A high-temperature durable epoxy resin coating and preparation method thereof

Abstract

The present invention discloses a kind of high temperature durable type epoxy resin coating and preparation method thereof, relate to the technical field of epoxy resin coating.The present invention first prepares novel epoxy resin with 1,3,5-tris (2-propynyloxy) benzene, 3-azidobutanol and glycidyl methacrylate as raw materials, novel epoxy resin has multiple functional groups, can improve the crosslinking degree of coating, the introduction of benzene ring and triazole structure can make epoxy resin coating have higher thermal stability, improve the heat resistance of coating;Secondly, 2-benzoyl-4,5-dichlorobenzoic acid is grafted onto calcium silicate, and then hydrolyzed to prepare novel hindered phenol antioxidant;Calcium silicate is used to load antioxidant, stable load platform can be provided for antioxidant, synergistic effect is produced by the active group on the surface and antioxidant, further improves antioxidant performance, improves the anti-aging performance of coating, extends the service life of coating.The high temperature durable type epoxy resin coating prepared by the present invention has high temperature resistant, durable effect.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin coatings, in particular to a high-temperature durable epoxy resin coating and a preparation method thereof. Background Art

[0002] In industries such as petroleum, chemical engineering, metallurgy, transportation, aerospace, electromechanical engineering, and weapons, equipment and structures often operate under high temperatures. Such environments can degrade material performance and even lead to accidents. High-temperature-resistant coatings effectively resist corrosion and wear caused by high temperatures, thereby extending the service life of the protected objects and reducing the need for repairs and replacements.

[0003] Epoxy resin is a key resin matrix in adhesives, coatings, and composite materials, enjoying widespread application. It exhibits strong cohesion, excellent adhesion, low cure shrinkage, good electrical insulation, robust stability, and excellent chemical resistance. Conventional epoxy curing compounds can typically withstand temperatures between 80°C and 100°C, while specially designed heat-resistant versions can reach 200°C or higher. However, as the scope of epoxy resin coatings continues to expand, their inherent heat resistance and durability are no longer sufficient to meet increasingly stringent requirements, making it difficult for traditional coatings to fully meet current application demands. Summary of the Invention

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

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a high-temperature durable epoxy resin coating, wherein the high-temperature durable epoxy resin coating is prepared by using 1,3,5-tris(2-propynyloxy)benzene, 3-azidobutanol and glycidyl methacrylate as raw materials to prepare a new epoxy resin, and then adding a new hindered phenol antioxidant.

[0006] Furthermore, the novel hindered phenol antioxidant is prepared by firstly using calcium silicate to load 2-benzoyl-4,5-dichlorobenzoic acid.

[0007] Furthermore, a method for preparing a high-temperature durable epoxy resin coating comprises the following preparation steps:

[0008] (1) 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol were mixed at a molar ratio of 1:1.2-1.5, dissolved in N,N-dimethylformamide (4-6 times the mass of 1,3,5-tris(2-propynyloxy)), stirred at 200-300 r / min for 10-15 min, added with ruthenium catalyst (0.02-0.04 times the mass of 1,3,5-tris(2-propynyloxy)benzene), and heated in an oil bath to 7 5-80°C, react for 5-8 hours, cool to room temperature, add chloroform 3-5 times the mass of 1,3,5-tris(2-propynyloxy)benzene, filter, and drip the filtrate dropwise into a n-hexane / chloroform mixture 10-13 times the mass of 1,3,5-tris(2-propynyloxy)benzene stirred at 800-1000 r / min, let stand for 12 hours, filter and obtain the solid, and dry in a vacuum drying oven at 40-45°C to constant weight to obtain the triazole compound;

[0009] (2) a triazole compound and glycidyl methacrylate are mixed in a molar ratio of 1:3.0-3.3, stirred at 100-200 r / min for 15-20 min, and a phosphazene base in an amount of 0.2-0.3 times the amount of the triazole compound is added under the protection of argon, the temperature is raised to 25-30° C., and the reaction is carried out for 1.0-1.5 h to obtain a mixed solution, the mixed solution is filtered through a basic alumina column, and 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° C. to a constant weight to obtain a novel epoxy resin;

[0010] (3) dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution 3 to 5 times by weight, adding activated nano-calcium silicate 1.1 to 1.7 times by weight of 2-benzoyl-4,5-dichlorobenzoic acid, stirring at 300 to 400 r / min for 10 to 15 minutes to obtain a mixture, adding p-toluenesulfonic acid 0.05 to 0.1 times by weight of the mixture, ultrasonicating at 30 to 40 kHz for 80 to 100 minutes, heating to 78 to 79° C., stirring at 700 to 800 r / min for 6 to 8 hours, and filtering to obtain a new hindered phenol antioxidant;

[0011] (4) Mixing by weight: 100-110 parts of the new epoxy resin, 14-16 parts of polyacrylate, 20-40 parts of curing agent, 5-10 parts of the new hindered phenol antioxidant, 0.3-0.7 parts of titanium dioxide, 0.05-0.1 parts of wetting dispersant, 0.03-0.07 parts of defoaming agent, and 10-15 parts of water; stirring; filtering; and degassing to obtain a high-temperature durable epoxy resin coating.

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

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

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

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

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

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

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

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

[0020] The present invention 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 epoxy resin is prepared using 1,3,5-tris(2-propynyloxy)benzene, 3-azidobutanol and glycidyl methacrylate as raw materials. 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol first undergo an azide-alkyne cycloaddition reaction to generate a complex triazole compound, and then the complex triazole compound undergoes an addition reaction with glycidyl methacrylate to obtain a new epoxy resin. The new epoxy resin has multiple functional groups, which can improve the crosslinking degree of the coating and enhance the mechanical properties of the coating. The introduction of benzene rings and triazole structures can make the epoxy resin coating have higher thermal stability and improve the heat resistance of the coating. At the same time, the triazole structure can also effectively absorb ultraviolet rays, avoiding direct damage to the coating by ultraviolet rays, and effectively extending the service life and appearance quality of the coating.

[0022] Secondly, the active hydroxyl groups on the surface of calcium silicate are first used to react with 2-benzoyl-4,5-dichlorobenzoic acid to graft 2-benzoyl-4,5-dichlorobenzoic acid onto the calcium silicate. Calcium silicate has good heat resistance, and adding it to epoxy resin coatings can further improve its high-temperature resistance. In addition, the use of calcium silicate to load antioxidants can provide a stable loading platform for antioxidants, and the synergistic effect between the active groups on the surface and the antioxidants can further improve the antioxidant performance. At the same time, it can also provide effective antioxidant protection in a wider temperature range, improve the anti-aging performance of the coating, and extend the service life of the coating. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the high-temperature durable epoxy resin coatings prepared in the following examples.

[0025] As for high temperature resistance, the high temperature durable epoxy resin coatings prepared in the embodiment and the comparative example of the same mass were poured into a mold and thermally cured at 80°C / 1h, 100°C / 3h, and 140°C / 2h to obtain an epoxy resin film. The epoxy resin film was added to a muffle furnace, heated to 400°C, maintained for 5 hours, and then cooled to room temperature and the surface of the sample was observed to see if there was any cracking or peeling.

[0026] Durability: The same mass of high-temperature durable epoxy resin coatings prepared in the embodiment and the comparative example were poured into a mold and thermally cured at 80°C / 1h, 100°C / 3h, and 140°C / 2h to obtain epoxy resin films. After the epoxy resin films were subjected to 16 hours of high-temperature sweat vapor corrosion, 6 hours of strong acid corrosion, 12 hours of strong alkali corrosion, and 100 hours of high-intensity ultraviolet irradiation, the surface of the samples was observed to see whether there was any cracking or falling off.

[0027] Adhesion: The same mass of high-temperature durable epoxy resin coatings prepared in the embodiment and the comparative example was poured into a mold and thermally cured at 80°C for 1 hour, 100°C for 3 hours, and 140°C for 2 hours to obtain epoxy resin films. The adhesion of the films was tested according to the test standard GB / T5210-2006 "Adhesion test for paints and varnishes by pull-off method".

[0028] Example 1

[0029] A method for preparing a high-temperature durable epoxy resin coating comprises the following steps:

[0030] (1) 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol were mixed at a molar ratio of 1:1.2, dissolved in N,N-dimethylformamide (4 times the mass of 1,3,5-tris(2-propynyloxy), stirred at 200 r / min for 10 min, and RuH2(CO)(PPh3)3 (0.02 times the mass of 1,3,5-tris(2-propynyloxy)benzene) as a ruthenium catalyst was added. The oil bath was heated to 75°C, reacted for 5 h, cooled to room temperature, and chloroform (3 times the mass of 1,3,5-tris(2-propynyloxy)benzene) was added. After filtering, the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (10:1 volume ratio) (10 times the mass of 1,3,5-tris(2-propynyloxy)) stirred at 800 r / min, and allowed to stand for 12 h. The solid was filtered and dried in a vacuum drying oven at 40°C to constant weight to obtain a triazole compound.

[0031] (2) A triazole compound and glycidyl methacrylate were mixed at a molar ratio of 1:3.0, stirred at 100 r / min for 15 min, and a phosphazene base in an amount 0.2 times the amount of the triazole compound was added under the protection of argon. The mixture was heated to 25°C and reacted for 1.0 h to obtain a mixed solution. The mixed solution was filtered through a basic alumina column and then added to n-hexane in an amount 6 times the mass of the mixed solution for precipitation. The solid was filtered and dried in a vacuum drying oven at 40°C to a constant weight to obtain a new epoxy resin.

[0032] (3) placing nano-calcium silicate with a particle size of 80 nm in a 30 wt % sodium hydroxide aqueous solution, dispersing it with 30 kHz ultrasonic waves for 30 min, soaking it for 6 h, adding hydrochloric acid dropwise until the pH is neutral, filtering the solid, washing it twice with deionized water, and drying it at 80° C. for 6 h to obtain activated nano-calcium silicate;

[0033] (4) 2-benzoyl-4,5-dichlorobenzoic acid was dissolved in an ethanol solution 3 times by weight, activated nano-calcium silicate 1.1 times by weight of 2-benzoyl-4,5-dichlorobenzoic acid was added, and the mixture was stirred at 300 r / min for 10 min to obtain a mixture, p-toluenesulfonic acid 0.05 times by weight of the mixture was added, ultrasonicated at 30 kHz for 80 min, heated to 78° C., stirred at 700 r / min for 6 h, and filtered to obtain a new hindered phenol antioxidant;

[0034] (5) Mixing by weight: 100 parts of the new epoxy resin, 14 parts of polyacrylate, 20 parts of hexamethylenetetramine, 5 parts of the new hindered phenol antioxidant, 0.3 parts of titanium dioxide, 0.05 parts of BYK-220S wetting and dispersing agent, 0.03 parts of BYK-054 defoaming agent, and 10 parts of water; stirring; filtering; and degassing to obtain a high-temperature durable epoxy resin coating.

[0035] Example 2

[0036] A method for preparing a high-temperature durable epoxy resin coating comprises the following steps:

[0037] (1) 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol were mixed at a molar ratio of 1:1.3, dissolved in N,N-dimethylformamide (5 times the mass of 1,3,5-tris(2-propynyloxy), stirred at 250 r / min for 13 min, and RuH2(CO)(PPh3)3 (0.03 times the mass of 1,3,5-tris(2-propynyloxy)benzene) as a ruthenium catalyst was added. The oil bath was heated to 76°C, reacted for 6 h, cooled to room temperature, and chloroform (4 times the mass of 1,3,5-tris(2-propynyloxy)benzene) was added. After filtering, the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (10:1 volume ratio) (12 times the mass of 1,3,5-tris(2-propynyloxy)) stirred at 900 r / min, and allowed to stand for 12 h. The solid was filtered and dried in a vacuum drying oven at 43°C to constant weight to obtain a triazole compound.

[0038] (2) A triazole compound and glycidyl methacrylate were mixed in a molar ratio of 1:3.2, stirred at 150 r / min for 17 min, and 0.2 times the amount of phosphazene base of the triazole compound was added under the protection of argon. The temperature was raised to 27°C and the reaction was carried out for 1.3 h to obtain a mixed solution. The mixed solution was filtered through a basic alumina column and then added to n-hexane 7 times the mass of the mixed solution for precipitation. The solid was filtered and dried in a vacuum drying oven at 43°C to constant weight to obtain a new epoxy resin;

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

[0040] (4) 2-benzoyl-4,5-dichlorobenzoic acid was dissolved in 4 times the mass of ethanol solution, activated nano-calcium silicate with a mass of 1.4 times the mass of 2-benzoyl-4,5-dichlorobenzoic acid was added, and the mixture was stirred at 350 r / min for 13 minutes to obtain a mixture, p-toluenesulfonic acid with a mass of 0.07 times the mass of the mixture was added, ultrasonicated at 35 kHz for 90 minutes, heated to 79°C, stirred at 750 r / min for 7 hours, and filtered to obtain a new hindered phenol antioxidant;

[0041] (5) Mix 105 parts of the new epoxy resin, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of the new hindered phenol antioxidant, 0.5 parts of titanium dioxide, 0.07 parts of BYK-220S wetting and dispersing agent, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water according to weight, stir, filter, and degas to obtain a high-temperature durable epoxy resin coating.

[0042] Example 3

[0043] A method for preparing a high-temperature durable epoxy resin coating comprises the following steps:

[0044] (1) 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol were mixed at a molar ratio of 1:1.5, dissolved in N,N-dimethylformamide (6 times the mass of 1,3,5-tris(2-propynyloxy), stirred at 300 r / min for 15 min, and RuH2(CO)(PPh3)3 ruthenium catalyst (0.04 times the mass of 1,3,5-tris(2-propynyloxy)benzene) was added. The oil bath was heated to 80°C, reacted for 8 h, cooled to room temperature, and chloroform (5 times the mass of 1,3,5-tris(2-propynyloxy)benzene) was added. After filtering, the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (10:1 volume ratio) (13 times the mass of 1,3,5-tris(2-propynyloxy)) stirred at 1000 r / min, and allowed to stand for 12 h. The solid was filtered and dried in a vacuum drying oven at 45°C to constant weight to obtain a triazole compound.

[0045] (2) A triazole compound and glycidyl methacrylate were mixed in a molar ratio of 1:3.3, stirred at 200 r / min for 20 min, and a phosphazene base in an amount 0.3 times the amount of the triazole compound was added under the protection of argon. The mixture was heated to 30°C and reacted for 1.5 h to obtain a mixed solution. The mixed solution was filtered through a basic alumina column and then added to n-hexane in an amount 8 times the mass of the mixed solution for precipitation. The solid was filtered and dried in a vacuum drying oven at 45°C to a constant weight to obtain a new epoxy resin.

[0046] (3) placing nano-calcium silicate with a particle size of 100 nm in a 40 wt % sodium hydroxide aqueous solution, dispersing it with 40 kHz ultrasonic waves for 60 min, soaking it for 8 h, adding hydrochloric acid dropwise until the pH is neutral, filtering the solid, washing it three times with deionized water, and drying it at 80° C. for 8 h to obtain activated nano-calcium silicate;

[0047] (4) 2-benzoyl-4,5-dichlorobenzoic acid was dissolved in an ethanol solution with a mass of 5 times, activated nano-calcium silicate with a mass of 1.7 times that of 2-benzoyl-4,5-dichlorobenzoic acid was added, and the mixture was stirred at 400 r / min for 15 minutes to obtain a mixture, p-toluenesulfonic acid with a mass of 0.1 times that of the mixture was added, ultrasonicated at 40 kHz for 100 minutes, heated to 79° C., stirred at 800 r / min for 8 hours, and filtered to obtain a new hindered phenol antioxidant;

[0048] (5) Mix 110 parts of the new epoxy resin, 16 parts of polyacrylate, 40 parts of hexamethylenetetramine, 10 parts of the new hindered phenol antioxidant, 0.7 parts of titanium dioxide, 0.1 parts of BYK-220S wetting and dispersing agent, 0.07 parts of BYK-054 defoaming agent, and 15 parts of water according to weight, stir, filter, and degas to obtain a high-temperature durable epoxy resin coating.

[0049] Comparative Example 1

[0050] The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: 3-azidobutanol and glycidyl methacrylate are mixed in a molar ratio of 1:1.2, stirred at 150 r / min for 17 min, 0.2 times the amount of the triazole compound of phosphazene base is added under the protection of argon, the temperature is raised to 27°C, and the reaction is carried out for 1.3 h to obtain a mixed solution, the mixed solution is filtered through an alkaline alumina column, and then precipitated in n-hexane 7 times the mass of the mixed solution, the solid is filtered, and dried in a vacuum drying oven at 43°C to constant weight to obtain a new epoxy resin; the remaining steps are the same as those in Example 2.

[0051] Comparative Example 2

[0052] The difference between Comparative Example 2 and Example 2 is that steps (1) and (2) are omitted, and step (5) is changed to: mixing, by weight, 105 parts of glycidyl methacrylate, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of a new hindered phenol antioxidant, 0.5 parts of titanium dioxide, 0.07 parts of BYK-220S wetting and dispersing agent, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water, stirring, filtering, and degassing to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those in Example 2.

[0053] Comparative Example 3

[0054] The difference between Comparative Example 3 and Example 2 is that there is no step (3), and step (4) is changed to: dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution 4 times the mass, adding nano-calcium silicate 1.4 times the mass of 2-benzoyl-4,5-dichlorobenzoic acid, stirring at 350 r / min for 13 min to obtain a mixture, adding p-toluenesulfonic acid 0.07 times the mass of the mixture, ultrasonicating at 35 kHz for 90 min, heating to 79° C., stirring at 750 r / min for 7 h, and filtering to obtain a new hindered phenol antioxidant; the remaining steps are the same as those in Example 2.

[0055] Comparative Example 4

[0056] Comparative Example 4 differs from Example 2 in that steps (3) and (4) are omitted, and step (5) is modified as follows: 105 parts of a novel epoxy resin, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of nano-calcium silicate, 0.5 parts of titanium dioxide, 0.07 parts of BYK-220S wetting and dispersing agent, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water are mixed, stirred, filtered, and degassed 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 omitted, and step (5) is changed to: 105 parts of a new epoxy resin, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of 2-benzoyl-4,5-dichlorobenzoic acid, 0.5 parts of titanium dioxide, 0.07 parts of BYK-220S wetting and dispersing agent, 0.05 parts of BYK-054 defoaming agent, and 13 parts of water are mixed in parts by weight, stirred, filtered, and defoamed to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those in Example 2.

[0059] Effect Examples

[0060] Table 1 below shows the performance analysis results of the high-temperature durable epoxy resin coatings of Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0061] Table 1

[0062]

[0063] From the comparison of the experimental data of Example 2 with those of Comparative Examples 1 and 2, it can be found that the present invention uses 1,3,5-tris(2-propynyloxy)benzene, 3-azidobutanol and glycidyl methacrylate as raw materials to prepare a new epoxy resin, 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol first undergo an azide-alkyne cycloaddition reaction to generate a complex triazole compound, and then the complex triazole compound undergoes an addition reaction with glycidyl methacrylate to obtain a new epoxy resin; the new epoxy resin has a variety of functional groups, which can improve the crosslinking degree of the coating and enhance the mechanical properties of the coating. The introduction of benzene ring and triazole structure can make the epoxy resin coating have higher thermal stability and improve the heat resistance of the coating. At the same time, the triazole structure can also effectively absorb ultraviolet rays, thereby avoiding direct damage to the coating by ultraviolet rays, and effectively extending the service life and appearance quality of the coating; from the comparison of the experimental data of Example 2 with that of Comparative Example 3, it can be found that without surface treatment of nano calcium silicate, the epoxy resin coating has a good thermal stability and good heat resistance. If activated, there will not be enough sites for 2-benzoyl-4,5-dichlorobenzoic acid to be grafted, thereby affecting the antioxidant performance and reducing the durability of the epoxy resin coating; from the comparison of the experimental data of Example 2 with Comparative Examples 4 and 5, it can be found that the present invention first utilizes the active hydroxyl groups on the surface of calcium silicate to undergo esterification reaction with the carboxyl groups of 2-benzoyl-4,5-dichlorobenzoic acid to graft 2-benzoyl-4,5-dichlorobenzoic acid onto the calcium silicate, and then hydrolyzes it to replace the chlorine atoms with hydroxyl groups to prepare a new hindered phenol antioxidant; calcium silicate has good heat resistance, and adding it to the epoxy resin coating can further improve its high temperature resistance, and using calcium silicate to load antioxidants can provide a stable loading platform for the antioxidants, and the active groups on the surface produce a synergistic effect with the antioxidants, further improving the antioxidant performance, and at the same time can also provide effective antioxidant protection in a wider temperature range, improve the anti-aging performance of the coating, and extend the service life of the coating.

[0064] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing a high-temperature durable epoxy resin coating, characterized in that: The method comprises the following preparation steps: (1) 1,3,5-tris(2-propynyloxy)benzene and 3-azidobutanol were mixed in a molar ratio of 1:1.2~1.5, dissolved in N,N-dimethylformamide (4~6 times the mass of 1,3,5-tris(2-propynyloxy)), stirred at 200~300 r / min for 10~15 min, added ruthenium catalyst (0.02~0.04 times the mass of 1,3,5-tris(2-propynyloxy)benzene), and heated in an oil bath to 7 5-80°C, react for 5-8 hours, cool to room temperature, add chloroform 3-5 times the mass of 1,3,5-tris(2-propynyloxy)benzene, filter, and drip the filtrate dropwise into a n-hexane / chloroform mixture 10-13 times the mass of 1,3,5-tris(2-propynyloxy)benzene stirred at 800-1000 r / min, let stand for 12 hours, filter and obtain the solid, and dry in a vacuum drying oven at 40-45°C to constant weight to obtain the triazole compound; (2) The triazole compound and glycidyl methacrylate are mixed in a molar ratio of 1:3.0~3.3, stirred at 100~200 r / min for 15~20 min, and 0.2~0.3 times the amount of the triazole compound of phosphazene base is added under the protection of argon. The temperature is raised to 25~30°C, and the reaction is carried out for 1.0~1.5 hours to obtain a mixed solution. The mixed solution is filtered through an alkaline alumina column and then added to n-hexane 6~8 times the mass of the mixed solution for precipitation. The solid is filtered and dried in a vacuum drying oven at 40~45°C to constant weight to obtain a new epoxy resin; (3) Dissolve 2-benzoyl-4,5-dichlorobenzoic acid in 3-5 times the mass of ethanol solution, add activated nano-calcium silicate in an amount of 1.1-1.7 times the mass of 2-benzoyl-4,5-dichlorobenzoic acid, stir at 300-400 r / min for 10-15 min to obtain a mixture, add p-toluenesulfonic acid in an amount of 0.05-0.1 times the mass of the mixture, ultrasonicate at 30-40 kHz for 80-100 min, heat to 78-79 ° C, stir at 700-800 r / min for 6-8 h, and filter to obtain a new hindered phenol antioxidant; (4) Mix 100-110 parts of the new epoxy resin, 14-16 parts of polyacrylate, 20-40 parts of curing agent, 5-10 parts of the new hindered phenol antioxidant, 0.3-0.7 parts of titanium dioxide, 0.05-0.1 parts of wetting and dispersing agent, 0.03-0.07 parts of defoaming agent and 10-15 parts of water according to weight, stir, filter and degas to obtain a high temperature durable epoxy resin coating.

2. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, wherein: The ruthenium catalyst in step (1) is RuH2(CO)(PPh3)3.

3. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, wherein: The n-hexane / chloroform mixture in step (1) is prepared by mixing n-hexane and chloroform in a volume ratio of 10:

1.

4. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, wherein: The activation of nano-calcium silicate in step (3) is as follows: placing the nano-calcium silicate in a 30-40 wt% sodium hydroxide aqueous solution, dispersing it with 30-40 kHz ultrasonic wave for 30-60 min, soaking it for 6-8 h, adding hydrochloric acid dropwise until the pH is neutral, filtering the solid, washing it with deionized water for 2-3 times, and drying it at 80° C. for 6-8 h to obtain the activated nano-calcium silicate.

5. The method for preparing a high-temperature durable epoxy resin coating according to claim 4, characterized in that: The particle size of the nano calcium silicate is 80-100 nm.

6. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, wherein: The curing agent in step (4) is hexamethylenetetramine and bismaleimide.

7. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, characterized in that: The wetting and dispersing agent in step (4) is any one of BYK-220S and BYK-333.

8. The method for preparing a high-temperature durable epoxy resin coating according to claim 1, characterized in that: The defoaming agent in step (4) is any one of BYK-071 and BYK-054.

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