Self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin and preparation method of self-cleaning anti-corrosion coating

Abstract

The invention relates to the field of coatings, and provides a self-cleaning anticorrosive coating containing fluorosilicone modified epoxy acrylic resin and a preparation method thereof.The coating is prepared from, by weight, 80-100 parts of fluorosilicone modified epoxy acrylic resin, 10-20 parts of modified silica sol, 5-10 parts of glass flakes, 0.05-2 parts of a catalyst, 1-4 parts of an initiator and 0.2-5 parts of a surfactant. 0.3-3 parts of graphene slurry and 400-500 parts of a solvent. The self-cleaning anticorrosive coating containing the fluorine-silicon modified epoxy acrylic resin has the characteristics of self-cleaning and corrosion resistance, and has better commercial application value.

Description

Technical Field

[0001] The invention relates to the field of coatings, and in particular to a self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. Background Art

[0002] In recent years, with the continuous development of science and technology and economy, self-cleaning anti-corrosion coatings form physical barriers to prevent harmful substances from contacting the surface of materials, thereby reducing or preventing the occurrence of corrosion, thereby significantly extending the service life of materials and providing comprehensive protection and beautification effects for materials. At the same time, it reduces maintenance costs, making it widely used in ships, railways, aircraft and other fields.

[0003] Epoxy acrylic resin has the advantages of low price, abundant sources, high hardness, good transparency and strong corrosion resistance, and is widely used in the field of coatings. However, epoxy acrylic resin still has some defects. For example, acrylic acid has a certain hydrophilicity, which makes the coating prepared from it have a high surface energy, thereby limiting its application in the field of self-cleaning; and epoxy acrylic resin will have problems of insufficient flexibility and stability after curing. In order to improve the self-cleaning performance of epoxy acrylic resin, the commonly used method is to compound fluorine-containing or silicon-containing substances with epoxy acrylic resin, but there are problems of poor compatibility and poor stability after mixing.

[0004] Patent CN 117700756A discloses a water-based perfluorosilicone-modified epoxy acrylate anti-graffiti resin and its preparation method and application. The anti-fouling graffiti resin is prepared by mixing silanized polyepoxy acrylic resin and perfluoroalkyl polyorganosiloxane, and has the advantages of low surface energy, excellent antifouling performance, high hardness, strong adhesion, etc., but does not solve the problem of insufficient flexibility and stability of epoxy acrylic resin after curing; Patent CN 103589297B discloses a photocurable composite coating containing a terminal vinyl fluorosilicone graft copolymer and a preparation method. The coating is prepared by adding a terminal vinyl fluorosilicone graft copolymer to an epoxy acrylic resin, and has water resistance, antifouling, anti-corrosion and other properties, but does not mention how to improve the compatibility and stability between the fluorosilicone graft copolymer and the epoxy acrylic resin.

[0005] Therefore, there is an urgent need in the market for a fluorine-containing silicon-modified epoxy acrylic resin coating with good self-cleaning and anti-corrosion properties. Summary of the invention

[0006] In view of the problems existing in the prior art, the present invention uses fluorine-silicon modified epoxy acrylic resin as the main raw material, adds modified silica sol, anti-corrosion filler glass flakes and surfactants, and synthesizes a self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin under the action of a catalyst and an initiator, which has the characteristics of self-cleaning and anti-corrosion.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On the one hand, the present invention provides a self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 80-100 parts of fluorine-silicon modified epoxy acrylic resin, 10-20 parts of modified silica sol, 5-10 parts of glass flakes, 0.05-2 parts of catalyst, 1-4 parts of initiator, 0.2-5 parts of surfactant, 0.3-3 parts of graphene slurry, and 400-500 parts of solvent.

[0009] Wherein, the initiator is benzoin ethyl ether or benzoin dimethyl ether; and the solvent is toluene.

[0010] In some embodiments of the present invention, the method for preparing the fluorosilicone-modified epoxy acrylic resin comprises the following steps:

[0011] (1) Add vinyl triethoxysilane to a reaction vessel, evacuate at 80-90° C., cool to 50-60° C., add hexamethylene diisocyanate and cobalt acetylacetonate in sequence under an inert atmosphere, stir, filter, and obtain product 1 for later use;

[0012] (2) Mix epoxy resin and ethyl acetate, stir, heat to 90-110° C., add tridecafluorooctyl methacrylate and benzoyl peroxide in sequence, reflux for 1-2 hours, cool to 80-90° C., add methacrylic acid dropwise, heat to 100-110° C., keep warm for reaction, stop the reaction when the acid value drops to 3.5-5.5 mg / g, cool to 65-75° C., filter, and obtain product 2 for standby use;

[0013] (3) The product 2 of step (2) and glycidyl methacrylate are mixed, the temperature is raised to 35-45° C., the product 1 of step (1) is added, and the mixture is stirred. Dodecyl mercaptan is added and the mixture is stirred to obtain a fluorosilicone-modified epoxy acrylic resin.

[0014] Wherein, in the step (2), the mass ratio of epoxy resin to tridecafluorooctyl methacrylate is 1:(0.4-0.7).

[0015] Preferably, in step (2), the mass ratio of epoxy resin to tridecafluorooctyl methacrylate is 1:0.55.

[0016] In some embodiments of the present invention, in step (1), the mass ratio of hexamethylene diisocyanate to vinyl triethoxysilane is 1:(4.5-5.5).

[0017] Preferably, in step (1), the mass ratio of hexamethylene diisocyanate to vinyl triethoxysilane is 1:5.

[0018] In some embodiments of the present invention, in step (3), the mass ratio of product 2, product 1 and dodecyl mercaptan is 1:(0.3-0.6):(0.04-0.06).

[0019] Preferably, in step (3), the mass ratio of product 2, product 1 and dodecyl mercaptan is 1:0.5:0.05.

[0020] Epoxy acrylic resin is currently the most widely used and largest-volume photocurable oligomer. Its cured coating film has the characteristics of high hardness, good gloss, corrosion resistance, and excellent heat resistance. It is one of the most widely used photosensitive resins in photocurable coatings. However, epoxy acrylic resin still has the defects of limited self-cleaning effect and insufficient flexibility after curing.

[0021] The applicant introduced organic fluorine methacrylate tridecafluorooctyl ester into epoxy resin to synthesize organic fluorine-modified epoxy resin, and then reacted with methacrylic acid to synthesize epoxy acrylic resin containing organic fluorine (product 2). The introduction of fluorine makes the epoxy acrylic resin hydrophobic, which is beneficial to the improvement of the self-cleaning property of the epoxy acrylic resin. Furthermore, the applicant used vinyl triethoxysilane and hexamethylene diisocyanate to cross-link under the action of catalyst cobalt acetylacetonate to prepare product 1, and used product 1 to modify the epoxy acrylic resin containing organic fluorine (product 2). On the one hand, the isocyanate group can improve the wear resistance and flexibility of the epoxy acrylic resin, thereby improving the defect of insufficient flexibility of the epoxy acrylic resin after curing. On the other hand, the organic silicon bond in vinyl triethoxysilane has both high strength and flexibility, and can provide good toughness. , and the vinyl group has high reactivity and a certain hydrophobicity, which is beneficial to promoting the self-cleaning performance of the epoxy acrylic resin; further, the applicant uses dodecyl mercaptan having a thiol structure to mix with the above-mentioned organic fluorine, isocyanate group and vinyl siloxane-modified epoxy acrylic resin to prepare a fluorosilicone-modified epoxy acrylic resin, and the thiol and the epoxy acrylic resin are cross-linked to form a dense and quasi-crystalline specific arrangement orientation, and the hydrophobic group of dodecyl mercaptan provides low surface energy, thereby improving the self-cleaning and corrosion resistance of the epoxy acrylic resin; in addition, the applicant controls the amount of vinyl triethoxysilane added to make it slightly excessive, so that the carbon-carbon double bonds in its structure may undergo a certain degree of cross-linking with the thiol of dodecyl mercaptan, thereby improving the stability of the fluorosilicone-modified epoxy acrylic resin.

[0022] In some embodiments of the present invention, the method for preparing the modified silica sol comprises the following steps:

[0023] 1) Boric acid, ethyl orthosilicate and anhydrous ethanol are mixed, stirred, heated to 65-75° C., deionized water is added, hydrochloric acid is added dropwise to adjust the pH to 3-4, condensed and refluxed for 3-4 hours, heated to 75-85° C., stirred for 2-3 hours, and silicon-boron doped silica sol is obtained for use;

[0024] 2) Add BNK-D6040 to the ethanol solution, stir, add acetic acid aqueous solution to adjust the pH to 3.5-4.5, stir for 50-70 minutes, add the silicon boron doped silica sol, MTMS and 2-hydroxypropane-1,2,3-tricarboxylic acid in step 1) in sequence, heat to 60-70° C., stir for 90-110 minutes, add n-butanol, stir for 20-40 minutes, and obtain the modified silica sol.

[0025] In some embodiments of the present invention, in step 1), the molar ratio of tetraethyl orthosilicate to boric acid is 1:(0.2-0.3).

[0026] Preferably, in step 1), the molar ratio of tetraethyl orthosilicate to boric acid is 1:0.24.

[0027] In some embodiments of the present invention, in step 2), the mass ratio of silicon-boron doped silica sol, BNK-D6040, MTMS and 2-hydroxypropane-1,2,3-tricarboxylic acid is 1:(0.6-0.9):(0.8-1):(0.05-0.15).

[0028] Preferably, in the step 2), the mass ratio of silicon-boron doped silica sol, BNK-D6040, MTMS and 2-hydroxypropane-1,2,3-tricarboxylic acid is 1:0.75:0.9:0.2.

[0029] Silica sol is a colloidal sol of inorganic polymer polysilicic acid with water as the dispersion medium. It can firmly adhere to the surface of substrates and filler particles. Adding it to coatings can make the coatings have stronger adhesion and improve the adhesion, impact strength, water resistance and weather resistance of the coating. However, silica sol has the problem that the silicon-oxygen bonds are too rigid and are prone to produce microcracks during the film-forming cross-linking process.

[0030] The applicant introduced silica sol into the coating by mechanical blending, so that the inorganic network of silica sol was introduced into the polymer network of fluorosilicone-modified epoxy acrylic resin to form an organic-inorganic hybrid material. The two networks intersected and penetrated each other, thereby increasing the crosslinking density of the system, thereby increasing the stability of the organic-inorganic hybrid material system; and the applicant prepared borosilicate-doped silica sol by hydrolysis and condensation reaction between boric acid as an additive and ethyl orthosilicate, forming an effective Si-OB chemical bond, thereby increasing the corrosion resistance, flame retardancy and hydrophobicity of the silica sol; and First, the applicant used the promoter BNK-D6040 and the silane coupling agent MTMS to modify the silicon-boron doped silica sol, thereby improving the hydrophobicity of the modified silica sol, and improving the stability and surface properties of the modified silica sol, thereby improving the self-cleaning performance of the coating and improving the problem that the silica sol is prone to cracks due to its high rigidity; finally, the applicant selected 2-hydroxypropane-1,2,3-tricarboxylic acid having both hydroxyl and carboxyl groups as a cross-linking agent, so that the modified silica sol has a large molecular weight and a cross-linking structure with spatial effects, thereby improving the stability of the modified silica sol.

[0031] In some embodiments of the present invention, the catalyst is bismuth ferrite.

[0032] In some embodiments of the present invention, the surfactant is a perfluorinated surfactant.

[0033] Another aspect of the present invention further provides a method for preparing the self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin described in the above technical solution, comprising the following steps:

[0034] S1, adding fluorine-silicon-modified epoxy acrylic resin, modified silica sol, glass flakes, surfactant and graphene slurry into the solvent, stirring for 30-50 minutes to obtain a mixed solution for standby use;

[0035] S2, adding the initiator and the catalyst to the mixed solution of step S1, stirring for 20-40 minutes, and obtaining the coating for use;

[0036] S3, coating the coating of step S2 on the tinplate sheet, and after forming, irradiating with ultraviolet light for 10-20 minutes to obtain a self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) The present invention uses fluorine-silicon modified epoxy acrylic resin as the main raw material, adds modified silica sol, anti-corrosion filler glass flakes and surfactants, and synthesizes a self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin under the action of a catalyst and an initiator. Through the synergistic effect of the various components, the coating has the advantages of self-cleaning and anti-corrosion.

[0039] (2) The present invention introduces organic fluorine methacrylate tridecafluorooctyl ester into epoxy resin to synthesize organic fluorine-modified epoxy resin, and then reacts with methacrylic acid to synthesize epoxy acrylic resin containing organic fluorine, and further introduces isocyanate group, vinyl triethoxysilane and thiol structure, so that the fluorine-silicon modified epoxy acrylic resin has good hydrophobicity and self-cleaning properties while also having good flexibility and stability.

[0040] (3) The present invention utilizes the principle that silica sol can improve the stability of coatings, and uses boric acid as an additive to synthesize borosilicate-doped silica sol, thereby improving the corrosion resistance and hydrophobicity of the modified silica sol, and further introduces a silane coupling agent and a cross-linking agent to give the modified silica sol a cross-linked structure, thereby improving the stability of the modified silica sol.

[0041] (4) The self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin prepared by the present invention has excellent self-cleaning and anti-corrosion properties, can be widely used in the coating field, and has good commercial application value. DETAILED DESCRIPTION

[0042] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0043] In the following embodiments and comparative examples, except for fluorosilicone-modified epoxy acrylic resin and modified silica sol, the other compound monomers and related reagents used can be purchased from the market. Among them, the surfactant is a product of our company, model Milliken BNK-4036; BNK-D6040 is a product of our company; the epoxy resin model is E51, purchased from Hebei Guansen Anticorrosion Materials Co., Ltd.; boric acid and hydrochloric acid are both analytically pure; tinplate sheets are purchased from Foshan Nanbeichao E-Commerce Co., Ltd.; graphene slurry is Changhui-GI3001B, purchased from Shenzhen Changhui New Materials Technology Co., Ltd.

[0044] Preparation Example 1

[0045] The synthesis method of fluorosilicone modified epoxy acrylic resin A comprises the following steps:

[0046] (1) Add 40 g of vinyl triethoxysilane into a reaction vessel, evacuate at 85 °C, cool to 55 °C, and heat under N 2 Under atmosphere, 8 g of hexamethylene diisocyanate and 2 g of cobalt acetylacetonate were added in sequence, stirred for 3 h, filtered, and product 1 was obtained for later use;

[0047] (2) 20 g of epoxy resin and 10 g of ethyl acetate were mixed, stirred for 20 min, heated to 100° C., 11 g of tridecafluorooctyl methacrylate and 0.3 g of benzoyl peroxide were added in sequence, refluxed for 1.5 h, cooled to 85° C., methacrylic acid was added dropwise, heated to 105° C., kept warm for reaction, and the acid value was measured every 30 min. When the acid value dropped to 4.5 mg / g, the reaction was stopped, the temperature was cooled to 70° C., and suction was filtered to obtain product 2 for standby use;

[0048] (3) 20 g of the product 2 of step (2) and 10 ml of glycidyl methacrylate were mixed, the temperature was raised to 40° C., 10 g of the product 1 of step (1) was added, and the mixture was stirred for 6 h. 1 g of dodecyl mercaptan was added, and the mixture was stirred for 30 min to obtain fluorosilicone-modified epoxy acrylic resin A.

[0049] Preparation Example 2

[0050] The specific implementation manner of fluorosilicone-modified epoxy acrylic resin B is the same as that of fluorosilicone-modified epoxy acrylic resin A, except that in step (1), the mass of vinyl triethoxy silane is replaced with 34 g.

[0051] Preparation Example 3

[0052] The specific implementation manner of fluorosilicone-modified epoxy acrylic resin C is the same as that of fluorosilicone-modified epoxy acrylic resin A, except that in step (3), the mass of product 1 is replaced with 5.5 g.

[0053] Preparation Example 4

[0054] The specific implementation manner of the fluorosilicone-modified epoxy acrylic resin D is the same as that of the fluorosilicone-modified epoxy acrylic resin A, except that in step (3), the mass of dodecyl mercaptan is replaced by 0.4 g.

[0055] Preparation Example 5

[0056] The synthesis method of modified silica sol A comprises the following steps:

[0057] 1) 0.024 mol of boric acid, 0.1 mol of ethyl orthosilicate and 0.14 mol of anhydrous ethanol were mixed, stirred, heated to 65-75° C., 3 ml of deionized water was added, hydrochloric acid was added dropwise to adjust the pH to 3.5, condensed and refluxed for 3.5 h, heated to 80° C., stirred for 2.5 h, and silicon-boron doped silica sol was obtained for use;

[0058] 2) Add 15g BNK-D6040 to 50ml 75wt% ethanol solution, stir for 20min, add 4wt% acetic acid aqueous solution to adjust pH=4, stir for 60min, add 20g silicon boron doped silica sol of step 1), 18g MTMS and 2g 2-hydroxypropane-1,2,3-tricarboxylic acid in sequence, heat to 65°C, stir for 100min, add 10g n-butanol, stir for 30min, and obtain modified silica sol A.

[0059] Preparation Example 6

[0060] The specific implementation manner of modified silica sol B is the same as that of modified silica sol A, except that in step 1), the molar number of boric acid is replaced with 0.015 mol.

[0061] Preparation Example 7

[0062] The specific implementation method of modified silica sol C is the same as that of modified silica sol A, except that in step 2), the mass of BNK-D6040 is replaced with 8 g.

[0063] Preparation Example 8

[0064] The specific implementation method of modified silica sol D is the same as that of modified silica sol A, except that in step 2), the mass of MTMS is replaced with 14 g.

[0065] Preparation Example 9

[0066] The specific implementation manner of modified silica sol E is the same as that of modified silica sol A, except that in step 2), the mass of 2-hydroxypropane-1,2,3-tricarboxylic acid is replaced with 0.5 g.

[0067] Example 1

[0068] A self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 90 parts of fluorine-silicon modified epoxy acrylic resin A, 15 parts of modified silica sol A, 7.5 parts of glass flakes, 1.025 parts of bismuth ferrite, 2.5 parts of benzoin ethyl ether, 2.5 parts of surfactant Milliken BNK-4036, 1.5 parts of graphene slurry, and 450 parts of toluene.

[0069] The preparation method of the self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin in this embodiment comprises the following steps:

[0070] S1, adding fluorosilicone modified epoxy acrylic resin A, modified silica sol A, glass flakes, surfactant Milliken BNK-4036 and graphene slurry into toluene, stirring for 40 minutes to obtain a mixed solution for standby use;

[0071] S2, adding benzoin ethyl ether and bismuth ferrite to the mixed solution of step S1, stirring for 30 minutes, and obtaining a coating for standby use;

[0072] S3, coating the coating of step S2 on the tinplate to a thickness of 0.03 mm, and after molding, ultraviolet light at a light intensity of 40 mW / cm 2 After irradiation under light intensity of 15 minutes, a self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin was obtained.

[0073] Example 2

[0074] A self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 90 parts of fluorine-silicon modified epoxy acrylic resin A, 10 parts of modified silica sol A, 5 parts of glass flakes, 0.05 parts of bismuth ferrite, 1 part of benzoin dimethyl ether, 0.2 parts of surfactant Milliken BNK-4036, 0.3 parts of graphene slurry, and 400 parts of toluene.

[0075] The preparation method of the self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin in this embodiment comprises the following steps:

[0076] S1, adding fluorosilicone modified epoxy acrylic resin A, modified silica sol A, glass flakes, surfactant Milliken BNK-4036 and graphene slurry into toluene, stirring for 30 minutes to obtain a mixed solution for standby use;

[0077] S2, adding benzoin dimethyl ether and bismuth ferrite to the mixed solution of step S1, stirring for 20 minutes, and obtaining a coating for standby use;

[0078] S3, coating the coating of step S2 on the tinplate to a thickness of 0.03 mm, and after forming, ultraviolet light at a light intensity of 40 mW / cm 2 After irradiation for 10 minutes under a light intensity of , a self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin was obtained.

[0079] Example 3

[0080] A self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 90 parts of fluorine-silicon modified epoxy acrylic resin A, 20 parts of modified silica sol A, 10 parts of glass flakes, 2 parts of bismuth ferrite, 4 parts of benzoin ethyl ether, 65 parts of surfactant Milliken BNK-4036, 3 parts of graphene slurry, and 500 parts of toluene.

[0081] The preparation method of the self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin in this embodiment comprises the following steps:

[0082] S1, adding fluorosilicone modified epoxy acrylic resin A, modified silica sol A, glass flakes, surfactant Milliken BNK-4036 and graphene slurry into toluene, stirring for 50 minutes, and obtaining a mixed solution for standby use;

[0083] S2, adding benzoin ethyl ether and bismuth ferrite to the mixed solution of step S1, stirring for 40 minutes, and obtaining a coating for standby use;

[0084] S3, coating the coating of step S2 on the tinplate to a thickness of 0.03 mm, and after forming, ultraviolet light at a light intensity of 40 mW / cm 2 After irradiation for 20 minutes under a light intensity of , a self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin was obtained.

[0085] Example 4

[0086] A self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 80 parts of fluorine-silicon modified epoxy acrylic resin A, 15 parts of modified silica sol A, 6 parts of glass flakes, 1 part of bismuth ferrite, 2 parts of benzoin ethyl ether, 62 parts of surfactant Milliken BNK-4036, 1 part of graphene slurry, and 420 parts of toluene.

[0087] The preparation method of the self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin in this embodiment is the same as that in Example 1.

[0088] Example 5

[0089] A self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin. The coating comprises the following raw materials in parts by weight: 100 parts of fluorine-silicon modified epoxy acrylic resin A, 15 parts of modified silica sol A, 8 parts of glass flakes, 1.5 parts of bismuth ferrite, 3 parts of benzoin ethyl ether, 64 parts of surfactant Milliken BNK-403, 2.5 parts of graphene slurry, and 480 parts of toluene.

[0090] The preparation method of the self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin in this embodiment is the same as that in Example 1.

[0091] Example 6

[0092] This embodiment provides a self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that fluorine-silicon modified epoxy acrylic resin B replaces fluorine-silicon modified epoxy acrylic resin A in equal amounts.

[0093] Example 7

[0094] This embodiment provides a self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the fluorine-silicon modified epoxy acrylic resin A is replaced by the fluorine-silicon modified epoxy acrylic resin C in equal amounts.

[0095] Example 8

[0096] This embodiment provides a self-cleaning anti-corrosion coating containing fluorine-silicon modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that fluorine-silicon modified epoxy acrylic resin D replaces fluorine-silicon modified epoxy acrylic resin A in equal amounts.

[0097] Example 9

[0098] This embodiment provides a self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified silica sol B replaces modified silica sol A in equal amounts.

[0099] Example 10

[0100] This embodiment provides a self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified silica sol C replaces modified silica sol A in equal amounts.

[0101] Embodiment 11

[0102] This embodiment provides a self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified silica sol D replaces modified silica sol A in equal amounts.

[0103] Example 12

[0104] This embodiment provides a self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified silica sol E replaces modified silica sol A in equal amounts.

[0105] Comparative Example 1

[0106] This comparative example provides a self-cleaning anticorrosive coating containing fluorine-silicon modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of epoxy acrylic resin is used to replace the fluorine-silicon modified epoxy acrylic resin A.

[0107] Epoxy acrylic resin was purchased from Langfang Xiangteng Chemical Co., Ltd.

[0108] Comparative Example 2

[0109] This comparative example provides a self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of silica sol is used to replace the modified silica sol A.

[0110] Silica sol was purchased from Jinan Hongtai Chemical Co., Ltd.

[0111] Performance Testing

[0112] The self-cleaning and anti-corrosion properties of the self-cleaning anti-corrosion coatings of the fluorine-containing silicon-modified epoxy acrylic resins of the above Examples 1-12 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1.

[0113] (1) Self-cleaning

[0114] The self-cleaning performance of the coating is judged by measuring its hydrophobicity. The contact angle of deionized water on the coating surface is measured using a contact angle meter at 25°C. The larger the contact angle, the better the hydrophobicity. A contact angle of more than 150° is super hydrophobic, which means it has good self-cleaning properties.

[0115] (2) Corrosion resistance

[0116] The corrosion resistance of the coating is judged by a salt spray test. The coating is scratched and placed in a salt spray environment of 5wt% sodium chloride aqueous solution for 7 days. After 7 days, the corrosion at the scratch is observed. If only a small amount of yellow corrosion products are produced at the scratch, the corrosion resistance is "good"; if there are yellow corrosion products in the area outside the scratch, but they are not in the form of flakes, the corrosion resistance is "fair"; if there are a large number of flaky yellow corrosion products in the area outside the scratch, the corrosion resistance is "poor", refer to standard GB / T 1771-91.

[0117] Table 1

[0118]

[0119]

[0120] It can be seen from the data in Table 1 that the self-cleaning anticorrosive coating containing fluorine-silicon modified epoxy acrylic resin in Examples 1-5 of the present invention has good self-cleaning and anticorrosion properties as a whole. Among them, Examples 6-8 respectively changed the addition ratio of the main components in the synthesis process of fluorine-silicon modified epoxy acrylic resin, so that the flexibility and stability of fluorine-silicon modified epoxy acrylic resin were reduced, resulting in the hydrophobic and anticorrosion modification effect of fluorine-silicon modified epoxy acrylic resin on the coating was not obvious, that is, the hydrophobicity and anticorrosion of the coating decreased; Examples 9-12 changed the ratio of boric acid, BNK-D6040 and MTMS and cross-linking agent 2-hydroxypropane-1,2,3-tricarboxylic acid in the modified silica sol, resulting in the anticorrosion and cross-linking stability of the modified silica sol decreased, and then the self-cleaning and anticorrosion properties of the coating decreased; Comparative Examples 1-2 respectively selected epoxy acrylic resin and silica sol to replace fluorine-silicon modified epoxy acrylic resin A and modified silica sol A in equal amounts, and the test found that the self-cleaning and anticorrosion properties of the coating showed poor results.

[0121] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A self-cleaning anti-corrosion coating of fluorine-silicon modified epoxy acrylic resin, It is characterized in that The coating comprises the following raw materials in parts by weight: 80-100 parts of fluorosilicone modified epoxy acrylic resin, 10-20 parts of modified silica sol, 5-10 parts of glass flakes, 0.05-2 parts of catalyst, 1-4 parts of initiator, 0.2-5 parts of surfactant, 0.3-3 parts of graphene slurry, and 400-500 parts of solvent.

2. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 1, It is characterized in that The preparation method of the fluorosilicone modified epoxy acrylic resin comprises the following steps: (1) Add vinyl triethoxysilane to a reaction vessel, evacuate at 80-90° C., cool to 50-60° C., add hexamethylene diisocyanate and cobalt acetylacetonate in sequence under an inert atmosphere, stir, filter, and obtain product 1 for later use; (2) Mix epoxy resin and ethyl acetate, stir, heat to 90-110° C., add tridecafluorooctyl methacrylate and benzoyl peroxide in sequence, reflux for 1-2 hours, cool to 80-90° C., add methacrylic acid dropwise, heat to 100-110° C., keep warm for reaction, stop the reaction when the acid value drops to 3.5-5.5 mg / g, cool to 65-75° C., filter, and obtain product 2 for standby use; (3) The product 2 of step (2) and glycidyl methacrylate are mixed, the temperature is raised to 35-45° C., the product 1 of step (1) is added, and the mixture is stirred. Dodecyl mercaptan is added and the mixture is stirred to obtain a fluorosilicone-modified epoxy acrylic resin.

3. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 2, It is characterized in that In the step (1), the mass ratio of hexamethylene diisocyanate to vinyl triethoxysilane is 1:(4.5-5.5).

4. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 2, It is characterized in that In the step (3), the mass ratio of product 2, product 1 and dodecyl mercaptan is 1:(0.3-0.6):(0.04-0.06).

5. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 1, It is characterized in that The preparation method of the modified silica sol comprises the following steps: 1) Boric acid, ethyl orthosilicate and anhydrous ethanol are mixed, stirred, heated to 65-75° C., deionized water is added, hydrochloric acid is added dropwise to adjust the pH to 3-4, condensed and refluxed for 3-4 hours, heated to 75-85° C., stirred for 2-3 hours, and silicon-boron doped silica sol is obtained for use; 2) Add BNK-D6040 to the ethanol solution, stir, add acetic acid aqueous solution to adjust the pH to 3.5-4.5, stir for 50-70 minutes, add the silicon boron doped silica sol, MTMS and 2-hydroxypropane-1,2,3-tricarboxylic acid in step 1) in sequence, heat to 60-70° C., stir for 90-110 minutes, add n-butanol, stir for 20-40 minutes, and obtain the modified silica sol.

6. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 5, It is characterized in that In the step 1), the molar ratio of tetraethyl orthosilicate to boric acid is 1:(0.2-0.3).

7. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 5, It is characterized in that In the step 2), the mass ratio of silicon-boron doped silica sol, BNK-D6040, MTMS and 2-hydroxypropane-1,2,3-tricarboxylic acid is 1:(0.6-0.9):(0.8-1):(0.05-0.15).

8. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 1, It is characterized in that The catalyst is bismuth ferrite.

9. The self-cleaning anticorrosive coating of fluorine-containing silicon-modified epoxy acrylic resin according to claim 1, It is characterized in that The surfactant is a perfluorinated surfactant.

10. A method for preparing a self-cleaning anticorrosive coating of a fluorine-containing silicon-modified epoxy acrylic resin according to any one of claims 1 to 9, It is characterized in that The following steps are involved: S1, adding fluorine-silicon-modified epoxy acrylic resin, modified silica sol, glass flakes, surfactant and graphene slurry into a solvent, stirring for 30-50 minutes to obtain a mixed solution for standby use; S2, adding the initiator and the catalyst to the mixed solution of step S1, stirring for 20-40 minutes, and obtaining the coating for use; S3, coating the coating of step S2 on the tinplate sheet, and after forming, irradiating with ultraviolet light for 10-20 minutes to obtain a self-cleaning anti-corrosion coating of fluorine-containing silicon-modified epoxy acrylic resin.

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