubber particles are used as an alloy carrier, improve the dispersion effect, are compatible with an epoxy resin system, participate in a cross-linking reaction, enhance the elasticity of rubber and the adhesion of epoxy resin, form a multi-cross-linked network structure, and ensure that the epoxy adhesive has good anti-aging and erosion-resistant properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy adhesives, in particular to a preparation method of an epoxy adhesive for a wind turbine generator concrete tower. BACKGROUND

[0002] With the rapid development of wind power technology, the single machine capacity of wind turbine generators is increasing, and the height of the tower is also rising. In order to reduce the transportation and hoisting cost and difficulty, and meet the demand of higher tower structure, the application of concrete tower drum in the wind power industry is becoming more and more widely. In the production and use of concrete tower drum (such as precast section connection, crack repair, bolt fixation, etc.), high performance epoxy adhesive plays a crucial role, and its performance is directly related to the overall structural strength, durability and operation safety of the tower.

[0003] The epoxy adhesive is used in the installation of the concrete tower, and the concrete tower is composed of several concrete tower sections. Each section of the concrete tower is spliced by several pipe pieces, the side vertical surface of the pipe piece is coated with adhesive, and the pipe pieces are connected into a whole ring by the adhesive and arc bolts. The top surface of each section of the concrete tower is coated with adhesive, and the adjacent two sections of the concrete tower are connected by the adhesive and steel strands.

[0004] The operating environment of the wind turbine generator is usually extremely harsh, especially for the wind turbine tower built on the sea, high altitude or gobi desert area. These environments are long-term exposed to high temperature, low temperature, large alternating cycle, continuous strong ultraviolet radiation, high humidity, salt spray corrosion and wind sand impact, etc. This puts forward very high requirements for the tower service materials, especially the epoxy adhesive used in the key bearing or sealing connection position.

[0005] At present, the epoxy adhesive commonly used in the field of civil construction or composite materials has significant deficiencies in dealing with the above extreme working conditions. Ordinary epoxy resin is prone to hydrolysis, oxidation and other chemical aging in a humid and hot environment, resulting in rising hardness, declining toughness, and decaying bonding strength. Its thermal stability and hydrophobicity are limited, and the performance deteriorates seriously after long-term exposure. Under the stress of complex humid and hot environment, the interface between the adhesive body and the concrete base or the adherend material is easy to become a weak link, causing water penetration along the interface or adhesive self-degradation, leading to debonding failure. The compatibility of the commonly used toughening agent with the epoxy resin is limited, and the dispersion uniformity is poor, which is easy to migrate or aggregate. The traditional premixed method cannot guarantee the uniform distribution of the toughening agent in the whole adhesive layer. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of an epoxy adhesive for a wind turbine generator concrete tower to solve the problems in the prior art.

[0007] In order to solve the above technical problems, the present application provides the following technical solutions: an epoxy adhesive for a concrete tower of a wind turbine generator system, which is prepared by mixing and adjusting A component and B component, wherein the mixing ratio of the A component and the B component is 3:1 by weight during construction, and the main components and the weight ratio of each component of the A component are as follows:

[0008]

[0009] The components and the weight ratio of each component of the B component are as follows:

[0010]

[0011] Further, the liquid bisphenol A epoxy resin has an epoxy equivalent weight of 196-227.

[0012] Further, the preparation method of the modified epoxy resin is as follows: the E44 epoxy resin and a solvent are mixed, nitrogen protection is performed, the temperature is increased to 80 DEG C, the epoxy resin is dissolved by stirring, a modifier is added, the viscosity is increased after reaction for 10-13 hours, the solvent is removed, and washing and drying are performed.

[0013] Further, the solvent is a mixture of ethylene glycol monobutyl ether and ethanol in a volume ratio of 2:1.

[0014] Further, the mass ratio of the modifier and the epoxy resin is 0.5-1.1:1.

[0015] Further, the preparation method of the modifier is as follows: 10 mmol of 5-amino-2-methylquinoline, 12 mmol of 4-allylbenzaldehyde, 15 mL of glacial acetic acid and 1 mmol of concentrated sulfuric acid are added, reflux reaction is performed at 135 DEG C for 8 hours, the temperature is then cooled to room temperature, 60 mL of water is poured in, extraction, standing, separation, drying, and removal of ethyl acetate under reduced pressure are performed to obtain the modifier.

[0016] Further, the preparation method of the modified rubber is as follows: the vinyl silicone rubber particles are taken, two nozzles are arranged at a vertical distance of 20 cm from the vinyl silicone rubber particles, the two nozzles form an included angle of 15-85 DEG, one nozzle sprays a low-melting-point alloy powder flow, and the other nozzle sprays high-temperature argon, the temperature is 130-180 DEG C, high-temperature argon is sprayed first for 30 seconds, then the low-melting-point alloy powder and the high-temperature argon are sprayed simultaneously for 1-10 minutes, and then the modified rubber is obtained by freezing at-18 DEG C for 30 minutes.

[0017] Further, the vinyl silicone rubber is methyl vinyl silicone rubber, and the mass percentage content of the vinyl chain segment is 5%-15%.

[0018] Further, the preparation method of the low-melting alloy used in the low-melting alloy powder flow is as follows: mixing bismuth powder, indium powder and tin powder according to the mass ratio of 32-50:10-20:15-32, mechanically grinding at 500 rpm for 20-40 h to obtain the low-melting alloy.

[0019] Further, the preparation method of the A component is as follows: mixing modified epoxy resin, ethanol and dimethylbenzene according to the mass ratio of 20-30:10-20:5-10, heating by oil bath, starting stirring when the epoxy resin is fully dissolved, slowly adding the initiator and allyl diethyl phosphate, gradually heating after all the addition, adding modified rubber, continuing stirring reaction, and performing the whole process in a closed reflux condensation system to avoid solvent evaporation; after the reaction is completed, cooling, then adding liquid bisphenol A epoxy resin, montmorillonite, silica fiber and silane coupling agent, and fully mixing to obtain the component A.

[0020] Further, the silica fiber is prepared according to the method of CN200410015679.8, and the length is 150 mu m.

[0021] Further, the silane coupling agent is at least one of kH-560, KH-570, A151, A171 or A172.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] (1) The present application uses heat-resistant aromatic heterocycle modified epoxy resin as the main base material of the epoxy adhesive, and the introduction of the heat-resistant aromatic heterocycle structure in the modified epoxy resin can improve the hydrophobic effect and thermal stability effect of the modified epoxy resin, and further improve the wet heat aging performance and mechanical properties of the epoxy adhesive.

[0024] (2) The present application adopts rubber particles coated with an alloy coating as one of the adhesives, and the alloy coating is composed of low-melting-point alloy powder. In the spraying process, the spraying distance is appropriately prolonged to promote the combination of the powder flow and the high-temperature gas flow, so as to ensure that the low-melting-point alloy can be melted into droplets and then wrapped on the surface of the rubber particles. The present application adopts rubber particles as an alloy carrier to improve the dispersion effect of the alloy in the epoxy adhesive. In the use process of the epoxy adhesive, since the pre-crosslinking temperature is higher than the temperature of the low-melting-point alloy, the alloy on the surface of the rubber particles is melted, is easy to be compatible with the epoxy resin system, and simultaneously exposes the vinyl silicone rubber to participate in the polymerization and crosslinking reaction of the double bond of the modified epoxy resin and the allyl diethyl phosphate, so as to realize the forced mutual solubility and the synergistic effect, organically combine the high elasticity of the rubber with the adhesion of the epoxy resin and the allyl diethyl phosphate, complement and strengthen each other to achieve the toughening and reinforcing effect, and the melted low-melting-point alloy is uniformly dispersed in the crosslinking network system and can form a multiple crosslinking network structure with other inorganic fillers, so as to ensure that the epoxy adhesive has good anti-aging performance and corrosion resistance.

[0025] (3) The prepared epoxy adhesive of the present application has a use temperature of 25-40℃, and can be cured at room temperature and can also adapt to different operating environment temperatures. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0027] Embodiment 1

[0028] An epoxy adhesive is prepared by mixing and adjusting A component and B component, and the mixing ratio of A component and B component is 3:1 by weight during construction, wherein,

[0029] The main components contained in the A component and the weight ratio of each component are as follows:

[0030]

[0031] The preparation method of the A component is as follows:

[0032] (1) 10 mmol of 5-amino-2-methylquinoline, 12 mmol of 4-allylbenzaldehyde, 15 mL of glacial acetic acid and 1 mmol of concentrated sulfuric acid are added, and refluxed at 135℃ for 8h, and then cooled to room temperature, poured into 60 mL of water, extracted with 20 mL of ethyl acetate for three times, and then placed, separated, and the upper organic phase was dried with anhydrous sodium sulfate for 2h, and then the ethyl acetate was evaporated under reduced pressure to obtain a modifier;

[0033] (2) E44 epoxy resin, solvent mixture, the volume ratio of ethylene glycol monobutyl ether and ethanol in the solvent is 2:1, nitrogen protection, heating to 80℃, stirring to dissolve the epoxy resin to obtain an epoxy resin solution with a mass concentration of 45%, then adding a modifier, the mass ratio of the modifier to the epoxy resin is 0.5:1, reacting for 10 hours, then removing the solvent, washing with ethanol for 6 times, and drying at 55℃ for 48 hours to obtain a modified epoxy resin;

[0034] (3) mixing bismuth metal powder with a particle size of 50 μm, indium powder with a particle size of 50 μm, and tin powder with a particle size of 50 μm at a mass ratio of 32:10:15, mechanically grinding at 500 rpm for 20 hours to obtain a low-melting-point alloy;

[0035] (4) taking vinyl silicone rubber particles with an average particle size of 0.1 mm, setting two nozzles at a vertical distance of 20 cm from the vinyl silicone rubber particles, the two nozzles being at an angle of 45°, one nozzle spraying a low-melting-point alloy powder flow at a flow rate of 5 g / min, and the other nozzle spraying high-temperature argon at a flow rate of 3 m 3 / min, a temperature of 130℃, and a pressure of 0.6 MPa, first spraying high-temperature argon for 30 seconds, then spraying the low-melting-point alloy powder at the same time for 3 minutes, and then freezing at -18℃ for 30 minutes to obtain a modified rubber;

[0036] (5) mixing the modified epoxy resin, ethanol, and xylene at a mass ratio of 20:10:5, heating to 113℃ in an oil bath, and then slowly adding dicumyl peroxide and allyl diethyl phosphate under stirring at a stirring speed of 20 rpm within 106 minutes after the epoxy resin is fully dissolved, gradually increasing the temperature to 124℃, adding the modified rubber, and continuing to stir for 238 minutes, the whole process being carried out in a closed reflux condensation system to avoid solvent evaporation; after the reaction is completed, cooling to 54℃, and then adding liquid bisphenol A epoxy resin, montmorillonite, silica fiber, and silane coupling agent, and fully mixing to obtain component A.

[0037] The components contained in component B and the weight ratio of each component are as follows:

[0038]

[0039] Example 2

[0040] An epoxy adhesive is prepared by mixing component A and component B, and the mixing ratio of component A and component B is 3:1 by weight during construction, wherein,

[0041] The main components contained in component A and the weight ratio of each component are as follows:

[0042]

[0043] The preparation method of the A component is as follows:

[0044] (1) 10 mmol of 5-amino-2-methylquinoline, 12 mmol of 4-allylbenzaldehyde, 15 mL of glacial acetic acid and 1 mmol of concentrated sulfuric acid are added, and the reaction is refluxed at 135°C for 8 h, and then cooled to room temperature, poured into 60 mL of water, extracted with 20 mL of ethyl acetate three times, and then separated. The upper organic phase is dried with anhydrous sodium sulfate for 2 h, and then the ethyl acetate is evaporated under reduced pressure to obtain the modifier;

[0045] (2) The E44 epoxy resin and the solvent are mixed, the volume ratio of ethylene glycol monobutyl ether to ethanol in the solvent is 2:1, and the mixture is stirred and heated to 80°C under nitrogen protection until the epoxy resin is dissolved to obtain an epoxy resin solution with a mass concentration of 45%. Then, the modifier is added, and the mass ratio of the modifier to the epoxy resin is 0.65:1. After 10 h of reaction, the viscosity increases, the solvent is removed, and the mixture is washed with ethanol for 6 times and dried at 55°C for 48 h to obtain the modified epoxy resin;

[0046] (3) Metal bismuth powder with a particle size of 50 μm, indium powder with a particle size of 200 μm and tin powder with a particle size of 200 μm are mixed in a mass ratio of 36:12.5:19, and then mechanically ground at 500 rpm for 20 h to obtain a low-melting-point alloy;

[0047] (4) Vinyl silicone rubber particles with an average particle size of 0.1 mm are taken, two nozzles are arranged at a vertical distance of 20 cm from the vinyl silicone rubber particles, the two nozzles are arranged at an angle of 45°, one nozzle sprays a low-melting-point alloy powder flow at a flow rate of 5 g / min, and the other nozzle sprays high-temperature argon at a flow rate of 3 m 3 / min, a temperature of 130°C and a pressure of 0.6 MPa. First, high-temperature argon is sprayed for 30 s, and then the low-melting-point alloy powder and the high-temperature argon are sprayed simultaneously for 3 min. Then, the mixture is frozen at -18°C for 30 min to obtain the modified rubber;

[0048] (5) The modified epoxy resin, ethanol and dimethylbenzene are mixed in a mass ratio of 20:10:5, and then heated to 113°C in an oil bath. When the epoxy resin is fully dissolved, the stirring is started, and the stirring speed is 20 rpm. Peroxydiisopropylbenzene and allyl diethyl phosphate are slowly added within 106-109 min. After the addition is completed, the temperature is gradually increased to 124°C. The modified rubber is added, and the stirring is continued for 238 min. The whole reaction is carried out in a closed reflux condensation system to avoid solvent evaporation. After the reaction is completed, the temperature is decreased to 54°C, and then liquid bisphenol A epoxy resin, montmorillonite, silica fiber and silane coupling agent KH-570 are added and mixed to obtain the component A.

[0049] The components contained in the B component and the weight ratio of each component are as follows:

[0050]

[0051] Embodiment 3

[0052] An epoxy adhesive is prepared by mixing component A and component B, and the mixing ratio of component A and component B is 3:1 by weight during construction, wherein,

[0053] The main components contained in component A and the weight ratio of each component are as follows:

[0054]

[0055] The preparation method of the A component is as follows:

[0056] (1) 10 mmol of 5-amino-2-methylquinoline, 12 mmol of 4-allylbenzaldehyde, 15 mL of glacial acetic acid and 1 mmol of concentrated sulfuric acid are added, and refluxed at 135°C for 8h, and then cooled to room temperature, poured into 60 mL of water, extracted with 20 mL of ethyl acetate three times, and then separated, and the upper organic phase is dried with anhydrous sodium sulfate for 2h, and then the ethyl acetate is removed under reduced pressure to obtain a modifier;

[0057] (2) The E44 epoxy resin and the solvent are mixed, the volume ratio of ethylene glycol monobutyl ether and ethanol in the solvent is 2:1, nitrogen protection is carried out, the temperature is raised to 80°C, and the epoxy resin is dissolved by stirring to obtain an epoxy resin solution with a mass concentration of 45%, the modifier is added, the mass ratio of the modifier to the epoxy resin is 0.8:1, the reaction is carried out for 12h, the viscosity is increased, the solvent is removed, and the modified epoxy resin is obtained by washing with ethanol for 6 times and drying at 55°C for 48h;

[0058] (3) The low-melting-point alloy is obtained by mixing 40:15:19 of bismuth powder with a particle size of 120μm, indium powder with a particle size of 100μm and tin powder with a particle size of 50μm by mechanical grinding at 500rpm for 30h;

[0059] (4) The average particle size of the vinyl silicone rubber particles is 0.1mm, two nozzles are set at a vertical distance of 20cm from the vinyl silicone rubber particles, the two nozzles form an angle of 65°, one nozzle sprays a low-melting-point alloy powder flow with a flow rate of 8g / min, and the other nozzle sprays high-temperature argon with a flow rate of 2m 3 / min, the temperature is 130°C, the pressure is 0.6MPa, high-temperature argon is sprayed first for 30s, then the low-melting-point alloy powder is sprayed at the same time for 7min, and then the modified rubber is obtained by freezing at-18°C for 30min;

[0060] (5) mixing modified epoxy resin, ethanol, dimethylbenzene according to the mass ratio of 25:15:8, heating to 113℃ in oil bath, when the epoxy resin is dissolved sufficiently, starting stirring, the stirring speed is 30rpm, slowly adding dicumyl peroxide, allyl diethyl phosphate within 106min, after adding completely, gradually heating to 124℃, adding modified rubber, continuing stirring for 238min, the whole process is in a closed reflux condensation system to avoid solvent evaporation; after the reaction is completed, cooling to 54℃, then adding liquid bisphenol A epoxy resin, montmorillonite, silica fiber, silane coupling agent A151, mixing thoroughly, obtaining component A.

[0061] The components contained in the B component and the weight ratio of each component are:

[0062]

[0063] Example 4

[0064] An epoxy adhesive is prepared by mixing and adjusting the A component and the B component, and the mixing ratio of the A component and the B component is 3:1 by weight during construction, wherein,

[0065] The main components contained in the A component and the weight ratio of each component are:

[0066]

[0067]

[0068] The preparation method of the A component is:

[0069] (1) adding 10mmol 5-amino-2-methylquinoline, 12mmol 4-allylbenzaldehyde, 15mL glacial acetic acid and 1mmol concentrated sulfuric acid, refluxing at 135℃ for 8h, then cooling to room temperature, pouring into 60mL water, extracting with 20mL ethyl acetate for three times, standing, separating the upper organic phase, drying with anhydrous sodium sulfate for 2h, then evaporating the ethyl acetate under reduced pressure, obtaining the modifier;

[0070] (2) mixing E44 epoxy resin and solvent, the volume ratio of ethylene glycol monobutyl ether and ethanol in the solvent is 2:1, protecting with nitrogen, heating to 80℃, stirring to dissolve the epoxy resin, obtaining an epoxy resin solution with a mass concentration of 45%, adding the modifier, the mass ratio of the modifier and the epoxy resin is 0.95:1, after reacting for 10-13h, the viscosity increases, removing the solvent, washing with ethanol for 6 times, drying at 55℃ for 48h, obtaining the modified epoxy resin;

[0071] (3) Bismuth metal powder with particle size of 170 μm, indium powder with particle size of 100 μm, and tin powder with particle size of 200 μm are mixed in a mass ratio of 44:17.5:27, and mechanically ground at 500 rpm for 30 h to obtain a low-melting alloy;

[0072] (4) Vinyl silicone rubber particles with an average particle size of 0.1 mm are taken, two nozzles are arranged at a vertical distance of 20 cm from the vinyl silicone rubber particles, the two nozzles form an angle of 65°, one nozzle sprays a low-melting alloy powder flow at a flow rate of 10 g / min, and the other nozzle sprays high-temperature argon at a flow rate of 3 m 3 / min, the temperature is 150℃, the pressure is 1.2 MPa, high-temperature argon is sprayed for 30 s first, then the low-melting alloy powder is sprayed at the same time, the spraying time is 10 min, and then the modified rubber is obtained by freezing at -18℃ for 30 min;

[0073] (5) Modified epoxy resin, ethanol, and dimethylbenzene are mixed in a mass ratio of 30:20:10, and an oil bath is heated to 116℃, when the epoxy resin is fully dissolved, stirring is started, the stirring speed is 40 rpm, dicumyl peroxide and allyl diethyl phosphate are slowly added within 109 min, after the addition is completed, the temperature is gradually increased to 126℃, the modified rubber is added, and the stirring reaction is continued for 240 min, the whole process is carried out in a closed reflux condensation system to avoid solvent evaporation; after the reaction is completed, the temperature is lowered to 56℃, then liquid bisphenol A epoxy resin, montmorillonite, silica fiber, and silane coupling agent A171 are added, and fully mixed to obtain component A.

[0074] The components contained in component B and the weight ratio of each component are as follows:

[0075]

[0076] Example 5

[0077] An epoxy adhesive is prepared by mixing component A and component B, and the mixing ratio of component A and component B is 3:1 by weight during construction, wherein,

[0078] The main components contained in component A and the weight ratio of each component are as follows:

[0079]

[0080] The preparation method of the A component is as follows:

[0081] (1) add 10 mmol 5-amino-2-methylquinoline, 12 mmol 4-allylbenzaldehyde, 15 mL glacial acetic acid and 1 mmol concentrated sulfuric acid, reflux at 135°C for 8 h, then cool to room temperature, pour into 60 mL water, extract with 20 mL ethyl acetate three times, stand, separate, take the upper organic phase, dry with anhydrous sodium sulfate for 2 h, then evaporate the ethyl acetate under reduced pressure, to obtain the modifier;

[0082] (2) mix the E44 epoxy resin and solvent, the volume ratio of ethylene glycol monobutyl ether and ethanol in the solvent is 2:1, protect with nitrogen, heat to 80°C, stir to dissolve the epoxy resin to obtain an epoxy resin solution with a mass concentration of 45%, add the modifier, the mass ratio of the modifier to the epoxy resin is 1.1:1, after 13 h of reaction, the viscosity increases, remove the solvent, wash with ethanol 6 times, dry at 55°C for 48 h, to obtain the modified epoxy resin;

[0083] (3) mix the metal bismuth powder with a particle size of 200 μm, indium powder with a particle size of 50 μm and tin powder with a particle size of 50 μm according to a mass ratio of 50:20:32, mechanically grind at 500 rpm for 40 h, to obtain the low-melting-point alloy;

[0084] (4) take the vinyl silicone rubber particles with an average particle size of 0.1 mm, set two nozzles at a vertical distance of 20 cm from the vinyl silicone rubber particles, the two nozzles form an angle of 85°, one nozzle sprays a low-melting-point alloy powder flow with a flow rate of 10 g / min, and the other nozzle sprays high-temperature argon with a flow rate of 3 m 3 / min, a temperature of 180°C and a pressure of 1.2 MPa, first spray the high-temperature argon for 30 s, then spray the low-melting-point alloy powder at the same time, the spraying time is 3 min, then freeze at -18°C for 30 min to obtain the modified rubber;

[0085] (5) mix the modified epoxy resin, ethanol and dimethylbenzene according to a mass ratio of 30:20:10, heat to 116°C in an oil bath, when the epoxy resin is fully dissolved, start stirring, the stirring speed is 40 rpm, slowly add dicumyl peroxide and allyl diethyl phosphate within 109 min, after all are added, gradually heat to 126°C, add the modified rubber, continue to stir for 240 min, the whole process is carried out in a closed reflux condensation system to avoid solvent evaporation; after the reaction is completed, cool to 56°C, then add liquid bisphenol A epoxy resin, montmorillonite, silica fiber and silane coupling agent A172, mix well to obtain component A.

[0086] The components contained in component B and the weight ratio of each component are as follows:

[0087]

[0088] The performance of the above-mentioned 5 formula samples was detected according to T / CECS10080-2020 “Epoxy adhesive for prefabricated segment assembly” including compressive strength, moisture and heat aging resistance, and the compressive strength test results are as follows in Table 1:

[0089] Table 1 Compressive strength test results of examples

[0090]

[0091]

[0092] The moisture and heat aging detection conditions are as follows: the bonded test piece is placed in 85℃ water for 14 days, then taken out, and the shear strength is tested according to GB / T7124-2008, and the test results are as follows:

[0093] Table 2 Moisture and heat aging test results of examples

[0094]

[0095] Comparative example 1

[0096] The difference between comparative example 1 and example 5 is that E44 epoxy resin is used instead of modified epoxy resin, and the rest of the formula amount and preparation method are the same as example 5.

[0097] Comparative example 2

[0098] The difference between comparative example 2 and example 5 is that no modified epoxy resin is added, and the rest of the formula amount and preparation method are the same as example 5.

[0099] Comparative example 3

[0100] The difference between comparative example 3 and example 5 is that vinyl silicone rubber particles are used instead of modified rubber, and the rest of the formula amount and preparation method are the same as example 5.

[0101] Comparative example 4

[0102] The difference between comparative example 4 and example 5 is that low-melting-point alloy is used instead of modified rubber, and the rest of the formula amount and preparation method are the same as example 5.

[0103] Comparative example 5

[0104] The difference between comparative example 5 and example 5 is that no modified rubber is added, and the rest of the formula amount and preparation method are the same as example 5.

[0105] Comparative example 6

[0106] The difference between comparative example 6 and example 5 is that no allyl diethyl phosphate is added, and the rest of the formula amount and preparation method are the same as example 5.

[0107] Comparative example 7

[0108] Comparative Example 7 differs from Example 5 in that the preparation method of component A is that each component is directly mixed sufficiently, and the remaining formulation amount and preparation method are the same as those of Example 5.

[0109] The above-mentioned 7 formula samples were respectively subjected to performance detection including compressive strength and moisture heat aging resistance according to T / CECS 10080-2020 "Epoxy Adhesive for Prefabricated Segment Assembly".

[0110] Table 3: Compressive strength test results of examples

[0111]

[0112]

[0113] The moisture heat aging detection condition is that the adhesive test piece is placed in 85 DEG C water, taken out after 14 days, and the shear strength is tested according to GB / T7124-2008, and the detection results are as follows:

[0114] Table 4: Moisture heat aging test results of examples

[0115]

[0116] The application uses heat-resistant aromatic heterocycle modified epoxy resin as the main base material, enhances the hydrophobicity and thermal stability, and improves the moisture heat aging resistance and mechanical properties. Surface alloy coating rubber particles are used as auxiliary materials, and the alloy melting is wrapped around the rubber particles by extending the spraying distance. Rubber particles are used as alloy carriers to improve the dispersion effect, are compatible with the epoxy resin system, participate in crosslinking reaction, enhance the adhesion of rubber elasticity and epoxy resin, form a multiple crosslinking network structure, and ensure that the epoxy adhesive has good aging resistance and corrosion resistance.

[0117] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the examples should be regarded as exemplary and non-limiting in any respect, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application. Any mark in the claims should not be regarded as limiting the involved claims.

Claims

1. An epoxy adhesive for a concrete tower of a wind turbine generator set, prepared by mixing component A and component B, characterized in that: The main components of the A component and the weight balance of each component are as follows: 50-70 parts of liquid bisphenol A epoxy resin 30-50 parts of modified epoxy resin 10-30 parts of modified rubber 5-10 parts of allyl diethyl phosphate 0.5-1 part initiator 5-15 parts of montmorillonite Silane coupling agent 0.1-1 parts 5-15 parts of silica fiber; The components of component B and the weight balance of each component are as follows: 20-40 parts of curing agent 1-5 parts of accelerator 5-15 parts of montmorillonite Silane coupling agent 0.1-1 part.

2. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 1, characterized in that: The preparation method of the modified epoxy resin is as follows: E44 epoxy resin and solvent are mixed, nitrogen is passed through, the temperature is raised to 80° C., and the epoxy resin is dissolved after stirring, and the modifier is added. After reacting for 10 to 13 hours, the solvent is removed, and the mixture is washed and dried.

3. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 2, characterized in that: The solvent is a mixture of ethylene glycol monobutyl ether and ethanol in a volume ratio of 2:

1.

4. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 2, characterized in that: The mass ratio of the modifier to the epoxy resin is 0.5-1.1:

1.

5. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 2, characterized in that: The preparation method of the modifier comprises the following steps: adding 10 mmol of 5-amino-2-methylquinoline, 12 mmol of 4-allylbenzaldehyde, 15 mL of glacial acetic acid and 1 mmol of concentrated sulfuric acid, reacting under reflux at 135° C. for 8 hours, cooling to room temperature, pouring into 60 mL of water, extracting, standing, separating, drying, and evaporating ethyl acetate under reduced pressure to obtain the modifier.

6. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 1, characterized in that: The modified rubber is prepared by taking vinyl silicone rubber particles, setting up two nozzles at a vertical distance of 20 cm from the vinyl silicone rubber particles, with the two nozzles forming an angle of 15-85 degrees, one nozzle spraying a low-melting-point alloy powder flow, and the other nozzle spraying high-temperature argon gas at a temperature of 130-180°C, first spraying the high-temperature argon gas for 30 seconds, and then simultaneously spraying the low-melting-point alloy powder for a spraying time of 1-10 minutes, and then freezing at -18°C for 30 minutes to obtain the modified rubber.

7. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 6, characterized in that: The low melting point alloy used in the low melting point alloy powder flow is prepared by mixing metal bismuth powder, indium powder and tin powder in a mass ratio of 32-50:10-20:15-32, and mechanically grinding at 500 rpm for 20-40 hours to obtain the low melting point alloy.

8. The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 1, characterized in that: The preparation method of the component A is as follows: modified epoxy resin, ethanol, and xylene are mixed in a mass ratio of 20-30:10-20:5-10, heated in an oil bath, stirred when the epoxy resin is fully dissolved, and slowly added with initiator and allyl diethyl phosphate. After all are added, the temperature is gradually increased, the modified rubber is added, and the stirring reaction is continued. The entire reaction is carried out in a closed reflux condensation system to prevent solvent volatilization; after the reaction is completed, the temperature is lowered, and liquid bisphenol A epoxy resin, montmorillonite, silica fiber, and silane coupling agent are added, and the mixture is fully mixed to obtain component A. 9 . The epoxy adhesive for a concrete tower of a wind turbine generator set according to claim 1 , wherein the silane coupling agent is at least one of KH-560, KH-570, A151, A171 or A172.

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