High-temperature durable epoxy resin coating and preparation method thereof

Abstract

The invention discloses a high-temperature durable epoxy resin coating and a preparation method thereof, and relates to the technical field of epoxy resin coatings. The novel epoxy resin is prepared from 1, 3, 5-tris (2-propynyloxy) benzene, 3-azido butanol and glycidyl methacrylate as raw materials, the novel epoxy resin has multiple functional groups, the crosslinking degree of the coating can be improved, the epoxy resin coating can have high thermal stability due to introduction of a benzene ring and a triazole structure, and the epoxy resin coating can be applied to the field of coating materials. The heat resistance of the coating is improved; secondly, grafting 2-benzoyl-4, 5-dichlorobenzoic acid onto calcium silicate, and then hydrolyzing to prepare a novel hindered phenol antioxidant; calcium silicate is used for loading the antioxidant, a stable loading platform can be provided for the antioxidant, and active groups on the surface and the antioxidant generate a synergistic effect, so that the oxidation resistance is further improved, the anti-aging performance of the coating is improved, and the service life of the coating is prolonged. The high-temperature durable epoxy resin coating prepared by the invention has the effects of high temperature resistance and durability.

Description

Technical Field

[0001] The 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 many industries such as petroleum, chemical, metallurgy, transportation, aerospace, electromechanical, weapons, etc., equipment and structures often need to operate under high temperature conditions. Such an environment may reduce the performance of materials and even cause accidents. High temperature resistant coatings can effectively resist corrosion and wear caused by high temperatures, thereby extending the service life of the protected objects and reducing the need for maintenance and replacement.

[0003] Epoxy resin is widely used as an important resin matrix in adhesives, coatings and 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 products can usually withstand temperatures of 80 to 100 degrees Celsius, while specially designed heat-resistant products can reach 200 degrees Celsius or higher. However, as the scope of use of epoxy resin coatings continues to expand, its original temperature resistance and durability are no longer sufficient to meet more stringent requirements, making it difficult for traditional coatings to fully meet current application needs. 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 solutions: a high temperature durable epoxy resin coating, wherein the high temperature durable epoxy resin coating is prepared by using 1,3,5-tri(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 to prepare the coating.

[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-tri(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-tri(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-tri(2-propynyloxy)benzene), and heated to 7 °C in an oil bath. 5-80°C, react for 5-8h, cool to room temperature, add chloroform 3-5 times the mass of 1,3,5-tris(2-propynyloxy)benzene, filter, and dropwise add the filtrate into a mixture of n-hexane / chloroform 10-13 times the mass of 1,3,5-tris(2-propynyloxy) stirred at 800-1000r / min, let stand for 12h, filter to obtain the solid, and dry in a vacuum drying oven at 40-45°C to constant weight to obtain a triazole compound;

[0009] (2) a triazole compound and glycidyl methacrylate are mixed at 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 mixture is reacted for 1.0-1.5 h to obtain a mixed solution, the mixed solution is filtered through an alkaline 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 of 3 to 5 times the mass, adding activated nano-calcium silicate of 1.1 to 1.7 times the mass 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 of 0.05 to 0.1 times the mass 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 novel hindered phenol antioxidant;

[0011] (4) Mix 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, stir, filter and degas 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 wave for 30-60min, soaking it for 6-8h, adding hydrochloric acid until the pH is neutral, filtering out the solid, washing it with deionized water for 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 80-100 nm.

[0016] Furthermore, in the step (4), the curing agent 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 and BYK-054.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] The 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] Firstly, a novel epoxy resin is prepared with 1,3,5-tri(2-propynyloxy)benzene, 3-azidobutanol and glycidyl methacrylate as raw materials; 1,3,5-tri(2-propynyloxy)benzene and 3-azidobutanol first undergo an azide-alkyne ring addition reaction to generate a complex triazole compound; then the complex triazole compound undergoes an addition reaction with glycidyl methacrylate to obtain a novel epoxy resin; the novel 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, 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 calcium silicate. Calcium silicate has good heat resistance. Adding it to epoxy resin coating can further improve its high temperature resistance. Moreover, using calcium silicate to load antioxidants can provide a stable loading platform for antioxidants, and the active groups on the surface can produce synergistic effects with antioxidants to 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 described embodiments 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 work 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 coating prepared in the following examples are as follows:

[0025] As for high temperature resistance, high temperature durable epoxy resin coatings of the same mass obtained 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 an epoxy resin film. The epoxy resin film was added into 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 falling off.

[0026] Durability: 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 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 if there were any cracks or peeling.

[0027] Adhesion: 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, and the adhesion thereof 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 preparation 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, added with RuH2(CO)(PPh3)3 ruthenium catalyst (0.02 times the mass of 1,3,5-tris(2-propynyloxy)benzene), heated to 75°C in an oil bath, reacted for 5 h, cooled to room temperature, added with chloroform (3 times the mass of 1,3,5-tris(2-propynyloxy)benzene), filtered, and the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (10:1 in a volume ratio) (10 times the mass of 1,3,5-tris(2-propynyloxy)) stirred at 800 r / min, allowed to stand for 12 h, filtered to obtain a solid, 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 of 0.2 times the amount of the triazole compound was added under the protection of argon, the temperature was raised to 25° C., and the mixture was reacted for 1.0 h to obtain a mixed solution, the mixed solution was filtered through an alkaline alumina column, and then precipitated by adding n-hexane in an amount of 6 times the mass of the mixed solution, the solid was filtered, and dried in a vacuum drying oven at 40° C. to a constant weight to obtain a novel 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 wave for 30 min, soaking it for 6 h, adding hydrochloric acid dropwise until the pH is neutral, filtering out 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) dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution of 3 times its mass, adding activated nano-calcium silicate of 1.1 times its mass, stirring at 300 r / min for 10 min to obtain a mixture, adding p-toluenesulfonic acid of 0.05 times its mass, ultrasonicating at 30 kHz for 80 min, heating to 78° C., stirring at 700 r / min for 6 h, and filtering to obtain a novel hindered phenol antioxidant;

[0034] (5) Mix 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 according to weight, stir, filter, and degas 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 preparation 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, added with RuH2(CO)(PPh3)3 ruthenium catalyst (0.03 times the mass of 1,3,5-tris(2-propynyloxy)benzene), heated to 76°C in an oil bath, reacted for 6 h, cooled to room temperature, added with chloroform (4 times the mass of 1,3,5-tris(2-propynyloxy)benzene), filtered, and the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (12 times the mass of 1,3,5-tris(2-propynyloxy)) mixed at a volume ratio of 10:1 and stirred at 900 r / min, allowed to stand for 12 h, filtered to obtain a solid, 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 at a molar ratio of 1:3.2, stirred at 150 r / min for 17 min, and a phosphazene base in an amount of 0.2 times the amount of the triazole compound was added under the protection of argon, the temperature was raised to 27° C., and the mixture was reacted for 1.3 h to obtain a mixed solution. The mixed solution was filtered through an alkaline alumina column and then added to n-hexane in an amount of 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 novel epoxy resin;

[0039] (3) placing nano-calcium silicate with a particle size of 90 nm in a 35 wt % sodium hydroxide aqueous solution, dispersing it with 35 kHz ultrasonic wave for 45 min, soaking it for 7 h, adding hydrochloric acid dropwise until the pH is neutral, filtering out the solid, washing it with deionized water three times, and drying it at 80° C. for 7 h to obtain activated nano-calcium silicate;

[0040] (4) dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution of 4 times its mass, adding activated nano-calcium silicate of 1.4 times its mass, stirring at 350 r / min for 13 min to obtain a mixture, adding p-toluenesulfonic acid of 0.07 times its mass, ultrasonicating at 35 kHz for 90 min, heating to 79° C., stirring at 750 r / min for 7 h, and filtering to obtain a novel 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 preparation 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, added with RuH2(CO)(PPh3)3 ruthenium catalyst (0.04 times the mass of 1,3,5-tris(2-propynyloxy)benzene), heated to 80°C in an oil bath, reacted for 8 h, cooled to room temperature, added with chloroform (5 times the mass of 1,3,5-tris(2-propynyloxy)benzene), filtered, and the filtrate was dripped dropwise into a mixture of n-hexane / chloroform (13 times the mass of 1,3,5-tris(2-propynyloxy)) mixed at a volume ratio of 10:1 and stirred at 1000 r / min, allowed to stand for 12 h, filtered to obtain a solid, 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 at a molar ratio of 1:3.3, stirred at 200 r / min for 20 min, and a phosphazene base in an amount of 0.3 times the amount of the triazole compound was added under the protection of argon, the temperature was raised to 30° C., and the mixture was reacted for 1.5 h to obtain a mixed solution. The mixed solution was filtered through an alkaline alumina column and then added to n-hexane in an amount of 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 constant weight to obtain a novel 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 wave for 60 min, soaking it for 8 h, adding hydrochloric acid dropwise until the pH is neutral, filtering out the solid, washing it with deionized water three times, and drying it at 80° C. for 8 h to obtain activated nano-calcium silicate;

[0047] (4) dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution of 5 times its mass, adding activated nano-calcium silicate of 1.7 times its mass, stirring at 400 r / min for 15 min to obtain a mixture, adding p-toluenesulfonic acid of 0.1 times its mass, ultrasonicating at 40 kHz for 100 min, heating to 79° C., stirring at 800 r / min for 8 h, and filtering to obtain a novel 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 triazole compound 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 of 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: 105 parts of glycidyl methacrylate, 15 parts of polyacrylate, 30 parts of hexamethylenetetramine, 8 parts of 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 are mixed by weight, stirred, filtered, and defoamed 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 there is no step (3), and step (4) is changed to: dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution of 4 times the mass, adding nano-calcium silicate of 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 of 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] The difference between Comparative Example 4 and Example 2 is that there are no steps (3) and (4), and step (5) is changed to: 105 parts of new 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 by weight, stirred, filtered, and defoamed to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those of Example 2.

[0057] Comparative Example 5

[0058] The difference between Comparative Example 5 and Example 2 is that there are no steps (3) and (4), and step (5) is changed to: 105 parts of 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 by weight, stirred, filtered, and defoamed to obtain a high-temperature durable epoxy resin coating; the remaining steps are the same as those of Example 2.

[0059] Effect example

[0060] Table 1 below shows the performance analysis results of high temperature durable epoxy resin coatings using 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 ring addition 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 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, 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 those 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 the calcium silicate is activated, there will not be enough sites for the grafting of 2-benzoyl-4,5-dichlorobenzoic acid, 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 those of 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 calcium silicate, and then hydrolyzes and replaces 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. Moreover, 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 to 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.

[0064] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A high temperature durable epoxy resin coating, characterized in that: 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.

2. A high temperature durable epoxy resin coating according to claim 1, characterized in that: The novel hindered phenol antioxidant is prepared by firstly utilizing calcium silicate to load 2-benzoyl-4,5-dichlorobenzoic acid.

3. 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-tri(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-tri(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-tri(2-propynyloxy)benzene), and heated to 7 °C in an oil bath. 5-80°C, react for 5-8h, cool to room temperature, add chloroform 3-5 times the mass of 1,3,5-tris(2-propynyloxy)benzene, filter, and dropwise add the filtrate into a mixture of n-hexane / chloroform 10-13 times the mass of 1,3,5-tris(2-propynyloxy) stirred at 800-1000r / min, let stand for 12h, filter to obtain the solid, and dry in a vacuum drying oven at 40-45°C to constant weight to obtain a triazole compound; (2) a triazole compound and glycidyl methacrylate are mixed at 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 mixture is reacted for 1.0-1.5 h to obtain a mixed solution, the mixed solution is filtered through an alkaline 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; (3) dissolving 2-benzoyl-4,5-dichlorobenzoic acid in an ethanol solution of 3 to 5 times the mass, adding activated nano-calcium silicate of 1.1 to 1.7 times the mass 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 of 0.05 to 0.1 times the mass 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 novel hindered phenol antioxidant; (4) Mix 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, stir, filter and degas to obtain a high temperature durable epoxy resin coating.

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

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

1.

6. The method for preparing a high temperature durable epoxy resin coating according to claim 3, characterized in that: The activation of nano calcium silicate in step (3) is to place the nano calcium silicate in a 30-40wt% sodium hydroxide aqueous solution, disperse it with 30-40kHz ultrasonic wave for 30-60min, soak it for 6-8h, add hydrochloric acid until the pH is neutral, filter out the solid, wash it with deionized water for 2-3 times, and dry it at 80°C for 6-8h to obtain the activated nano calcium silicate.

7. The method for preparing a high temperature durable epoxy resin coating according to claim 6, characterized in that: The particle size of the nano calcium silicate is 80-100 nm.

8. The method for preparing a high temperature durable epoxy resin coating according to claim 3, characterized in that: The curing agent in step (4) is hexamethylenetetramine and bismaleimide.

9. The method for preparing a high temperature durable epoxy resin coating according to claim 3, characterized in that: The wetting and dispersing agent in step (4) is any one of BYK-220S and BYK-333.

10. The method for preparing a high temperature durable epoxy resin coating according to claim 3, characterized in that: The defoaming agent in step (4) is any one of BYK-071 and BYK-054.

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