Antibacterial fluorine-modified epoxy vinyl ester resin, its production method, and general-purpose anticorrosive paint in which a plurality of mechanisms cooperate

Abstract

The present invention discloses an antibacterial fluorine-modified epoxy vinyl ester resin, a method for producing the same, and a general-purpose anticorrosive paint in which a plurality of mechanisms cooperate. The antibacterial fluorine-modified epoxy vinyl ester resin of the present invention is obtained by reacting a raw material containing a fluorine-containing acrylate monomer, an indole-based compound, and an epoxy vinyl ester resin. The general-purpose anticorrosive paint in which a plurality of mechanisms of the present invention cooperate has ultra-high density, high strength and toughness, and strong sealing properties, and is excellent in resistance to neutral salt spray, acidic salt spray and acidic atmosphere, and heat and humidity resistance. In the fields of ocean engineering, petrochemical power generation construction, aerospace technology, and defense industry, for various metal substrates, in a very harsh corrosion environment where a plurality of corrosion factors are combined and strengthened, it provides effective long-term corrosion protection and greatly extends the service life of the metal substrate.

Description

Technical Field

[0001] The present invention relates to the technical field of anticorrosive paints, and specifically, to an antibacterial fluorine-modified epoxy vinyl ester resin, a method for producing the same, and a general-purpose anticorrosive paint in which a plurality of mechanisms cooperate with each other.

Background Art

[0002] Corrosive media react spontaneously and slowly under natural conditions, causing damage and deterioration of metal materials, and significantly shortening the service life in the fields of ocean engineering, petrochemical power generation construction, aerospace technology, and the defense industry. Organic paints are widely used in the field of metal protection due to their unique advantages such as low cost, rapid construction, and strong corrosion resistance.

[0003] Currently, most anticorrosive paints are based on a single anticorrosive mechanism, and continue to use conventional classical systems such as resins, pigments, and fillers. Epoxy resins, polyurethane resins, fluorine resins, etc. are used for the resins, and the provision of anticorrosion behavior under specific working conditions is mainly based on only the control of the pigment and filler system, but there are few reports on the research on strengthening and suppressing corrosion factors by designing a specific molecular structure of the resin system. The above manufacturing method has great limitations, and the anticorrosive coatings obtained according to the conventional classical system can only be applied to specific uses. In harsh environments such as corrosion of marine equipment and ships by marine microorganisms, the complex and changeable environment in mountainous areas where condensation and moisture are likely to occur, freezing damage of coatings in extremely cold environments, high temperature, high humidity, and strong salinity corrosion environment in tropical seas, and severe acid rain erosion, multiple damage mechanisms act alternately, and the protection period of the coating for metal materials is significantly shortened. Conventional anticorrosive paints cannot simultaneously cope with the above complex and harsh environments and have no versatility.

[0004] CN101189311A discloses a paint composition comprising an epoxy resin, a curing agent, and inorganic chopped fibers, which is mainly used for anticorrosion of the inner and outer sides of steel pipes. Due to the directional arrangement of chopped fibers of a specific length, the coating skeleton is strengthened, and the abrasion resistance and crack resistance of the surface coating of the steel pipe with a specific curvature are effectively improved. However, due to the uneven dispersion of chopped fibers in the matrix system, the balance of stress received by the paint matrix is disrupted, which can effectively improve the abrasion resistance and crack resistance of the anticorrosive paint, but significantly reduces the resistance and sealing performance of the coating against the penetration of the medium.

[0005] EP2966134A1 discloses an anticorrosive paint composition composed of an epoxy resin, a curing agent, a silane coupling agent, oxidized polyethylene wax, and a filler pigment, which is mainly used to prevent seawater corrosion of the inner wall of a ballast tank. By introducing oxidized polyethylene wax, the rheology during the construction process of the anticorrosive paint is effectively improved. The use of this type of anticorrosive paint is limited by the substrate to be protected, and long-term corrosion protection cannot be achieved for light metals.

[0006] CN114032003A discloses an anticorrosive paint for ships composed of an epoxy resin, a modified basalt flake / carbon nitride composite material, and a zinc oxide / graphene composite material co-doped with samarium and copper. The present invention uses a general epoxy resin system and only adjusts the amount of functional fillers such as zinc oxide and graphene from a physical perspective to improve the sealing and corrosion resistance mechanisms, but there is insufficient data support regarding weather resistance.

[0007] Anti-corrosion coatings are coatings widely used in fields such as modern industry, transportation, energy, and ocean engineering. Under different corrosion conditions, the anti-corrosion mechanisms of anti-corrosion coatings are different, each with its own focus. As a result, the types of anti-corrosion coatings are complex and diverse. Due to different raw materials and production processes, the raw materials of anti-corrosion coatings become diverse, the price increases, and the production cost rises. The difference in the construction process significantly increases the labor cost of painters, and the difference in use and management significantly increases the maintenance cost. The production and use of general-purpose anti-corrosion coatings is one way to effectively eliminate the differentiation of each process, significantly reduce costs, and strictly comply with the country's energy conservation and emission reduction, carbon peak and carbon neutrality policies. Furthermore, due to the synergistic effect of multiple anti-corrosion mechanisms, it is urgent to realize performance improvement, develop new high-performance general-purpose long-term anti-corrosion coatings, and meet the anti-corrosion needs in various industries from underground and sea to space, and from traditional industries to emerging industries.

[0008] With the progress of science and technology and the development of society, many metal substrate structure projects need to withstand more severe usage environments. Corrosion factors such as extreme cold and heat, alternating effects of moisture, high salinity ocean spray, strong aging deterioration, and continuous damage over a wide latitude range cause very strong damage to metal substrates. Among organic anti-corrosion coatings, epoxy resin is widely used in the field of anti-corrosion coatings due to its excellent mechanical properties, chemical properties, and designability. Although anti-corrosion coatings based on epoxy resin have excellent performance advantages, there are still many problems during use. The conventional hydroxy groups of epoxy resin form hydrogen bond complexes with water molecules, which significantly reduces the water resistance of conventional epoxy anti-corrosion coatings. The repeated drying and wetting effects caused by various forms of water such as rain, dew, snow, frost, and seawater media with corrosion factors reduce the anti-corrosion effect of the anti-corrosion coating and shorten the protection period. In addition, the double bonds of the benzene ring in epoxy resin are easily affected by ultraviolet photolysis. When exposed to strong ultraviolet rays in the marine environment, the anti-corrosion coating is prone to powdering and peeling. The anti-corrosion coating is based on conventional epoxy resin and depends on a single anti-corrosion mechanism, which protects metal substrates from corrosion under harsh conditions such as deep ocean and extended space fields, but this is far from meeting the needs of related applications.

[0009] Therefore, currently, there is a need for anti-corrosion coatings with multiple anti-corrosion mechanisms suitable for complex and harsh environments.

Summary of the Invention

Problems to be Solved by the Invention

[0010] To solve the problems of the prior art, the present invention discloses an antibacterial fluorine-modified epoxy vinyl ester resin, a method for producing the same, and a general-purpose anticorrosive paint in which a plurality of mechanisms cooperate. The general-purpose anticorrosive paint in which a plurality of mechanisms of the present invention cooperate has ultra-high density, high strength and toughness, and strong sealing properties, and is excellent in resistance to neutral salt spray, acid salt spray and acidic atmosphere, and heat and humidity resistance. The general-purpose anticorrosive paint in which a plurality of mechanisms of the present invention cooperate provides effective long-term corrosion protection for various metal substrates in the fields of ocean engineering, petrochemical power generation construction, aerospace technology, and defense industry under a very harsh corrosion environment in which a plurality of corrosion factors are combined and strengthened, and greatly extends the service life of the metal substrate.

Means for Solving the Problems

[0011] One of the objects of the present invention is to provide an antibacterial fluorine-modified epoxy vinyl ester resin.

[0012] The structural formula of the antibacterial fluorine-modified epoxy vinyl ester resin is as follows.

Chemical formula

[0013] Another object of the present invention is to provide a method for producing an antibacterial fluorine-modified epoxy vinyl ester resin, which includes a step of reacting a raw material containing a fluorine-containing acrylate monomer, an indole-based compound, and an epoxy vinyl ester resin to obtain the antibacterial fluorine-modified epoxy vinyl ester resin, which is one of the objects of the present invention.)

[0014] In one preferred embodiment of the present invention, the structural formula of the fluorine-containing acrylate monomer is represented by the following formula, [Chemical formula] (wherein R1 is one of -H, -CH3, -CH2CH3, and R f is one of -CH2CF3, -CH2CF2CHFCF3, -CH2(CF2)5CHF2, -CH2CH2(CF2)5CF3.) The fluorine-containing acrylate monomer is preferably one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluorooctyl methacrylate, more preferably one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, and / or the structural formula of the indole-based compound is represented by the following formula, [Chemical formula] (wherein R2 is one of -H, -CH2CH=C(CH3)2, -CH2CH(OH)C(OH)(CH3)2.) The indole compound is preferably at least one of alkaloid (dihydroxyisoechinulin A), indole alkaloid (Neoechinulin A), and echinulin, more preferably at least one of indole alkaloid (Neoechinulin A) and echinulin, and / or The structural formula of the epoxy vinyl ester resin is represented by the following formula. [Chemical formula] (Here, n = 10 to 30, and R4 and R5 are the same or different and are each independently -H or -CH3.)

[0015] Preferably, the epoxy vinyl ester resin is one or more of bisphenol F epoxy vinyl ester resin and bisphenol A epoxy vinyl ester resin having the above structure.

[0016] In one preferred embodiment of the present invention, The molar ratio of the amounts of use of the epoxy vinyl ester resin, fluorine-containing acrylate monomer, and indole compound is 1:(1 to 3):(1 to 3), preferably 1:(2 to 3):(2 to 3).

[0017] In one preferred embodiment of the present invention, The temperature of the reaction is 85 to 100 °C, preferably 90 to 96 °C, and / or the time of the reaction is 5 to 7 h, preferably 5.5 to 6.5 h.

[0018] The manufacturing method of the antibacterial fluorine-modified epoxy vinyl ester resin described in the present invention preferably adds organic solvent 1 (the mass ratio of organic solvent 1 to epoxy vinyl ester resin is 1:0.2 to 1) to a four-necked flask equipped with a temperature control device, a condensation device, a stirring device, a nitrogen introduction tube, and a liquid constant-rate dropping device, raises the temperature of the system to 85 to 100 °C, and adds a mixture of a fluorine-containing acrylate monomer, an indole-based compound, an epoxy vinyl ester resin, and an azo-based initiator to the dropping device (in the mixture, the molar ratio of the usage amounts of the epoxy vinyl ester resin, the fluorine-containing acrylate monomer, and the indole-based compound is 1:(1 to 3):(1 to 3), and the usage amount of the azo-based initiator is 0.2 to 1.5% of the mass of the mixture), and drops it into the four-necked flask at a constant rate within 1.5 to 2.5 h. After keeping warm for 1 to 3 h, a mixed solution of a peroxide-based initiator and organic solvent 2 (the mass ratio of the mixed solution of the peroxide-based initiator and organic solvent 2 to the epoxy vinyl ester resin is 0.1 to 0.6:1, and the content of the peroxide-based initiator in the mixed solution of the peroxide-based initiator and organic solvent 2 is 1 to 6 wt%) is added, and the dropping is completed within 0.2 to 1 h. After keeping warm for 1 to 3 h, the temperature is lowered and the material is taken out, including the step of obtaining the antibacterial fluorine-modified epoxy vinyl ester resin.

[0019] Preferably, The organic solvent 1 and the organic solvent 2 are the same or different, and each independently is one or more of n-butanol, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, cyclohexanone, preferably one of a mixture of xylene and n-butanol, a mixture of xylene and propylene glycol monomethyl ether, and / or The azo-based initiator is at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, 2,2'-bis(2-imidazolin-2-yl)[2,2'-azobispropane]·2 hydrochloride, preferably at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, and / or The peroxide initiator is at least one of benzoyl peroxide, 2-ethylhexanoyl-t-butyl peroxide, dilauroyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, t-butyl peroxybenzoate, t-butyl peroxypivalate, di-t-butyl peroxide, cumene hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, di(2-phenoxyethyl) peroxydicarbonate, t-butyl peroxybenzoate, preferably at least one of benzoyl peroxide, t-butyl peroxybenzoate, 2-ethylhexanoyl-t-butyl peroxide.

[0020] Yet another object of the present invention is to provide a general-purpose anticorrosive paint in which a plurality of mechanisms including the antibacterial fluorine-modified epoxy vinyl ester resin which is one of the objects of the present invention or the antibacterial fluorine-modified epoxy vinyl ester resin produced by the method which is another object of the present invention cooperate with each other.

[0021] In one preferred embodiment of the present invention, the general-purpose anticorrosive paint in which the plurality of mechanisms cooperate with each other includes component A and component B. Component A includes an interpenetrating network high-density epoxy resin, a corrosion inhibitor, a pigment / filler, an auxiliary agent, and solvent A. The interpenetrating network high-density epoxy resin includes a blend of an antibacterial fluorine-modified epoxy vinyl ester resin and an epoxy resin. Based on 100 parts by weight of the interpenetrating network high-density epoxy resin, the antibacterial fluorine-modified epoxy vinyl ester resin is 35 to 60 parts by weight, preferably 40 to 50 parts by weight. The interpenetrating network high-density epoxy resin is 100 parts by weight. The corrosion inhibitor is 40 to 60 parts by weight, preferably 45 to 55 parts by weight. The pigment / filler is 40 to 60 parts by weight, preferably 45 to 55 parts by weight. The auxiliary agent is 3 to 5 parts by weight, preferably 3.5 to 4.5 parts by weight, The solvent A is 50 to 100 parts by weight, preferably 60 to 80 parts by weight, The component B includes a two-dimensional micro / nano material preliminary dispersion slurry, an amine-based curing agent, and a solvent B. The two-dimensional micro / nano material preliminary dispersion slurry is produced from components including a two-dimensional micro / nano material, a solvent C, and an amino-functional silane coupling agent. Based on 100 parts by weight of the interpenetrating network high-density epoxy resin, The two-dimensional micro / nano material preliminary dispersion slurry is 3 to 10 parts by weight, preferably 5 to 8 parts by weight, The amine-based curing agent is 40 to 60 parts by weight, preferably 45 to 55 parts by weight, The solvent B is 5 to 20 parts by weight, preferably 10 to 15 parts by weight, and / or The range of the ratio of the usage amounts of the component A and the component B is (3 to 5):1.

[0022] In one preferred embodiment of the present invention, The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol epoxy resin, and / or The corrosion inhibitor is one or more of zinc chromate, zinc phosphate, 8-hydroxyquinoline, aluminum tripolyphosphate, and 2-isopropylimidazoline, and / or The pigment / filler is one or more of silica, titanium dioxide, carbon black, red iron oxide, barium sulfate, mica powder, and calcium carbonate, and / or The auxiliary agent is one or more of a dispersant, an antifoaming agent, and a leveling agent, and / or The dispersant is a normal dispersant in this field. In the present invention, preferably, it may be at least one of HT-5000 (Han Tai Chemical Industry), HT-5020 (Han Tai Chemical Industry), HT-5040 (Han Tai Chemical Industry), WinSperse 3030 (Weipos New Materials Shandong Co., Ltd.), WinSperse 3140 (Weipos New Materials Shandong Co., Ltd.), Lencolo1103 (Guangdong Lanke Road New Materials Co., Ltd.), and / or The defoaming agent is a normal defoaming agent in this field. In the present invention, preferably, it may be at least one of UV-225 (Daejeon Chemical), DS-100 (Daejeon Chemical), silicone defoaming agent HT-508 (Han Tai Chemical Industry), AMXP902 (Anmei Technology Co., Ltd.), and / or The leveling agent is a normal leveling agent in this field. In the present invention, preferably, it may be at least one of Xinnuo (registered trademark) WE-D819C (Anhui Jiazhixin Nuo Chemical Co., Ltd.), GS5750 (GS Chemical), GS5411 (GS Chemical), IOTA-3000 (Anhui Aiyota Silicone Oil Co., Ltd.), and / or The two-dimensional micro-nano material is one or more of graphene oxide and its derivatives, boron nitride, molybdenum disulfide, flaky silver powder, glass flakes, mica flakes, basic zinc sulfate micron flakes, and / or The amino-functional silane coupling agent is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and / or The amine-based curing agent is one or more of phenolic amine, polyamide, aromatic amine, alicyclic amine, and / or The solvent A and the solvent B are the same or different, and each independently is preferably one or more of xylene, methyl isobutyl ketone, methyl isobutyl pentanone, butyl acetate, n-butanol, cyclohexanone, and / or The solvent C is one or two of xylene and n-butanol.

[0023] The method for producing the two-dimensional micro / nano material preliminary dispersion slurry of the present invention preferably comprises putting 60-80% of the two-dimensional micro / nano material and the solvent C at the bottom of a three-necked flask, heating to 60-65 °C, and dropping a mixture of an amino-functional silane coupling agent and the remaining 20-40% of the solvent C into the flask at a constant rate. At this time, the mass ratio of the two-dimensional micro / nano material, the solvent C, and the amino-functional silane coupling agent is 1:5-10:0.03-0.1, heating the reaction system uniformly by stirring, discharging the generated heat in a timely manner, setting the stirring reaction time to 1-2 h, and including the step of producing the two-dimensional micro / nano material preliminary dispersion slurry.

[0024] A further object of the present invention is to provide a method for producing a general-purpose anticorrosive paint in which components A and B are each mixed in the above-mentioned amounts, and then components A and B are mixed in the above-mentioned ratio to obtain a general-purpose anticorrosive paint in which the plurality of mechanisms cooperate.

[0025] The present invention preferably can adopt the following specific technical solutions.

[0026] The method for producing component A preferably comprises sequentially weighing 100 parts by weight of an interpenetrating network high-density epoxy resin, 40-60 parts by weight of a corrosion inhibitor, 40-60 parts by weight of a pigment / filler, 3-5 parts by weight of an auxiliary agent, and 50-100 parts by weight of a solvent A, mixing and dispersing at a rotation speed of 2500 rpm for 15 min, and putting it into a high-speed grinder to grind to a fineness of 60 μm or less to obtain component A.

[0027] The method for producing component B preferably comprises mixing 3-10 parts by weight of a two-dimensional micro / nano material preliminary dispersion slurry, 40-60 parts by weight of an amine-based curing agent, and 5-20 parts by weight of a solvent B, stirring uniformly to obtain component B, and Mix Component A and Component B in a usage ratio of (3 to 5):1 to obtain a general-purpose anticorrosive paint in which the plurality of mechanisms cooperate, including this step.

[0028] When in use, the general-purpose anticorrosive paint in which the plurality of mechanisms of the present invention cooperate can be applied as an anticorrosive coating to a steel substrate, a stainless steel substrate, and a ceramic substrate that require anticorrosion by brush coating, spray coating, and roll coating.

Advantages of the Invention

[0029] The beneficial effects of the present invention are as follows. In the design of the general-purpose anticorrosive paint in which a plurality of mechanisms cooperate, the formulation of the anticorrosive paint is designed using a dual mechanism of a suppression effect and a shielding effect. As a result, the obtained paint has a three-dimensional spatial network system with ultra-high density, a two-dimensional micro-nano material skeleton construction system with strong sealing properties, and an interpenetrating network matrix with high strength, toughness, and wear resistance.

[0030] In the present invention, an antibacterial fluorine-modified epoxy vinyl ester resin and an interpenetrating network high-density epoxy resin based on an epoxy resin are used as the matrix resin of a general-purpose anticorrosive paint in which a plurality of mechanisms cooperate. Here, a fluorine-containing side chain is introduced into the fluorine-modified epoxy vinyl ester resin. During the coating formation process, fluorine segments tend to move to the surface of the anticorrosive paint and are arranged in a predetermined direction. The constructed hydrophobic protection barrier enhances the energy barrier for corrosion particles to penetrate into the interior of the coating. By designing the interpenetrating network matrix resin, the distance between epoxy resin molecular segment nodes is further shortened, and the density and sealing performance are further improved. In the marine environment, considering that the chemicals secreted during the corrosion process of microorganisms have high permeability, an indole-based compound is introduced into the resin body to exert a corrosion inhibition effect on microorganisms. In the present invention, a two-dimensional micro-nano material having a unique lamellar structure is chemically modified to improve its uniform dispersibility and anti-aggregation property. An aminosilane coupling agent is used to pre-disperse the two-dimensional micro-nano material to prepare a two-dimensional micro-nano material pre-dispersed slurry. The surface of the two-dimensional micro-nano material has amino active groups and can form a chemical bond with the epoxy groups of the epoxy resin. The two-dimensional micro-nano materials are oriented and scattered at a specific density within the three-dimensional space network of the resin, effectively changing the diffusion path of corrosion particles into the matrix, preventing the corrosion particles from reaching the matrix, or extending the time until the corrosion particles reach the matrix, further enhancing the inhibition effect and shielding effect of the anticorrosive paint.

[0031] The general-purpose anticorrosive paint developed according to the present invention, in which a plurality of mechanisms cooperate, meets the anticorrosion needs of various metal substrates under various corrosion conditions in the fields of ocean engineering, petrochemical power generation construction, aerospace technology, and the defense industry.

Embodiments for Carrying Out the Invention

[0032] Hereinafter, the present invention will be described in detail with reference to specific examples. However, the following examples are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. It is necessary to point out that some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the content of the present invention are still included in the protection scope of the present invention.

[0033] For conditions not specifically described in the examples, conventional conditions or conditions recommended by the manufacturer shall be followed.

[0034] All raw materials used in the examples are commercially available raw materials.

[0035] The structural formula of the indole alkaloid (Neoechinulin A) (Hubei Wande Chemical Industry Co., Ltd.) used in the example is as follows.

Chemical formula

[0036] Production of antibacterial fluorine-modified epoxy vinyl ester resin S1 Add 44.3 g of a mixed solvent of xylene / butyl acetate (mass ratio of xylene to butyl acetate is 1:1) to a four-necked flask equipped with a temperature control device, a condensing device, a stirring device, a nitrogen inlet tube, and a liquid constant-rate dropping device. Introduce nitrogen gas into the reaction system and heat it to 90°C. Separately, 6.5 g (0.0162 mol) of dodecafluoroheptyl methacrylate, 4 g (0.0124 mol) of indole alkaloid (Neoechinulin A), and bisphenol A epoxy vinyl ester resin (Langfang Shengzi Anticorrosive Materials Co., Ltd., model UPR-FRP, its structural formula:

Chemical formula

[0037] Production of antibacterial fluorine-modified epoxy vinyl ester resin S2 44.6 g of a mixed solvent of xylene / n-butanol (mass ratio of xylene to n-butanol is 1:1) was added to a four-necked flask equipped with a temperature control device, a condenser, a stirrer, a nitrogen inlet tube, and a liquid constant-rate dropping device. Nitrogen gas was introduced into the reaction system, and the temperature was raised to 95 °C. Separately, 7.7 g (0.0458 mol) of trifluoroethyl methacrylate, 4 g (0.0124 mol) of indole alkaloid (Neoechinulin A), and bisphenol F epoxy vinyl ester resin (901 epoxy hexenyl resin manufactured by Langfang Rongjie Anticorrosive Materials Co., Ltd., its structural formula: [Chemical formula] (Here, n = 19, and R4 and R5 are -H.) 36 g (0.0067 mol), and 0.4 g of azobisisobutyronitrile were uniformly mixed and uniformly dropped into the reaction system within 2 h. After the dropping was completed, the mixture was kept warm for 2 h, and then, within 0.5 h, a mixed solution of 0.3 g of 2-ethylhexanoyl-t-butyl peroxide and 6.5 g of xylene was dropped, kept warm for 2 h, cooled, and the material was taken out to obtain a light yellow antibacterial fluorine-modified epoxy vinyl ester resin S2 having the following structural formula. [Chemical formula] (Here, n = 19, R f is -CH2CF3, R1 is -CH3, R4 and R5 are -H, and R2 and R3 are -H.)

[0038] Production of antibacterial fluorine-modified epoxy vinyl ester resin S3 Add 42.5 g of a mixed solvent of xylene / cyclohexanone (mass ratio of xylene to cyclohexanone is 1:1) to a four-necked flask equipped with a temperature control device, a condenser, a stirrer, a nitrogen inlet tube, and a liquid constant-rate dropping device. Introduce nitrogen gas into the reaction system and heat it to 95°C. Separately, weigh 7.5 g (0.03 mol) of hexafluorobutyl methacrylate, 4 g (0.0124 mol) of indole alkaloid (Neoechinulin A), 38.6 g (0.0066 mol) of bisphenol A epoxy vinyl ester resin (Langfang Shengzi Anticorrosion Materials Co., Ltd., model UPR-FRP), and 0.6 g of azobisisobutyronitrile, mix them uniformly, and uniformly drop them into the reaction system within 2 h. After the dropping is completed, keep the temperature for 2 h, and then drop a mixed solution of 0.3 g of 2-ethylhexanoyl-t-butyl peroxide and 6.5 g of xylene within 0.5 h, keep the temperature for 2 h, cool down, and take out the material to obtain a light yellow antibacterial fluorine-modified epoxy vinyl ester resin S3 with the following structural formula. [Chemical formula] (Here, n = 19, R f is -CH2CF2CHFCF3, R1 is -CH3, R4 and R5 are -CH3, and R2 and R3 are -H.)

[0039] Production of graphene oxide preliminary dispersion slurry T1 Put 12.6 g of graphene oxide powder and 64.8 g of xylene at the bottom of a three-necked flask, heat it up to 60 °C, and slowly drop a mixture of 1 g of aminoethylaminoethylaminopropyltrimethoxysilane (Silquest A-1130) and 21.6 g of xylene into the flask at a constant rate while keeping the temperature constant. Stir for 1.5 h to prepare a preliminary dispersion slurry T1 of graphene oxide.

[0040] Preparation of preliminary dispersion slurry T2 of boron nitride Put 11.5 g of boron nitride powder and 65.7 g of xylene at the bottom of a three-necked flask, heat it up to 65 °C, and slowly drop a mixture of 0.8 g of aminopropyltriethoxysilane and 22 g of xylene into the flask at a constant rate while keeping the temperature constant. Stir for 1.5 h to prepare a preliminary dispersion slurry T2 of boron nitride.

[0041] Preparation of preliminary dispersion slurry T3 of molybdenum disulfide Put 14.6 g of molybdenum disulfide powder and 63.6 g of xylene at the bottom of a three-necked flask, heat it up to 60 °C, and slowly drop a mixture of 0.6 g of aminoethylaminoethylaminopropyltrimethoxysilane (Silquest A-1130) and 21.2 g of xylene into the flask at a constant rate while keeping the temperature constant. Stir for 2 h to prepare a preliminary dispersion slurry T3 of molybdenum disulfide. Details of each component of an example of a general-purpose anticorrosive paint in which multiple mechanisms cooperate, which is manufactured using antibacterial fluorine-modified epoxy vinyl ester resins S1 to S3, two-dimensional micro / nano material preliminary dispersion slurries T1 to T3, and other anticorrosive paint components, are shown in Table 1 and Table 2, and details of each component of the comparative example are shown in Table 3.

[0042]

Table 1

[0043]

Table 2

[0044]

Table 3

[0045] The manufacturing process of the general-purpose anti-corrosion paint in which multiple mechanisms in Examples 1 to 7 cooperate is as follows (the usage amounts of each component are shown in Tables 1 and 2).

[0046] Manufacture of Component A: Weigh the interpenetrating network high-density epoxy resin, corrosion inhibitor, functional filler, auxiliary agent, and Solvent A in sequence, disperse them at a rotation speed of 2500 rpm for 15 minutes, put them into a high-speed grinder, and grind them until the fineness is 60 μm or less.

[0047] Manufacture of Component B: Mix the two-dimensional micro-nano material preliminary dispersion slurry, amine-based curing agent, and Solvent B, stir them uniformly, and prepare for use.

[0048] In Examples 1 to 7, all of Component A and Component B obtained in the usage amounts shown in Tables 1 and 2 are uniformly mixed respectively to obtain a general-purpose anti-corrosion paint in which multiple mechanisms cooperate. Then apply it on a tin plate and cure it at room temperature for 24 hours to obtain a general-purpose anti-corrosion coating in which multiple mechanisms cooperate with a coating thickness in the range of 170 ± 20 μm.

[0049] The manufacture of the anti-corrosion paints in Comparative Examples 1 to 4 is carried out in the same manner as in Example 1 (the usage amounts of each component in Comparative Examples 1 to 4 are shown in Table 3). In Comparative Examples 1 to 4, all of Component A1 and Component B1 obtained in the usage amounts shown in Table 3 are uniformly mixed respectively to obtain an anti-corrosion paint (in each comparative example, the same amount of mica powder with anti-corrosion effect is added instead of the two-dimensional micro-nano material preliminary dispersion slurry). Then apply it on a tin plate and cure it at room temperature for 24 hours to obtain an anti-corrosion coating with a coating thickness in the range of 170 ± 20 μm.

[0050] Table 4 is an index of the performance for obtaining the general-purpose anti-corrosion coating in which multiple mechanisms of the present invention cooperate

[0051]

Table 4

[0052]

Table 5

[0053] From Table 4 and Table 5, it was found that the general anti-corrosion paint in which a plurality of mechanisms produced in Examples 1 to 7 cooperate has significantly better adhesion than the paints of Comparative Examples 1 to 4. The reason is that the interpenetrating network of the modified epoxy vinyl ester resin and the epoxy resin improves the bonding strength with the substrate. In the curing agent system, the two-dimensional micro-nano material preliminary dispersion slurry is modified with a silane coupling agent having an amino functional group, and the amino silane coupling agent plays a role in improving the adhesion. In the general anti-corrosion paint in which a plurality of mechanisms produced in Examples 1 to 7 cooperate, in the neutral salt spray resistance test, the damp heat resistance test and the cathodic disbondment resistance test, the performance is significantly better than the performance of Comparative Examples 1 to 4. The factors are the hydrophobic protection barrier by the fluorine segment, the dense sealing effect by the interpenetrating network of the matrix resin, the microbial corrosion resistance by the antibacterial group, and the two-dimensional sheet nano material effectively changes the diffusion path of the corrosion particles into the matrix, prevents the corrosion particles from reaching the matrix, or extends the time until the corrosion particles reach the matrix. In addition, because the two-dimensional nano material has a high specific surface area and mechanical properties, it is widely used to improve the corrosion resistance of anti-corrosion paints.

[0054] Specific embodiments of the present invention will be described in detail in conjunction with the table, but this should not be understood as limiting the protection scope of this patent. Various modifications and deformations that can be made by those skilled in the art without creative efforts within the scope described in the claims are still included in the protection scope of this patent.

Claims

1. An antibacterial fluorine-modified epoxy vinyl ester resin, the structural formula of which is represented by the following formula. 【Chemical 1】 (Here, R １ is one of -H, -CH ３ , -CH ２ CH ３ , and R ２ is one of -H, -CH ２ CH = C(CH ３ ) ２ , -CH ２ CH(OH)C(OH)(CH ３ ) ２ , and R ３ is -H or -CH ２ CH = C(CH ３ ) ２ , and R ｆ is -CH ２ CF ３ , -CH ２ CF ２ CHFCF ３ , -CH ２ (CF ２ ) ５ CHF ２ , -CH ２ CH ２ (CF ２ ) ５ CF ３ , and R ４ and R ５ are the same or different and each independently is -H or -CH ３ , and n = 10 to 30. )

2. Said R １ is -H or -CH ３ , and / or said R ２ is -H or -CH ２ CH(OH)C(OH)(CH ３ ) ２ , and / or said R ３ is -H, and / or said R ｆ is -CH ２ (CF ２ ) ５ CHF ２ or -CH ２ CH ２ (CF ２ ) ５ CF ３ , and / or said n = 15 to 25. The antibacterial fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that.

3. A method for producing the antibacterial fluorine-modified epoxy vinyl ester resin according to any one of Claims 1 to 2, comprising the step of reacting a raw material containing a fluorine-containing acrylate monomer, an indole-based compound, and an epoxy vinyl ester resin to obtain the antibacterial fluorine-modified epoxy vinyl ester resin.

4. The structural formula of the fluorine-containing acrylate monomer is represented by the following formula, 【Chemical Formula 2】 (Here, R １ is one of -H, -CH ３ , -CH ２ CH ３ , and R ｆ is one of -CH ２ CF ３ , -CH ２ CF ２ CHFCF ３ , -CH ２ (CF ２ ) ５ CHF ２ , -CH ２ CH ２ (CF ２ ) ５ CF ３ .) The fluorine-containing acrylate monomer is preferably one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluorooctyl methacrylate, and / or The structural formula of the indole-based compound is represented by the following formula, [Chemical Formula 3] (Here, R ２ is one of -H, -CH ２ CH = C(CH ３ ) ２ , -CH ２ CH(OH)C(OH)(CH ３ ) ２ , and R ３ is -H or -CH ２ CH = C(CH ３ ) ２ .) The indole-based compound is preferably at least one of alkaloid (dihydroxyisoeculin A), indole alkaloid (Neoeculin A), echinulin, more preferably at least one of indole alkaloid (Neoeculin A), echinulin, and / or The structural formula of the epoxy vinyl ester resin is represented by the following formula, which is a feature of the production method according to Claim 3. [Chemical Formula 4] (Here, n is from 10 to 30, and R ４ , and R ５ are the same or different and each independently is -H or -CH ３ .)

5. The molar ratio of the usage amounts of the epoxy vinyl ester resin, the fluorine-containing acrylate monomer, and the indole-based compound is 1:(1 - 3):(1 - 3), preferably 1:(2 - 3):(2 - 3), which is a feature of the production method according to Claim 3.

6. The temperature of the reaction is 85 - 100 °C, preferably 90 - 96 °C, and / or the time of the reaction is 5 - 7 h, preferably 5.5 - 6.5 h, which is a feature of the production method according to Claim 3.

7. A general-purpose anticorrosive paint in which a plurality of mechanisms cooperate, containing the antibacterial fluorine-modified epoxy vinyl ester resin according to any one of Claims 1 to 2, or the antibacterial fluorine-modified epoxy vinyl ester resin produced by the method according to any one of Claims 3 to 6.

8. Comprising Component A and Component B, Component A contains an interpenetrating network high-density epoxy resin, a corrosion inhibitor, a pigment / filler, an auxiliary agent, and a solvent A. The interpenetrating network high-density epoxy resin includes a blend of an antibacterial fluorine-modified epoxy vinyl ester resin and an epoxy resin. Based on 100 parts by weight of the interpenetrating network high-density epoxy resin, the antibacterial fluorine-modified epoxy vinyl ester resin is 35 to 60 parts by weight, preferably 40 to 50 parts by weight. The interpenetrating network high-density epoxy resin is 100 parts by weight. The corrosion inhibitor is 40 to 60 parts by weight, preferably 45 to 55 parts by weight. The pigment / filler is 40 to 60 parts by weight, preferably 45 to 55 parts by weight. The auxiliary agent is 3 to 5 parts by weight, preferably 3.5 to 4.5 parts by weight. The solvent A is 50 to 100 parts by weight, preferably 60 to 80 parts by weight. Component B contains a two-dimensional micro / nano material preliminary dispersion slurry, an amine-based curing agent, and a solvent B. The two-dimensional micro / nano material preliminary dispersion slurry is produced from a component containing a two-dimensional micro / nano material, a solvent C, and an amino-functional silane coupling agent. Based on 100 parts by weight of the interpenetrating network high-density epoxy resin. The two-dimensional micro / nano material preliminary dispersion slurry is 3 to 10 parts by weight, preferably 5 to 8 parts by weight. The amine-based curing agent is 40 to 60 parts by weight, preferably 45 to 55 parts by weight. The solvent B is 5 to 2 parts by weight, preferably 10 to 15 parts by weight, and / or The range of the ratio of the usage amounts of Component A and Component B is (3 to 5):

1. The general-purpose anticorrosive paint according to claim 7, characterized in that a plurality of mechanisms cooperate.

9. The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol epoxy resin, and / or The corrosion inhibitor is one or more of zinc chromate, zinc phosphate, 8-hydroxyquinoline, aluminum tripolyphosphate, and 2-isopropylimidazoline, and / or The pigment / filler is one or more of silica, titanium dioxide, carbon black, red iron oxide, barium sulfate, mica powder, and calcium carbonate, and / or The auxiliary agent is one or more of a dispersant, an antifoaming agent, and a leveling agent, and / or The two-dimensional micro / nano material is one or more of graphene oxide and its derivatives, boron nitride, molybdenum disulfide, flaky silver powder, glass flakes, mica flakes, and basic zinc sulfate micron flakes, and / or The amino-functional silane coupling agent is one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane, and N-aminoethyl-3-aminopropylmethyldimethoxysilane, and / or The amine-based curing agent is one or more of phenolamine, polyamide, aromatic amine, and alicyclic amine, and / or The solvent A and the solvent B are the same or different, and each independently is preferably one or more of xylene, methyl isobutyl ketone, methyl isobutyl pentanone, butyl acetate, n-butanol, and cyclohexanone, and / or The solvent C is one or two of xylene and n-butanol. The general-purpose anticorrosive paint in which the plurality of mechanisms according to claim 8 cooperate is characterized by this.

10. A method for producing a general-purpose anticorrosive paint in which a plurality of mechanisms cooperate, the method including the step of mixing each component of component A and component B in the above usage amounts, and then mixing component A and component B in the ratio of the above usage amounts to obtain the general-purpose anticorrosive paint in which the plurality of mechanisms cooperate, according to any one of claims 8 to 9.

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