WO2024002117A1 - Antibacterial fluorine-modified epoxy vinyl ester resin, method for preparing same, and multi-mechanism synergistic universal anti-corrosion coating - Google Patents

Abstract

Disclosed are an antibacterial fluorine-modified epoxy vinyl ester resin, a method for preparing same, and a multi-mechanism synergistic universal anti-corrosion coating. The antibacterial fluorine-modified epoxy vinyl ester resin of the present invention is obtained by reaction of raw materials including a fluorinated acrylate monomer, an indole compound, and an epoxy vinyl ester resin. The multi-mechanism synergistic universal anti-corrosion coating of the present invention has ultra-compactness, high strength and toughness, and strong sealing performance, and features excellent neutral salt spray resistance, acid salt spray/acid atmosphere resistance, and moisture-heat resistance, and thus can provide high-efficiency and long-term corrosion protection effects for various metal substrates in the fields of marine engineering, petrochemistry, electric power, buildings, aerospace technologies, and national defense industry under the coupling enhancement effect of various corrosion factors and the abnormal harsh corrosion environments and greatly prolong the service life of the metal substrates.

Description

An antibacterial fluorine-modified epoxy vinyl ester resin and its preparation method and multi-mechanism synergistic universal anti-corrosion coating Technical field

The invention relates to the technical field of anti-corrosion coatings, and specifically relates to an antibacterial fluorine-modified epoxy vinyl ester resin and its preparation method and multi-mechanism synergistic universal anti-corrosion coatings.

Background technique

Corrosive media react spontaneously and slowly under natural conditions, causing damage and deterioration of metal materials, greatly shortening their service life in the fields of marine engineering, petrochemical power construction, aerospace technology and national defense industry. Organic coatings are widely used in the field of metal protection due to their unique advantages such as low cost, fast construction, and strong corrosion resistance.

At present, most anti-corrosion coatings are based on a single anti-corrosion mechanism and continue to use original classic systems such as resins, pigments and fillers. The resins use epoxy resin, polyurethane resin and fluorocarbon resin, etc. The provision of corrosion protection behavior under specific working conditions is mostly based on pigments and fillers. Control of the system, but there are few reports on research on the enhancement and inhibition behavior of corrosion factors through the design of specific molecular structures of the resin system. The above preparation method has great limitations. The anti-corrosion coating obtained according to the original classic system can only meet the application in specific occasions. Corrosion of offshore engineering equipment and ships by marine microorganisms, complex and changeable environments in mountainous areas prone to condensation and moisture, freezing damage of coatings in extremely cold environments, strong corrosive environments with high temperatures, humidity and salt in tropical seas, and severe acid rain erosion and other harsh environments Multiple damage mechanisms act alternately, greatly shortening the protection period of the coating on metal materials. Traditional anti-corrosion coatings cannot meet the above complex and harsh environments at the same time and are not versatile.

CN101189311A discloses a coating composition, which is composed of epoxy resin, curing agent, and inorganic chopped fibers. It is mainly used for corrosion protection inside and outside steel pipes. The directional arrangement of chopped fibers with specific lengths provides a skeleton reinforcement for the coating, effectively improving the wear resistance and anti-cracking performance of the surface coating with a certain curvature of the steel pipe. The uneven dispersion of chopped fibers in the matrix system causes an imbalance of stress and strain experienced by the coating matrix. Although it can effectively improve the wear resistance and cracking resistance of anti-corrosion coatings, it will significantly reduce the coating's resistance to media penetration and sealing performance.

EP2966134A1 discloses an anti-corrosion coating composition composed of epoxy resin, curing agent, silane coupling agent, oxidized polyethylene wax and filling pigment. It is mainly used to prevent seawater corrosion of the inner wall of the ballast tank and the oxidized polyethylene wax. It is introduced to effectively improve the rheology during the construction process of anti-corrosion coatings. The use of this kind of anti-corrosion coatings is limited by the substrate to be protected, and it cannot achieve long-term corrosion protection for light metals.

CN114032003A discloses an anti-corrosion coating for ships composed of epoxy resin, modified basalt flake/carbon nitride composite material, and zinc oxide/graphene composite material co-doped with samarium and copper. This 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 strong sealing and anti-corrosion mechanism, but lacks data support for weather resistance.

Anticorrosive coating is a coating widely used in modern industry, transportation, energy, marine engineering and other sectors. Under different corrosion conditions, the anti-corrosion mechanisms of anti-corrosion coatings are different and each has its own emphasis, resulting in a wide variety of anti-corrosion coatings. The differences in raw materials and production processes of anti-corrosion coatings result in a variety of raw materials and high prices, thus increasing production costs. Differences in the construction process greatly increase the labor costs of painting technicians, and differences in use and management greatly increase maintenance costs. The production and use of general anti-corrosion coatings is one of the ways to effectively eliminate the differentiation of each chain link, greatly reduce costs, and closely follow the national energy conservation, emission reduction and carbon peak carbon neutrality policies. In addition, combined with the coupling effect of multiple anti-corrosion mechanisms, performance upgrades are achieved, and new high-performance universal long-lasting anti-corrosion coatings are developed to meet the urgent needs for corrosion protection in various industries, from underground oceans to space, from traditional industries to emerging industries.

With the advancement of science and technology and social development, a large number of metal-based structural projects need to withstand more severe service environments. Corrosion factors such as the alternating effects of extreme cold, humidity and heat in a wide latitude, ocean high salt spray, strong aging and sustained damage, cause extremely strong damage to metal substrates. Among organic anti-corrosion coatings, epoxy resin is widely used in the field of anti-corrosion coatings because of its excellent mechanical properties, chemical properties and designability. Although anti-corrosion coatings based on epoxy resin have good performance advantages, there are still many problems during use. The hydroxyl groups in traditional epoxy resins form hydrogen bond complexes with water molecules, which greatly weakens the water resistance of traditional epoxy anti-corrosion coatings. The different forms of water, rain, dew, snow, frost and seawater medium doped with corrosive factors can repeatedly dry out anti-corrosion coatings. During the alternating damage process of wet action, the corrosion protection effect of anti-corrosion coatings is greatly reduced and the protection period is shortened. In addition, the double bonds in the benzene ring of epoxy resin are easily affected by ultraviolet photolysis. Strong ultraviolet light exposure in the marine environment causes anti-corrosion coatings to easily powder and fall off. Anti-corrosion coatings are based on traditional epoxy resin and rely on a single anti-corrosion mechanism to protect metal substrates from corrosion under harsh conditions in ocean depth and space expansion, which is far from meeting the needs of relevant applications.

Therefore, there is currently a need for a multi-anticorrosion mechanism anticorrosive coating suitable for complex and harsh environments.

Contents of the invention

In order to solve the problems in the prior art, the present invention provides an antibacterial fluorine-modified epoxy vinyl ester resin, its preparation method and a multi-mechanism synergistic universal anti-corrosion coating. The multi-mechanism synergistic universal anti-corrosion coating of the present invention has ultra-dense, high strength and toughness, strong sealing properties, and excellent resistance to neutral salt spray, acid salt spray/acidic atmosphere, and moisture and heat resistance. The multi-mechanism synergistic universal anti-corrosion coating of the present invention can be used for various metal substrates in the fields of marine engineering, petrochemical power construction, aerospace technology and national defense industry. It can enhance the coupling effect of multiple corrosion factors and operate in extremely harsh corrosive environments. It provides efficient long-term corrosion protection and greatly extends the service life of metal substrates.

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

The structural formula of the antibacterial fluorine modified epoxy vinyl ester resin is:

Among them, R ₁ is one of -H, -CH ₃ and -CH ₂ CH ₃ , preferably -H or -CH ₃ , more preferably -CH ₃ ; R ₂ is -H, -CH ₂ CH=C One of (CH ₃ ) ₂ and -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ , preferably -H or -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ , more Preferably it is -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ ; R ₃ is -H or -CH ₂ CH=C(CH ₃ ) ₂ , preferably -H; R _f is -CH ₂ CF ₃ , -CH ₂ CF ₂ CHFCF ₃ , -CH ₂ (CF ₂ ) ₅ CHF ₂ , One of -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ , preferably -CH ₂ (CF ₂ ) ₅ CHF ₂ or -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ , more preferably -CH ₂ C ₆ F ₁₃ ; R ₄ and R ₅ are the same or different, and each is independently -H or -CH ₃ ; n=10-30, preferably n=15-25, more preferably n=17-22.

The second object of the present invention is to provide a method for preparing the antibacterial fluorine-modified epoxy vinyl ester resin, which is one of the objects of the present invention, including combining a fluorinated acrylate monomer, an indole compound and an epoxy vinyl ester resin. The step of reacting raw materials including ester resin to obtain the antibacterial fluorine-modified epoxy vinyl ester resin.

In a preferred embodiment of the invention,

The structural formula of the fluorine-containing acrylate monomer is: Among them, R ₁ is one of -H, -CH ₃ and -CH ₂ CH ₃ ; 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 ; the fluorine-containing acrylate monomer is preferably trifluoroethyl methacrylate, hexafluorobutyl methacrylate, or dodecafluoroheptyl methacrylate One or more of esters, tridecafluorooctyl methacrylate; more preferably, one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, or Several kinds; and/or,

The structural formula of the indole compound is: Wherein, R ₂ is one of -H, -CH ₂ CH=C(CH ₃ ) ₂ and -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ ; the indole compound is preferably dihydroxyisoechinulin and/or,

The structural formula of the epoxy vinyl ester resin is:

Wherein, n=10-30, R ₄ and R ₅ are the same or different, and each is independently -H or -CH ₃ ;

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.

In a preferred embodiment of the invention,

The molar ratio of the epoxy vinyl ester resin, fluorine-containing acrylate monomer, and indole compound is 1: (1-3): (1-3), preferably 1: (2-3): ( 2-3).

In a preferred embodiment of the invention,

The reaction temperature is 85-100°C, preferably 90-96°C; and/or the reaction time is 5-7h, preferably 5.5-6.5h.

The preparation method of the antibacterial fluorine-modified epoxy vinyl ester resin of the present invention preferably includes: adding an organic solvent to a four-necked flask equipped with a temperature control device, a condensation device, a stirring device, a nitrogen introduction pipe and a liquid dripping device at a uniform speed 1 (The mass ratio of organic solvent 1 to epoxy vinyl ester resin is 1:0.2-1, raise the system to 85-100°C, and add fluorine-containing acrylate monomer, indole compounds, and cyclic compounds to the dripping device. A mixture of oxyvinyl ester resin and azo initiator (in the mixture, the molar ratio of epoxy vinyl ester resin, fluorine-containing acrylate monomer, and indole compound is 1: (1-3) (1-3), the amount of azo initiator is 0.2-1.5% of the mass of the mixture), and is added dropwise to the four-necked flask at a uniform speed within 1.5-2.5h, and is kept warm for 1-3h, and then added The mass ratio of the mixture of oxidation initiator and organic solvent 2 (the mass ratio of the mixture of peroxide initiator and organic solvent 2 to epoxy vinyl ester resin is 0.1-0.6:1, the mass ratio of peroxide initiator and organic solvent 2 The content of the peroxide initiator in the mixed liquid is 1-6wt%), the dripping is completed within 0.2-1h, the temperature is maintained for 1-3h, the temperature is cooled and the material is discharged to obtain the antibacterial fluorine-modified epoxy vinyl ester resin.

Preferably,

The organic solvent 1 and the organic solvent 2 are the same or different, and are each independently one of n-butanol, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, and cyclohexanone. Or several, preferably one of a mixture of xylene and n-butanol, a mixture of xylene and propylene glycol monomethyl ether; and/or,

The azo initiator is azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanitrile, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride At least one of, preferably at least one of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptanitrile; and/or,

The peroxide initiator is benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dodecanoyl peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate. , Bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, di-tert-butyl peroxide, cumene hydroperoxide, At least one of dicumyl peroxide, p-alkane hydrogen peroxide, bis(2-phenoxyethyl)peroxydicarbonate, and tert-butyl peroxybenzoate, preferably benzoyl peroxide, At least one of tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate.

The third object of the present invention is to provide a multi-mechanism synergistic universal anti-corrosion coating, which contains the antibacterial fluorine-modified epoxy vinyl ester resin of one of the objects of the present invention or the antibacterial fluorine-modified epoxy vinyl ester resin prepared by the method of the second object of the present invention. Epoxy vinyl ester resin.

In a preferred embodiment of the invention,

The multi-mechanism synergistic universal anti-corrosion coating includes component A and component B;

The A component includes interpenetrating network high-density epoxy resin, corrosion inhibitors, pigments and fillers, additives and solvent A; the interpenetrating network high-density epoxy resin includes blended antibacterial fluorine-modified epoxy vinyl Ester resins and epoxy resins;

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 B component includes two-dimensional micro-nano material pre-dispersed slurry, amine curing agent and solvent B; the two-dimensional micro-nano material pre-dispersed slurry consists of two-dimensional micro-nano material, solvent C and amino functional group silane coupling agent Prepared from the components included;

Based on 100 parts by weight of interpenetrating network high-density epoxy resin,

Two-dimensional micro-nano material pre-dispersed slurry 3 to 10 parts by weight; preferably 5 to 8 parts by weight;

Amine curing agent 40-60 parts by weight; preferably 45-55 parts by weight;

Solvent B 5-20 parts by weight; preferably 10-15 parts by weight; and/or,

The dosage ratio range of the A component and the B component is (3-5):1.

In a preferred embodiment of the invention,

The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenolic 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 pigments and fillers are one or more of silica, titanium dioxide, carbon black, iron red, barium sulfate, mica powder, and calcium carbonate; and/or,

The auxiliary agent is one or more of a dispersant, a defoaming agent, and a leveling agent; and/or,

The dispersant is a conventional dispersant in this field. In the present invention, it can be preferably HT-5000 (Hantai Chemical), HT-5020 (Hantai Chemical), HT-5040 (Hantai Chemical), WinSperse 3030 (Vipos) New Materials Shandong Co., Ltd.), WinSperse 3140 (Vipos New Materials Shandong Co., Ltd.), Lencolo1103 (Guangdong Lankelu New Materials Co., Ltd.); and/or,

The defoaming agent is a conventional defoaming agent in this field. In the present invention, it can be preferably UV-225 (Daejeon Chemical), DS-100 (Daejeon Chemical), silicone defoamer HT-508 (Hantai Chemical), At least one of AMXP902 (Anmei Technology Co., Ltd.); and/or,

The leveling agent is a conventional leveling agent in this field. In the present invention, it may be preferably At least one of WE-D819C (Anhui Jiazhi Xinnuo Chemical Co., Ltd.), GS5750 (GS Chemical), GS5411 (GS Chemical), IOTA-3000 (Anhui Ayota 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, and basic zinc sulfate micron flakes; and/ or,

The amino functional silane coupling agent is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane One or more of N-aminoethyl-3-aminopropylmethyldimethoxysilane; and/or,

The amine curing agent is one or more of phenolic amine, polyamide, aromatic amine, and alicyclic amine; and/or,

The solvent A and the solvent B are the same or different, and each independently preferably is one of xylene, methyl isobutyl ketone, methyl isobutyl amyl ketone, butyl acetate, n-butanol, and cyclohexanone, or Several kinds; and/or,

The solvent C is one or both of xylene and n-butanol.

The preparation method of the two-dimensional micro-nano material pre-dispersed slurry of the present invention preferably includes: placing the two-dimensional micro-nano material and 60-80% solvent C at the bottom of a three-necked flask, raising the temperature to 60-65°C, and adding dropwise to the flask at a uniform speed. A mixture of amino functional silane coupling agent and the remaining 20-40% solvent C. At this time, the mass ratio of the two-dimensional micro-nano material, solvent C and amino amino functional silane coupling agent is 1:5-10:0.03-0.1, Stirring allows the reaction system to be heated evenly, and the generated heat can be dissipated in time. The stirring reaction time is 1-2 hours, and the two-dimensional micro-nano material pre-dispersed slurry is obtained.

The fourth object of the present invention is to provide a method for preparing a multi-mechanism synergistic universal anti-corrosion coating according to the third object of the present invention, which includes: mixing each component of component A and component B according to the stated dosage, and then mixing A Component and component B are mixed according to the dosage ratio to obtain the multi-mechanism synergistic universal anti-corrosion coating.

The present invention can preferably adopt the following specific technical solutions:

The preparation method of component A preferably includes: sequentially weighing 100 parts by weight of interpenetrating network high-density epoxy resin, 40-60 parts by weight of corrosion inhibitor, 40-60 parts by weight of pigments and fillers, 3-5 parts by weight of additives, and solvent A 50-100 parts by weight, mix and disperse for 15 minutes at 2500 rpm, place it in a fast grinder and grind until the fineness is below 60 μm to obtain component A;

The preparation method of component B preferably includes: mixing 3-10 parts by weight of two-dimensional micro-nano material pre-dispersed slurry, amine 40-60 parts by weight of similar curing agent, 5-20 parts by weight of solvent B, mix and stir evenly to obtain component B;

The multi-mechanism synergistic universal anti-corrosion coating is obtained by mixing component A and component B in a dosage ratio of (3-5):1.

The multi-mechanism synergistic universal anti-corrosion coating of the present invention can be applied as an anti-corrosion coating on steel substrates, stainless steel substrates and ceramic substrates that require corrosion protection within the applicable period by brushing, spraying and roller coating.

The beneficial effects of the present invention are: the design of multi-mechanism collaborative universal anti-corrosion coatings carries out anti-corrosion coating formula design through dual mechanisms of inhibition and shielding, and the resulting coating has an ultra-dense three-dimensional space network system and a strongly closed two-dimensional micro-nano material skeleton Construction system, high strength, toughness and wear-resistant interpenetrating network matrix.

In the present invention, an interpenetrating network high-density epoxy resin based on antibacterial fluorine-modified epoxy vinyl ester resin and epoxy resin is used as the matrix resin of a multi-mechanism synergistic universal anti-corrosion coating, in which fluorine-modified epoxy vinyl ester The resin introduces fluorine-containing side chains. During the coating formation process, the fluorine segments tend to migrate to the surface of the anti-corrosion coating and are oriented. The hydrophobic protective barrier constructed increases the energy barrier for corrosion particles to enter the inside of the coating. The matrix resin design of the interpenetrating network further shortens the distance between the epoxy resin molecular segment nodes and enhances its dense sealing performance. Based on the marine environment, the chemical substances secreted during microbial corrosion have stronger permeability, and the resin body introduces indole compounds to provide corrosion inhibitory effects on microorganisms. In the present invention, two-dimensional micro-nano materials with a unique lamellar structure are chemically modified to improve their uniform dispersion and anti-agglomeration properties, and pre-dispersed two-dimensional micro-nano materials are prepared using aminosilane coupling agents containing aminosilane coupling agents. Slurry, two-dimensional micro-nano materials have amino active groups on the surface, which can establish chemical bonds with the epoxy groups in the epoxy resin. The two-dimensional micro-nano materials are oriented and interspersed in the three-dimensional space network of the resin at a specific density, effectively changing the corrosion particles. The diffusion path to the substrate blocks or prolongs the time for corrosion particles to reach the substrate, further increasing the inhibitory and shielding effect of anti-corrosion coatings.

The multi-mechanism synergistic universal anti-corrosion coating developed by the present invention meets the corrosion protection needs of various metal substrates under various corrosion conditions in the fields of marine engineering, petrochemical power construction, aerospace technology and national defense industry.

Detailed ways

The present invention will be described in detail below with reference to specific examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the protection scope of the present invention. Those skilled in the art will make reference to the present invention based on the content of the present invention. Some non-essential improvements and adjustments made by the invention still fall within the protection scope of the invention.

If the specific conditions are not specified in the examples, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer.

The raw materials used in the examples are all conventional commercially available raw materials.

The structural formula of Neoechinulin A indole alkaloid (Hubei Wonder Chemical Co., Ltd.) used in the examples is:

Among them, R ₂ and R ₃ are -H.

Preparation of antibacterial fluorine modified epoxy vinyl ester resin S1:

In a four-necked flask equipped with a temperature control device, a condensation device, a stirring device, a nitrogen inlet pipe and a liquid dripping device, add 44.3g of xylene/butyl acetate (the mass ratio of xylene to butyl acetate is 1 ( 0.0065mol) bisphenol A epoxy vinyl ester resin (Langfang Shengzi Anticorrosive Materials Co., Ltd., model UPR-FRP, its structural formula is:

Among them, n = 19, R ₄ and R ₅ are -CH ₃ ) and 0.5g azobisisovaleronitrile were mixed evenly, and evenly added dropwise to the reactant within 2h system, after the dropwise addition is completed, after 2 hours of incubation, continue to add dropwise a mixed solution of 0.2g tert-butyl peroxybenzoate and 6.5g xylene within 0.5 hours, incubate for 2 hours, cool down and discharge, and obtain a light yellow antibacterial fluorine modified ring. Oxyvinyl ester resin S1, its structural formula is as follows:

Among them, n=19, R _f is -CH ₂ (CF ₂ ) ₅ CHF ₂ , R ₁ is -CH ₃ , R ₄ and R ₅ are -CH ₃ , and R ₂ and R ₃ are -H.

Preparation of antibacterial fluorine modified epoxy vinyl ester resin S2:

In a four-necked flask equipped with a temperature control device, a condensation device, a stirring device, a nitrogen inlet pipe and a liquid dripping device, add 44.6g of xylene/n-butanol (the mass ratio of xylene to n-butanol is 1 :1) Mixed solvent, add nitrogen to the reaction system, raise the temperature to 95°C, and weigh 7.7g (0.0458mol) trifluoroethyl methacrylate, 4g (0.0124mol) Neoechinulin A indole alkaloid, 36g (0.0067mol) mol) bisphenol F epoxy vinyl ester resin (Langfang Rongjie Anticorrosive Materials Co., Ltd. 901 epoxy hexenyl resin, its structural formula is:

Among them, n = 19, R ₄ and R ₅ are -H) and 0.4g azobisisobutyronitrile were mixed evenly, and evenly added dropwise to the reaction system within 2h. After the dropwise addition was completed, after incubation for 2h, continue to add 0.5 A mixed solution of 0.3g tert-butyl peroxy-2-ethylhexanoate and 6.5g xylene was added dropwise within h, kept for 2h, cooled and discharged, to obtain a light yellow antibacterial fluorine-modified epoxy vinyl ester resin S2, which The structural formula is as follows:

Among them, n=19, R _f is -CH ₂ CF ₃ , R ₁ is -CH ₃ , R ₄ and R ₅ are -H, and R ₂ and R ₃ are -H.

Preparation of antibacterial fluorine modified epoxy vinyl ester resin S3:

In a four-necked flask equipped with a temperature control device, a condensation device, a stirring device, a nitrogen inlet pipe and a liquid dripping device, add 42.5g of xylene/cyclohexanone (the mass ratio of xylene to cyclohexanone is 1 ( 0.0066mol) bisphenol A epoxy vinyl ester resin (Langfang Shengzi Anticorrosive Materials Co., Ltd., model UPR-FRP) and 0.6g azobisisobutyronitrile were mixed evenly, and evenly added dropwise to the reaction system within 2 hours. After the dropwise addition is completed, after 2 hours of incubation, continue to add dropwise a mixed solution of 0.3g tert-butyl peroxy-2-ethylhexanoate and 6.5g xylene within 0.5 hours, incubate for 2 hours, cool down and discharge, to obtain light yellow antibacterial fluorine. Modified epoxy vinyl ester resin S3, its structural formula is as follows:

Among them, n=19, R _f is -CH ₂ CF ₂ CHFCF ₃ , R ₁ is -CH ₃ , R ₄ and R ₅ are -CH ₃ , and R ₂ and R ₃ are -H.

Preparation of graphene oxide pre-dispersed slurry T1:

Place 12.6g of graphene oxide powder and 64.8g of xylene at the bottom of a three-necked flask, raise the temperature to 60°C, and add 1g of aminoethylaminoethylaminopropyltrimethoxysilane (Momentive A-1130) dropwise into the flask at a constant rate. )and A mixture of 21.6g xylene was stirred for 1.5 hours while keeping the temperature constant to prepare graphene oxide pre-dispersed slurry T1.

Preparation of boron nitride pre-dispersed slurry T2:

Place 11.5g boron nitride powder and 65.7g xylene at the bottom of a three-necked flask, raise the temperature to 65°C, and add a mixture of 0.8g aminopropyltriethoxysilane and 22g xylene dropwise into the flask at a constant rate, keeping the temperature constant. Change and stir for 1.5h to obtain boron nitride pre-dispersed slurry T2.

Preparation of molybdenum disulfide pre-dispersed slurry T3:

Place 14.6g of molybdenum disulfide powder and 63.6g of xylene at the bottom of a three-necked flask, raise the temperature to 60°C, and add 0.6g of aminoethylaminoethylaminopropyltrimethoxysilane (Momentive A- 1130) and 21.2g of xylene, keep the temperature unchanged, and stir for 2 hours to prepare molybdenum disulfide pre-dispersed slurry T3.

Examples of multi-mechanism synergistic universal anti-corrosion coatings prepared based on antibacterial fluorine-modified epoxy vinyl ester resins S1-S3, two-dimensional micro-nano material pre-dispersed slurries T1-T3, and other anti-corrosion coating components are detailed in Table 1 and Table 2, and the details of each component of the comparative example are shown in Table 3.

Table 1

Table 2

table 3

The preparation process of the multi-mechanism synergistic universal anti-corrosion coating of Examples 1-7 is as follows (the amounts of each component are shown in Tables 1 and 2):

The preparation process of component A is as follows: weigh the interpenetrating network high-density epoxy resin, corrosion inhibitor, and functional filler in sequence. Materials, additives, and solvent A are dispersed at 2500 rpm for 15 minutes, and ground in a fast grinder until the fineness is below 60 μm;

The preparation process of component B is: two-dimensional micro-nano material pre-dispersed slurry, amine curing agent, and solvent B. Mix and stir evenly before use.

Mix the A component and B component obtained in Examples 1-7 according to the amounts shown in Table 1 and Table 2 evenly to obtain a multi-mechanism synergistic universal anti-corrosion coating. After coating on the tinplate, it is cured at room temperature for 24 hours to obtain multiple The mechanism cooperates with the universal anti-corrosion coating, and the coating thickness range is 170±20μm.

The preparation process of the anticorrosive coating of Comparative Examples 1-4 is the same as that of Example 1 (the dosage of each component of Comparative Examples 1-4 is shown in Table 3). The A1 component and The B1 components are all mixed evenly to obtain an anti-corrosion coating (in each comparative example, the two-dimensional micro-nano material pre-dispersed slurry is replaced with mica powder with anti-corrosion effect in equal amounts). It is coated on the tinplate and cured at room temperature for 24 hours. An anti-corrosion coating was obtained with a coating thickness range of 170±20μm.

Table 4 shows the performance indicators achieved by the multi-mechanism collaborative universal anti-corrosion coating of the present invention.

Table 4

Table 5 shows the performance indicators achieved by the anti-corrosion coating of the comparative example.

table 5

It can be seen from Table 4 and Table 5 that the multi-mechanism synergistic universal anti-corrosion coating prepared in Examples 1-7 is significantly better than the coating of Comparative Examples 1-4 in adhesion performance. The reason is that the modified epoxy vinyl ester resin and The interpenetrating network of epoxy resin enhances the bonding strength with the substrate, and in the curing agent system, the two-dimensional micro-nano material pre-dispersed slurry is modified with a silane coupling agent with amino functional groups. The amino silane coupling agent Plays an adhesion promoting role. The performance of the multi-mechanism synergistic universal anti-corrosion coating prepared in Examples 1-7 is significantly better than that of Comparative Examples 1-4 in neutral salt spray resistance test, damp heat resistance test and cathodic stripping resistance test. The reason is mainly due to the fluorine segment The hydrophobic protective barrier, the dense sealing effect of the matrix resin interpenetrating network, the antimicrobial group's resistance to microbial corrosion, and the two-dimensional sheet nanomaterials effectively change the diffusion path of corrosion particles to the matrix, blocking or prolonging the time for corrosion particles to reach the matrix. And two-dimensional nanomaterials have high specific surface area and mechanical properties, making them widely used to improve the corrosion resistance of anti-corrosion coatings.

Although the specific embodiments of the present invention are described in detail in conjunction with tables, this should not be understood as limiting the scope of protection of this patent. Within the scope described in the claims, those skilled in the art without experience Various modifications and transformations that can be made through creative work are still within the scope of protection of this patent.

Claims (10)

An antibacterial fluorine-modified epoxy vinyl ester resin, the structural formula of the antibacterial fluorine-modified epoxy vinyl ester resin is:
Among them, R ₁ is one of -H, -CH ₃ and -CH ₂ CH ₃ ; R ₂ is -H, -CH ₂ CH＝C(CH ₃ ) ₂ , -CH ₂ CH(OH)C(OH )(CH ₃ ) ₂ ; R ₃ is -H or -CH ₂ CH＝C(CH ₃ ) ₂ ; R _f is -CH ₂ CF ₃ , -CH ₂ CF ₂ CHFCF ₃ , -CH ₂ ( One of CF ₂ ) ₅ CHF ₂ , -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ; R ₄ and R ₅ are the same or different, each independently -H or -CH ₃ , n=10-30 . Antibacterial fluorine modified epoxy vinyl ester resin as claimed in claim 1, characterized in that: The R ₁ is -H or -CH ₃ ; and/or, the R ₂ is -H or -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ ; and/or, the R ₃ is -H; and/or, the R _f is -CH ₂ (CF ₂ ) ₅ CHF ₂ or -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ; and/or, the n=15-25. A method for preparing an antibacterial fluorine-modified epoxy vinyl ester resin as claimed in any one of claims 1 to 2, including fluorine-containing acrylate monomers, indole compounds and epoxy vinyl ester resin. The step of reacting the raw materials to obtain the antibacterial fluorine-modified epoxy vinyl ester resin. The preparation method according to claim 3, characterized in that: The structural formula of the fluorine-containing acrylate monomer is: Among them, R ₁ is one of -H, -CH ₃ and -CH ₂ CH ₃ ; 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 ; the fluorine-containing acrylate monomer is preferably trifluoroethyl methacrylate ester, one or more of hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, and tridecafluorooctyl methacrylate; and/or, The structural formula of the indole compound is: Among them, R ₂ is one of -H, -CH ₂ CH=C(CH ₃ ) ₂ and -CH ₂ CH(OH)C(OH)(CH ₃ ) ₂ ; R ₃ is -H or -CH ₂ CH=C(CH ₃ ) ₂ ; the indole compound is preferably at least one of dihydroxyisoechinulin A alkaloid, Neoechinulin A indole alkaloid, and echinulin A indole alkaloid, and more preferably Neoechinulin A indole alkaloid , at least one of echinulin and echinosporin; and/or, The structural formula of the epoxy vinyl ester resin is: Wherein, n is 10-30, R ₄ and R ₅ are the same or different, and each is independently -H or -CH ₃ . The preparation method according to claim 3, characterized in that: The molar ratio of the epoxy vinyl ester resin, fluorine-containing acrylate monomer, and indole compound is 1: (1-3): (1-3), preferably 1: (2-3): ( 2-3). The preparation method according to claim 3, characterized in that: The reaction temperature is 85-100°C, preferably 90-96°C; and/or the reaction time is 5-7h, preferably 5.5-6.5h. A multi-mechanism synergistic universal anti-corrosion coating, comprising the antibacterial fluorine-modified epoxy vinyl ester resin described in any one of claims 1-2 or the antibacterial fluorine-modified ring prepared by the method described in any one of claims 3-6 Oxygen vinyl ester resin. The multi-mechanism synergistic universal anti-corrosion coating as claimed in claim 7, characterized by: The multi-mechanism synergistic universal anti-corrosion coating includes component A and component B; The A component includes interpenetrating network high-density epoxy resin, corrosion inhibitors, pigments and fillers, additives and solvent A; the interpenetrating network high-density epoxy resin includes blended antibacterial fluorine-modified epoxy vinyl Ester resins and epoxy resins; 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 B component includes two-dimensional micro-nano material pre-dispersed slurry, amine curing agent and solvent B; the two-dimensional micro-nano material pre-dispersed slurry consists of two-dimensional micro-nano material, solvent C and amino functional group silane coupling agent Prepared from the components included; Based on 100 parts by weight of interpenetrating network high-density epoxy resin,
Two-dimensional micro-nano material pre-dispersed slurry 3 to 10 parts by weight; preferably 5 to 8 parts by weight;
Amine curing agent: 40 to 60 parts by weight; preferably 45 to 55 parts by weight;
Solvent B 5 to 20 parts by weight; preferably 10 to 15 parts by weight; and/or, The dosage ratio range of the A component and the B component is (3-5):1. The multi-mechanism synergistic universal anti-corrosion coating as claimed in claim 8, characterized by: The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenolic 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 pigments and fillers are silica, titanium dioxide, carbon black, iron red, barium sulfate, mica powder, carbonic acid One or more types of calcium; and/or, The auxiliary agent is one or more of a dispersant, a defoaming 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 aminopropyltriethoxysilane, aminopropyltrimethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane One or more of N-aminoethyl-3-aminopropylmethyldimethoxysilane; and/or, The amine curing agent is one or more of phenolic amine, polyamide, aromatic amine, and alicyclic amine; and/or, The solvent A and the solvent B are the same or different, and each independently preferably is one of xylene, methyl isobutyl ketone, methyl isobutyl amyl ketone, butyl acetate, n-butanol, and cyclohexanone, or Several kinds; and/or, The solvent C is one or both of xylene and n-butanol. A method for preparing a multi-mechanism synergistic universal anti-corrosion coating as described in any one of claims 8-9, including: mixing each component of A component and B component according to the stated dosage, and then mixing A component and B component The components are mixed according to the dosage ratio to obtain the multi-mechanism synergistic universal anti-corrosion coating.