Preparation method of high-temperature durable epoxy resin coating

Abstract

The application discloses a preparation method of high-temperature durable epoxy resin paint and relates to the technical field of epoxy resin paint.The application first prepares a novel epoxy resin by taking 1,3,5-tri(2-propynyl oxy) benzene, 3-azido butanol and glycidyl methacrylate as raw materials, the novel epoxy resin has multiple functional groups, can improve the crosslinking degree of the paint, the introduction of benzene rings and triazole structures can make the epoxy resin paint have high thermal stability, and can improve the heat resistance of the paint; secondly, 2-benzoyl-4,5-dichlorobenzoic acid is grafted onto calcium silicate, and then a novel hindered phenolic antioxidant is prepared by hydrolysis; the antioxidant is loaded on the calcium silicate, the stable loading platform can be provided for the antioxidant, the surface active groups can produce a synergistic effect with the antioxidant, the antioxidant performance is further improved, the anti-aging performance of the paint is improved, and the service life of the paint is prolonged. The high-temperature durable epoxy resin paint prepared by the application has the effects of high-temperature resistance and durability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin coating, in particular to a preparation method of high-temperature durable epoxy resin coating. BACKGROUND

[0002] In many industries such as petroleum, chemical industry, metallurgy, transportation, aerospace, electromechanical and weapons, equipment and structures often need to operate under high temperature conditions. Such an environment can reduce the performance of materials, and even cause accidents. High-temperature resistant coatings can effectively resist corrosion and wear caused by high temperature, thereby prolonging the service life of the protected object and reducing the need for maintenance and replacement.

[0003] Epoxy resin is widely used as an important adhesive, coating and resin matrix in composite materials. It has strong cohesion, excellent adhesion, low curing shrinkage, good electrical insulation properties, strong stability, and good resistance to chemicals. Ordinary epoxy curing materials can generally withstand temperatures of 80 to 100 degrees Celsius, while specially designed heat-resistant products can reach 200 degrees Celsius or higher. However, as the application range of epoxy resin coatings continues to expand, its original temperature resistance and durability are not enough to meet more stringent requirements, making it difficult for traditional coatings to fully meet current application needs. SUMMARY

[0004] The purpose of the present application is to provide a high-temperature durable epoxy resin coating to solve the problems in the prior art.

[0005] To solve the above technical problems, the present application provides the following technical scheme: a high-temperature durable epoxy resin coating, which is prepared from 1,3,5-tris(2-propynyl oxy) benzene, 3-azido butanol and glycidyl methacrylate as raw materials to prepare a new type of epoxy resin, and then adding a new type of hindered phenolic antioxidant.

[0006] Further, the new type of hindered phenolic antioxidant is prepared by first loading 2-benzoyl-4,5-dichlorobenzoic acid on calcium silicate.

[0007] Further, a preparation method of a high-temperature durable epoxy resin coating, comprising the following preparation steps:

[0008] (1) 1,3,5-tris(2-propynyl)phenol and 3-azidobutanol are mixed in a molar ratio of 1:1.2~1.5, dissolved in N,N-dimethylformamide in an amount of 4~6 times the mass of 1,3,5-tris(2-propynyl)phenol, stirred at 200~300 r / min for 10~15 min, 1,3,5-tris(2-propynyl)phenol ruthenium catalyst is added in an amount of 0.02~0.04 times the mass of 1,3,5-tris(2-propynyl)phenol, the oil bath is heated to 75~80℃, and the reaction is carried out for 5~8 h, then cooled to room temperature, 1,3,5-tris(2-propynyl)phenol chloroform is added in an amount of 3~5 times the mass of 1,3,5-tris(2-propynyl)phenol, after filtration, the filtrate is added dropwise into 1,3,5-tris(2-propynyl)phenol / n-hexane / chloroform mixture stirred at 800~1000 r / min, and the mixture is allowed to stand for 12 h, then the solid is filtered and dried in a vacuum drying oven at 40~45℃ until the weight is constant to obtain the triazole compound;

[0009] (2) The triazole compound is mixed with glycidyl methacrylate in a molar ratio of 1:3.0~3.3, stirred at 100~200 r / min for 15~20 min, and under the protection of argon, phosphazene base is added in an amount of 0.2~0.3 times the mass of the triazole compound, heated to 25~30℃, and reacted for 1.0~1.5 h to obtain a mixed solution, which is filtered through an alkaline aluminum oxide column, then precipitated by adding n-hexane in an amount of 6~8 times the mass of the mixed solution, the solid is filtered and dried in a vacuum drying oven at 40~45℃ until the weight is constant to obtain the novel epoxy resin;

[0010] (3) 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in ethanol in an amount of 3~5 times the mass of 2-benzoyl-4,5-dichlorobenzoic acid, activated nano calcium silicate is added in an amount of 1.1~1.7 times the mass of 2-benzoyl-4,5-dichlorobenzoic acid, stirred at 300~400 r / min for 10~15 min to obtain a mixture, p-toluenesulfonic acid is added in an amount of 0.05~0.1 times the mass of the mixture, ultrasonic treatment is carried out at 30~40 kHz for 80~100 min, heated to 78~79℃, and stirred at 700~800 r / min for 6~8 h to obtain the novel hindered phenolic antioxidant;

[0011] (4) The novel epoxy resin 100~110 parts, polyacrylate 14~16 parts, curing agent 20~40 parts, novel hindered phenolic antioxidant 5~10 parts, titanium white 0.3~0.7 parts, wetting dispersant 0.05~0.1 parts, defoaming agent 0.03~0.07 parts, and water 10~15 parts are mixed according to weight parts, stirred, filtered, and defoamed to obtain the high-temperature durable epoxy resin coating.

[0012] Further, the ruthenium catalyst in step (1) is RuH2(CO)(PPh3)3.

[0013] Further, the n-hexane / chloroform mixture in step (1) is prepared by mixing n-hexane and chloroform at a volume ratio of 10:1.

[0014] Further, in step (3), the activated nano calcium silicate is prepared by placing the nano calcium silicate in a 30-40wt% sodium hydroxide aqueous solution, ultrasonic dispersing at 30-40 kHz for 30-60 min, soaking for 6-8 h, adding hydrochloric acid dropwise until the pH is neutral, filtering to obtain the solid, washing with deionized water for 2-3 times, and drying at 80℃ for 6-8 h.

[0015] Further, the particle size of the nano calcium silicate is 80-100 nm.

[0016] Further, in step (4), the curing agent is hexamethylenetetramine and bismaleimide.

[0017] Further, in step (4), the wet dispersing agent is any one of BYK-220S or BYK-333.

[0018] Further, in step (4), the defoaming agent is any one of BYK-071 or BYK-054.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] The present application prepares a high-temperature durable epoxy resin coating, which effectively prolongs the service life on the basis of improving the high-temperature resistance of the epoxy resin coating.

[0021] First, a new type of epoxy resin is prepared by using 1,3,5-tris(2-propynyl)benzene, 3-azido butanol and glycidyl methacrylate as raw materials, 1,3,5-tris(2-propynyl)benzene and 3-azido butanol first undergo azide-alkyne cycloaddition to form complex triazole compounds, and then the complex triazole compounds and glycidyl methacrylate undergo addition reaction to obtain the new type of epoxy resin; the new type of epoxy resin has multiple functional groups, which can improve the crosslinking degree of the coating, enhance the mechanical properties of the coating, the introduction of benzene ring and triazole structure can make the epoxy resin coating have high thermal stability, improve the heat resistance of the coating, and the triazole structure can also effectively absorb ultraviolet rays, avoiding the direct damage of ultraviolet rays to the coating, effectively prolonging the service life and appearance quality of the coating.

[0022] Secondly, the active hydroxyl group on the surface of calcium silicate is used to react with 2-benzoyl-4,5-dichlorobenzoic acid, and 2-benzoyl-4,5-dichlorobenzoic acid is grafted onto the calcium silicate. The calcium silicate has good heat resistance, and can further improve the high temperature resistance of the epoxy resin coating when added into the epoxy resin coating. The antioxidant is loaded on the calcium silicate, which can provide a stable loading platform for the antioxidant. Through the synergistic effect of the active groups on the surface and the antioxidant, the antioxidant performance is further improved, and effective antioxidant protection can be provided in a wider temperature range, the anti-aging performance of the coating is improved, and the service life of the coating is prolonged. DETAILED DESCRIPTION

[0023] 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, not 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 scope of protection of the present application.

[0024] In order to more clearly illustrate the method provided by the present application, the following examples are used for detailed description. In the following examples, the test methods of various indexes of the high temperature durable epoxy resin coating prepared are as follows:

[0025] High temperature resistance: the same mass of the high temperature durable epoxy resin coating prepared in the examples and the comparative examples is poured into a mold, and heat curing is carried out at 80℃ / 1h, 100℃ / 3h and 140℃ / 2h to obtain an epoxy resin film. The epoxy resin film is heated to 400℃ in a muffle furnace and kept for 5 hours. After cooling to room temperature, the surface of the sample is observed to see whether there is cracking or peeling.

[0026] Durable performance: the same mass of the high temperature durable epoxy resin coating prepared in the examples and the comparative examples is poured into a mold, and heat curing is carried out at 80℃ / 1h, 100℃ / 3h and 140℃ / 2h to obtain an epoxy resin film. The epoxy resin film is subjected to high temperature sweat corrosion for 16 hours, strong acid corrosion for 6 hours, strong alkali corrosion for 12 hours and high intensity ultraviolet radiation for 100 hours. After that, the surface of the sample is observed to see whether there is cracking or peeling.

[0027] Adhesion: the same mass of the high temperature durable epoxy resin coating prepared in the examples and the comparative examples is poured into a mold, and heat curing is carried out at 80℃ / 1h, 100℃ / 3h and 140℃ / 2h to obtain an epoxy resin film. The adhesion of the epoxy resin film is tested according to the test standard of GB / T5210-2006 "Color paint and varnish, pull-off method for adhesion test".

[0028] Example 1

[0029] A preparation method of a high-temperature durable epoxy resin coating, comprising the following preparation steps:

[0030] (1) 1,3,5-tris(2-propynyl)benzene and 3-azido butanol are mixed in a molar ratio of 1:1.2, dissolved in N,N-dimethylformamide with a mass of 4 times that of 1,3,5-tris(2-propynyl), stirred at 200 r / min for 10 min, 1,3,5-tris(2-propynyl)benzene is added with a mass of 0.02 times that of RuH2(CO)(PPh3)3 ruthenium catalyst, the oil bath is warmed to 75°C, and the reaction is carried out for 5 h, then cooled to room temperature, 1,3,5-tris(2-propynyl)benzene is added with a mass of 3 times that of chloroform, after filtration, the filtrate is added dropwise into 1,3,5-tris(2-propynyl) with a mass of 10 times that of the mixture of n-hexane / chloroform mixed in a volume ratio of 10:1 stirred at 800 r / min, and then left to stand for 12 h, the solid is filtered and dried in a vacuum drying oven at 40°C until the weight is constant to obtain a triazole compound;

[0031] (2) The triazole compound is mixed with glycidyl methacrylate in a molar ratio of 1:3.0, stirred at 100 r / min for 15 min, 0.2 times the amount of phosphazene base of the triazole compound is added under the protection of argon, warmed to 25°C, and reacted for 1.0 h to obtain a mixed solution, the mixed solution is filtered through an alkaline aluminum oxide column, then added into n-hexane with a mass of 6 times that of the mixed solution for precipitation, the solid is filtered and dried in a vacuum drying oven at 40°C until the weight is constant to obtain a novel epoxy resin;

[0032] (3) The nano calcium silicate with a particle size of 80 nm is placed in a 30 wt% sodium hydroxide aqueous solution, ultrasonically dispersed at 30 kHz for 30 min, soaked for 6 h, and hydrochloric acid is added dropwise until the pH is neutral, then the solid is filtered, washed with deionized water for 2 times, and dried at 80°C for 6 h to obtain activated nano calcium silicate;

[0033] (4) 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in an ethanol solution with a mass of 3 times that of the 2-benzoyl-4,5-dichlorobenzoic acid, 1.1 times the mass of the activated nano calcium silicate of the 2-benzoyl-4,5-dichlorobenzoic acid is added, stirred at 300 r / min for 10 min to obtain a mixture, 0.05 times the mass of the p-methylbenzenesulfonic acid of the mixture is added, ultrasonically treated at 30 kHz for 80 min, warmed to 78°C, and stirred at 700 r / min for 6 h, then filtered to obtain a novel hindered phenolic antioxidant;

[0034] (5) The novel epoxy resin 100 parts, polyacrylate 14 parts, hexamethylenetetramine 20 parts, novel hindered phenolic antioxidant 5 parts, titanium white 0.3 parts, BYK-220S wetting dispersant 0.05 parts, BYK-054 defoaming agent 0.03 parts, and water 10 parts are mixed according to weight parts, stirred, filtered, and defoamed to obtain a high-temperature durable epoxy resin coating.

[0035] Example 2

[0036] A preparation method of a high-temperature durable epoxy resin coating, comprising the following preparation steps:

[0037] (1) 1,3,5-tris(2-propynyl)benzene and 3-azido butanol are mixed at a molar ratio of 1:1.3, dissolved in N,N-dimethylformamide with a mass of 5 times that of 1,3,5-tris(2-propynyl), stirred at 250 r / min for 13 min, 1,3,5-tris(2-propynyl)benzene is added with a mass of 0.03 times that of RuH2(CO)(PPh3)3 ruthenium catalyst, the oil bath is heated to 76°C, and the reaction is carried out for 6 h, then cooled to room temperature, 1,3,5-tris(2-propynyl)benzene is added with a mass of 4 times that of chloroform, after filtration, the filtrate is added dropwise into 1,3,5-tris(2-propynyl) with a mass of 12 times that of a mixture of n-hexane / chloroform mixed at a volume ratio of 10:1 stirred at 900 r / min, stand for 12 h, filter the solid, and dry in a vacuum drying oven at 43°C until constant weight to obtain a triazole compound;

[0038] (2) The triazole compound is mixed with glycidyl methacrylate at a molar ratio of 1:3.2, stirred at 150 r / min for 17 min, 0.2 times the amount of phosphazene base of the triazole compound is added under the protection of argon, heated to 27°C, and reacted for 1.3 h to obtain a mixed solution, the mixed solution is filtered through an alkaline aluminum oxide column, then the mixed solution is added into n-hexane with a mass of 7 times that of the mixed solution, precipitated, filtered to obtain the solid, and dried in a vacuum drying oven at 43°C until constant weight to obtain a novel epoxy resin;

[0039] (3) The nano calcium silicate with a particle size of 90 nm is placed in a 35 wt% sodium hydroxide aqueous solution, dispersed by ultrasonic waves at 35 kHz for 45 min, soaked for 7 h, and hydrochloric acid is added dropwise until the pH is neutral, then the solid is filtered, washed with deionized water for 3 times, and dried at 80°C for 7 h to obtain activated nano calcium silicate;

[0040] (4) 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in an ethanol solution with a mass of 4 times that of 2-benzoyl-4,5-dichlorobenzoic acid, 1.4 times the activated nano calcium silicate of 2-benzoyl-4,5-dichlorobenzoic acid is added, stirred at 350 r / min for 13 min to obtain a mixture, 0.07 times p-toluenesulfonic acid of the mixture is added, ultrasonic waves are applied at 35 kHz for 90 min, heated to 79°C, and stirred at 750 r / min for 7 h, then filtered to obtain a novel hindered phenolic antioxidant;

[0041] (5) mixing by weight parts, mixing new type epoxy resin 105 parts, polyacrylate 15 parts, methenamine 30 parts, new type hindered phenolic antioxidant 8 parts, titanium white 0.5 parts, BYK-220S wetting dispersant 0.07 parts, BYK-054 defoaming agent 0.05 parts, water 13 parts, stirring, filtering, defoaming after getting high temperature durable type epoxy resin coating.

[0042] Example 3

[0043] A preparation method of a high temperature durable type epoxy resin coating, comprising the following preparation steps:

[0044] (1) 1,3,5-tri(2-propynyl) benzene and 3-azido butanol are mixed in a molar ratio of 1:1.5, dissolved in N,N-dimethylformamide with a mass of 6 times that of 1,3,5-tri(2-propynyl), stirred at 300 r / min for 15 min, 1,3,5-tri(2-propynyl) benzene is added with a mass of 0.04 times that of RuH2(CO)(PPh3)3 ruthenium catalyst, the oil bath is heated to 80℃, and the reaction is carried out for 8 h, then cooled to room temperature, 1,3,5-tri(2-propynyl) benzene is added with a mass of 5 times that of chloroform, after filtration, the filtrate is added dropwise into 1,3,5-tri(2-propynyl) with a mass of 13 times that of n-hexane / chloroform mixture mixed in a volume ratio of 10:1 stirred at 1000 r / min, stand for 12 h, filter the solid, and dry in a vacuum drying oven at 45℃ until constant weight to obtain a triazole compound;

[0045] (2) the triazole compound is mixed with glycidyl methacrylate in a molar ratio of 1:3.3, stirred at 200 r / min for 20 min, 0.3 times the amount of phosphazene base of the triazole compound is added under the protection of argon, heated to 30℃, and reacted for 1.5 h to obtain a mixed solution, the mixed solution is filtered through an alkaline aluminum oxide column, then 8 times the mass of n-hexane is added to the mixed solution to precipitate, the solid is filtered, and dried in a vacuum drying oven at 45℃ until constant weight to obtain a new type epoxy resin;

[0046] (3) the nano calcium silicate with a particle size of 100 nm is placed in a 40wt% sodium hydroxide aqueous solution, ultrasonically dispersed at 40 kHz for 60 min, soaked for 8 h, and hydrochloric acid is added dropwise until the pH is neutral, the solid is filtered, washed with deionized water for 3 times, and dried at 80℃ for 8 h to obtain activated nano calcium silicate;

[0047] (4) 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in 5 times of ethanol solution by mass, 1.7 times of activated nano calcium silicate of 2-benzoyl-4,5-dichlorobenzoic acid by mass is added, stirring at 400 r / min for 15 min to obtain a mixture, 0.1 times of p-methylbenzenesulfonic acid of the mixture by mass is added, ultrasonic treatment at 40 kHz for 100 min, the temperature is raised to 79℃, stirring at 800 r / min for 8 h, and then filtering to obtain a new hindered phenolic antioxidant;

[0048] (5) mixing by weight parts, mixing 110 parts of new epoxy resin, 16 parts of polyacrylate, 40 parts of hexamethylenetetramine, 10 parts of new hindered phenolic antioxidant, 0.7 parts of titanium white, 0.1 parts of BYK-220S wetting dispersant, 0.07 parts of BYK-054 defoaming agent, and 15 parts of water, stirring, filtering, and defoaming to obtain a high-temperature durable epoxy resin coating.

[0049] Comparative Example 1

[0050] Comparative Example 1 is different from Example 2 in that there is no step (1), and step (2) is changed to: mixing 3-azidobutanol and glycidyl methacrylate at a molar ratio of 1:1.2, stirring at 150 r / min for 17 min, adding 0.2 times of phosphazene base of triazole compound by mass under the protection of argon, raising the temperature to 27℃, and reacting for 1.3 h to obtain a mixed solution. The mixed solution is filtered through an alkaline aluminum oxide column, then precipitated by adding 7 times of n-hexane of the mixed solution by mass, filtered to obtain a solid, and dried in a vacuum drying oven at 43℃ until constant weight to obtain a new epoxy resin. The remaining steps are the same as those of Example 2.

[0051] Comparative Example 2

[0052] Comparative Example 2 is different from Example 2 in that there is no step (1) and (2), and step (5) is changed to: mixing by weight parts, mixing 105 parts of glycidyl methacrylate, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of new hindered phenolic antioxidant, 0.5 parts of titanium white, 0.07 parts of BYK-220S wetting dispersant, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water, stirring, filtering, and defoaming to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those of Example 2.

[0053] Comparative Example 3

[0054] The difference between Comparative Example 3 and Example 2 is that step (3) is not included, and step (4) is changed to: 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in an ethanol solution with a mass of 4 times, 2-benzoyl-4,5-dichlorobenzoic acid is added with a mass of 1.4 times of nano calcium silicate, stirring at 350 r / min for 13 min to obtain a mixture, 0.07 times of p-toluenesulfonic acid is added to the mixture, ultrasonic treatment is performed at 35 kHz for 90 min, the temperature is increased to 79℃, and stirring is performed at 750 r / min for 7 h, and a new hindered phenolic antioxidant is obtained by filtration; the remaining steps are the same as those in Example 2.

[0055] Comparative Example 4

[0056] The difference between Comparative Example 4 and Example 2 is that steps (3) and (4) are not included, and step (5) is changed to: mixing by weight parts, mixing 105 parts of a new epoxy resin, 15 parts of a polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of nano calcium silicate, 0.5 parts of titanium white, 0.07 parts of BYK-220S wetting dispersant, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water, stirring, filtering, and defoaming to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those in Example 2.

[0057] Comparative Example 5

[0058] The difference between Comparative Example 5 and Example 2 is that steps (3) and (4) are not included, and step (5) is changed to: mixing by weight parts, mixing 105 parts of a new epoxy resin, 15 parts of a polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of 2-benzoyl-4,5-dichlorobenzoic acid, 0.5 parts of titanium white, 0.07 parts of BYK-220S wetting dispersant, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water, stirring, filtering, and defoaming to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those in Example 2.

[0059] Effect Example

[0060] The performance analysis results of the high-temperature durable epoxy resin coatings of Examples 1 to 3 and Comparative Examples 1 to 4 of the present application are shown in Table 1 below.

[0061] Table 1

[0062]

[0063] From the experimental data comparison of the example 2 and the comparative examples 1 and 2, it can be found that the novel epoxy resin is prepared by taking 1,3,5-tris(2-propynoxy)benzene, 3-azido butanol and glycidyl methacrylate as raw materials, 1,3,5-tris(2-propynoxy)benzene and 3-azido butanol first undergo azide-alkyne cycloaddition to generate complex triazole compounds, and then the complex triazole compounds and glycidyl methacrylate undergo addition reaction to generate the novel epoxy resin; the novel epoxy resin has multiple functional groups, can improve the crosslinking degree of the coating, enhance the mechanical properties of the coating, the introduction of benzene ring and triazole structure can make the epoxy resin coating have high thermal stability, improve the heat resistance of the coating, meanwhile, the triazole structure can also effectively absorb ultraviolet rays, avoid the direct damage of the ultraviolet rays to the coating, effectively prolong the service life and appearance quality of the coating; from the experimental data comparison of the example 2 and the comparative example 3, it can be found that without surface activation of the nano calcium silicate, there is not enough site for 2-benzoyl-4,5-dichlorobenzoic acid to graft, thereby affecting the antioxidant performance and reducing the durability of the epoxy resin coating; from the experimental data comparison of the example 2 and the comparative examples 4 and 5, it can be found that the esterification reaction of the active hydroxyl group on the surface of the calcium silicate and the carboxyl group of 2-benzoyl-4,5-dichlorobenzoic acid is first utilized to graft 2-benzoyl-4,5-dichlorobenzoic acid onto the calcium silicate, and then the hydroxyl group is used to replace the chlorine atom to prepare the novel hindered phenolic antioxidant; the calcium silicate has good heat resistance, can further improve the high temperature resistance of the epoxy resin coating after being added into the epoxy resin coating, and the use of the calcium silicate to load the antioxidant can provide a stable loading platform for the antioxidant, produce synergistic effect with the antioxidant through the active groups on the surface, further improve the antioxidant performance, and also can provide effective antioxidant protection in a wider temperature range, improve the anti-aging performance of the coating and prolong the service life of the coating.

[0064] It is apparent for those skilled in the art that the present application is not limited to the details of the above-described exemplary embodiments, but can be implemented in other concrete forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all aspects as illustrative and not restrictive, and the scope of the present application is defined by the appended claims rather than the above description, and it is intended to embrace all changes falling within the meaning and range of equivalents of the claims. Any mark in the claims should not be considered as limiting the involved claims.

Claims

1. A method for producing a high-temperature durable epoxy resin coating, characterized by, The preparation steps include: (1) 1,3,5-tri(2-propynyl) benzene and 3-azido butanol are mixed at a molar ratio of 1:1.3, dissolved in N,N-dimethylformamide with a mass of 5 times that of 1,3,5-tri(2-propynyl) benzene, stirred at 250 r / min for 13 min, 1,3,5-tri(2-propynyl) benzene is added with a mass of 0.03 times that of RuH2(CO)(PPh3)3 ruthenium catalyst, the oil bath is warmed to 76℃, and the reaction is carried out for 6 h, then cooled to room temperature, 1,3,5-tri(2-propynyl) benzene is added with a mass of 4 times that of chloroform, after filtration, the filtrate is added dropwise into 1,3,5-tri(2-propynyl) benzene with a mass of 12 times mixed with n-hexane / chloroform at a volume ratio of 10:1 stirred at 900 r / min, and then left to stand for 12 h, the solid is filtered and dried in a vacuum drying oven at 43℃ until the weight is constant to obtain a triazole compound; (2) The triazole compound is mixed with glycidyl methacrylate at a molar ratio of 1:3.2, stirred at 150 r / min for 17 min, 0.2 times the amount of phosphazene base is added under the protection of argon, the temperature is raised to 27℃, and the reaction is carried out for 1.3 h to obtain a mixed solution, the mixed solution is filtered through an alkaline aluminum oxide column, then 7 times the mass of n-hexane is added to the mixed solution to precipitate, the solid is filtered and dried in a vacuum drying oven at 43℃ until the weight is constant to obtain a novel epoxy resin; (3) The particle size of the nano calcium silicate is 90 nm, which is placed in a 35 wt% sodium hydroxide aqueous solution, and is dispersed by ultrasonic wave at 35 kHz for 45 min, soaked for 7 h, and then hydrochloric acid is added dropwise until the pH is neutral, the solid is filtered, washed with deionized water for 3 times, and dried at 80℃ for 7 h to obtain activated nano calcium silicate; (4) 2-benzoyl-4,5-dichlorobenzoic acid is dissolved in a solution with a mass of 4 times that of ethanol, 1.4 times the mass of activated nano calcium silicate is added, stirred at 350 r / min for 13 min to obtain a mixture, 0.07 times the mass of p-toluenesulfonic acid is added, ultrasonic wave is applied at 35 kHz for 90 min, the temperature is raised to 79℃, and stirring is carried out at 750 r / min for 7 h, and then filtration is performed to obtain a novel hindered phenolic antioxidant; (5) The novel epoxy resin 105 parts, polyacrylate 15 parts, hexamethylenetetramine 30 parts, novel hindered phenolic antioxidant 8 parts, titanium white 0.5 parts, BYK-220S wetting dispersant 0.07 parts, BYK-054 defoaming agent 0.05 parts, and water 13 parts are mixed according to weight parts, stirred, filtered, and defoamed to obtain a high-temperature durable epoxy resin coating.

Images