Primer-topcoat anticorrosive paint and preparation method thereof

Abstract

The invention relates to the field of anticorrosive paint, in particular to primer-topcoat anticorrosive paint and a preparation method thereof, which are used for solving the problems that the existing primer-topcoat anticorrosive paint is not ideal in anticorrosive performance, the coating is easy to damage to crack and fall off, the anticorrosive effect cannot be continuously provided after cracking and falling off, and the long-term anticorrosive requirement cannot be met. According to the anti-corrosion coating, the anti-corrosion cross-linked emulsion serves as a main raw material, the pentaerythritol tetrakis (3-mercaptopropionic acid) serves as a cross-linking agent, a compact anti-corrosion coating can be formed on the surface of a metal matrix, the anti-corrosion coating has excellent anti-corrosion performance, contact and corrosion of a corrosion medium to the metal matrix are effectively prevented, and the corrosion resistance of the metal matrix is improved. The anti-corrosion coating can still keep good performance under the severe environment condition, the service life of the anti-corrosion coating is prolonged, the anti-corrosion coating contains the naphthalene ring bis-imidazole onium salt and the zinc phosphate, corrosion inhibition treatment can be conducted on a metal matrix after the coating is damaged, and the protection effect of the anti-corrosion coating is further improved.

Description

Technical Field

[0001] The present invention relates to the field of anti-corrosion coatings, and in particular to a bottom-and-top integrated anti-corrosion coating and a preparation method thereof. Background Art

[0002] Corrosion is a common problem in metal structures, seriously impacting their service life and safety. To prevent corrosion, metal surfaces are typically coated with anti-corrosion coatings. Traditional anti-corrosion coatings typically consist of a primer and a topcoat, making the application process cumbersome. Furthermore, compatibility issues between the different layers can affect the overall performance of the coating.

[0003] A new type of anti-corrosion coating that combines the functions of a primer and a topcoat, allowing for a single application to create a coating with both anti-corrosion and decorative properties. This simplifies the construction process and improves efficiency, while also reducing interfacial issues between the coatings and enhancing adhesion and corrosion resistance. However, the corrosion resistance of currently available anti-corrosion coatings on the market is suboptimal. The coatings are easily damaged, cracking, and flaking. Once cracked or flaked, they no longer provide corrosion protection, failing to meet long-term corrosion protection requirements.

[0004] Therefore, it is of great practical significance to develop a bottom-surface integrated anti-corrosion coating and a preparation method thereof. Summary of the Invention

[0005] In order to overcome the above-mentioned technical problems, the purpose of the present invention is to provide a bottom-and-top integrated anti-corrosion coating and a preparation method thereof, which solves the problem that the existing bottom-and-top integrated anti-corrosion coating has unsatisfactory anti-corrosion performance, the coating is easily damaged and cracked and falls off, and after cracking and falling off, it can no longer provide anti-corrosion effect and cannot meet the needs of long-term anti-corrosion.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A bottom-and-top integrated anti-corrosion coating comprising the following components in parts by weight:

[0008] 55-65 parts of anticorrosive cross-linked emulsion, 0.2-1.4 parts of naphthalene ring bisimidazole salt, 2-4 parts of propylene glycol methyl ether, 0.3-0.5 parts of zinc phosphate, 0.5-0.7 parts of wetting agent, 0.1-0.3 parts of defoaming agent, 5.5-9.5 parts of barium sulfate, 2-6 parts of titanium dioxide, 0.3-1.1 parts of cross-linking agent, 0.2-0.4 parts of thickener and 0.1-0.3 parts of antioxidant;

[0009] Wherein, the anticorrosive cross-linked emulsion is prepared by the following steps:

[0010] Step a1: resveratrol, epichlorohydrin, and tetrabutylammonium bromide are added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen is introduced for protection. The mixture is stirred at a temperature of 25-30° C. and a stirring rate of 200-300 r / min for 10-20 minutes, and then the temperature is raised to 90-95° C. and the stirring reaction is continued for 6-8 hours. The temperature is then lowered to 60-65° C. and sodium hydroxide solution is added, and the stirring reaction is continued for 5-6 hours. After the reaction is completed, the reaction product is cooled to room temperature, and then washed with distilled water 3-5 times, and then the solvent is removed by rotary evaporation to obtain a polyepoxy monomer;

[0011] Step a2: Add styrene, butyl acrylate, methyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate, a polyepoxy monomer, hydroxyethyl acrylate, a compound emulsifier and deionized water to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and stir the reaction at a temperature of 25-30°C and a stirring rate of 200-300 r / min for 30-40 minutes. Then, add the compound initiator under the condition of raising the temperature to 70-75°C and continue stirring the reaction for 30-40 minutes. Then, raise the temperature to 90-95°C and continue stirring the reaction for 2-4 hours. After the reaction is completed, cool the reaction product to room temperature to obtain an anti-corrosion cross-linked emulsion.

[0012] As a further solution of the present invention: the usage ratio of the resveratrol, epichlorohydrin, tetrabutylammonium bromide and sodium hydroxide solution in step a1 is 10 mmol: 130-150 mmol: 0.8-1.2 g: 70-80 mL.

[0013] As a further solution of the present invention: the mass fraction of the sodium hydroxide solution in step a1 is 20-30%.

[0014] As a further embodiment of the present invention, the amount ratio of the styrene, butyl acrylate, methyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate, polyepoxy monomer, hydroxyethyl acrylate, compound emulsifier, deionized water and compound initiator in step a2 is 18-22 g: 10-12 g: 4-6 g: 3-5 g: 2-8 g: 1-7 g: 0.5-1.5 g: 0.2-0.4 g: 60-70 mL: 0.3-0.5 g.

[0015] As a further solution of the present invention: the compound emulsifier in step a2 is a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1.

[0016] As a further solution of the present invention: the composite initiator in step a2 is a mixture of cumene hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1.

[0017] As a further solution of the present invention: the naphthyl ring bisimidazolium salt is prepared by the following steps:

[0018] 1-Octyl imidazole, 2,6-bis(bromomethyl)naphthalene and anhydrous toluene are added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen protection is introduced. The mixture is stirred and reacted for 30-40 minutes at a temperature of 25-30° C. and a stirring rate of 200-300 r / min. The mixture is then heated to 110-120° C. and the stirring reaction is continued for 10-15 hours. After the reaction is completed, the reaction product is cooled to room temperature, and the solvent is removed by rotary evaporation. The product is then added to anhydrous tetrahydrofuran, allowed to stand for 2-3 hours, and then centrifuged. The precipitate is washed with anhydrous acetone 2-3 times, and then placed in a vacuum drying oven and dried at a temperature of 40-45° C. for 4-6 hours to obtain a naphthalene ring bisimidazole salt.

[0019] As a further embodiment of the present invention, the usage ratio of the 1-octylimidazole, 2,6-bis(bromomethyl)naphthalene and anhydrous toluene is 20 mmol:10 mmol:80-90 mL.

[0020] As a further solution of the present invention: a method for preparing a bottom-and-top integrated anti-corrosion coating comprises the following steps:

[0021] Step 1: Weigh 55-65 parts of anticorrosive cross-linked emulsion, 0.2-1.4 parts of naphthalene ring bisimidazolium salt, 2-4 parts of propylene glycol methyl ether, 0.3-0.5 parts of zinc phosphate, 0.5-0.7 parts of wetting agent, 0.1-0.3 parts of defoaming agent, 5.5-9.5 parts of barium sulfate, 2-6 parts of titanium dioxide, 0.3-1.1 parts of cross-linking agent, 0.2-0.4 parts of thickener and 0.1-0.3 parts of antioxidant according to weight parts, and set aside;

[0022] Step 2: Add the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 800-1000r / min to obtain a bottom-to-top integrated anti-corrosion coating.

[0023] As a further solution of the present invention: the wetting agent is a mixture of VOK-490 wetting and dispersing agent and Tego4100 wetting agent in a mass ratio of 1:1.

[0024] As a further solution of the present invention: the defoaming agent is BYK-1790 defoaming agent.

[0025] As a further embodiment of the present invention: the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionate).

[0026] As a further solution of the present invention: the thickener is sodium carboxymethyl cellulose.

[0027] As a further solution of the present invention: the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1.

[0028] Beneficial effects of the present invention:

[0029] The present invention discloses a bottom-surface integrated anticorrosive coating and a preparation method thereof. The method comprises the following steps: mixing an anticorrosive cross-linking emulsion, a naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, a wetting agent, a defoaming agent, barium sulfate, titanium dioxide, a cross-linking agent, a thickener, and an antioxidant to obtain a bottom-surface integrated anticorrosive coating. The anticorrosive coating uses the anticorrosive cross-linking emulsion as a main raw material and uses pentaerythritol tetrakis(3-mercaptopropionic acid) as a cross-linking agent. The anticorrosive coating can form a dense anticorrosive coating on the surface of a metal substrate. The anticorrosive coating has excellent anticorrosive performance and effectively prevents corrosion media from being formed. The anti-corrosion coating can prevent the contact and erosion of the metal substrate by the substance, and the anti-corrosion coating can still maintain good performance under harsh environmental conditions, thereby extending the service life of the anti-corrosion coating. The anti-corrosion coating contains naphthalene ring bisimidazolium salt and zinc phosphate, which can perform corrosion inhibition treatment on the metal substrate after the coating is damaged, thereby further improving the protective effect of the anti-corrosion coating. At the same time, the preparation method is simple in process and easy to operate, and is suitable for large-scale industrial production. The anti-corrosion coating prepared has the functions of both primer and topcoat, and can be applied in one time, which simplifies the construction process and improves construction efficiency.

[0030] In the process of preparing the bottom-and-top integrated anti-corrosion coating, an anti-corrosion cross-linked emulsion is first prepared. First, resveratrol and epichlorohydrin are reacted, and multiple hydroxyl groups on the resveratrol and epichlorohydrin undergo a ring-opening-closing reaction, thereby introducing multiple epoxy groups to obtain a multi-epoxy monomer. Since the multi-epoxy monomer contains hydroxyl groups, it is polymerized with styrene, butyl acrylate, methyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate and hydroxyethyl acrylate under the action of a composite initiator to form a polymer to obtain an anti-corrosion cross-linked emulsion; the polymer molecular structure of the anti-corrosion cross-linked emulsion contains a large number of fluorine-containing groups, which gives the anti-corrosion coating excellent chemical resistance. At the same time, its molecular structure also contains a large number of epoxy groups, which react with pentaerythritol tetrakis(3-mercaptopropionate) ester with multiple thiol groups to form a dense three-dimensional cross-linked network structure, thereby improving the density of the anti-corrosion coating and further improving the chemical resistance of the anti-corrosion coating, thereby effectively protecting the metal substrate and improving the anti-corrosion performance of the metal substrate.

[0031] In the process of preparing the bottom-and-top integrated anti-corrosion coating, a naphthalene ring bisimidazole salt is also prepared. 1-octylimidazole and 2,6-bis(bromomethyl)naphthalene are reacted, and the imidazole ring on the 1-octylimidazole reacts with the bromine atom on the 2,6-bis(bromomethyl)naphthalene to form an imidazolium cation, thereby obtaining a naphthalene ring bisimidazole salt. The imidazolium cation on the naphthalene ring bisimidazole salt can electrostatically adsorb the negatively charged area formed on the surface of the metal substrate due to corrosion, thereby forming a continuous and dense protective film on the metal surface, thereby effectively preventing the corrosive medium from corroding the metal substrate surface. In addition, the film can be used in combination with the anti-rust effect of zinc phosphate, thereby significantly improving the corrosion resistance of the metal. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0033] Example 1:

[0034] This embodiment is a method for preparing a bottom-to-top integrated anti-corrosion coating, comprising the following steps:

[0035] Step S1: 10 mmol of resveratrol, 130 mmol of epichlorohydrin, and 0.8 g of tetrabutylammonium bromide were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 200 r / min for 10 minutes, and then the temperature was raised to 90° C. and the stirring reaction was continued for 6 hours. The temperature was then lowered to 60° C. and 70 mL of a 20% sodium hydroxide solution was added and the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was cooled to room temperature, washed with distilled water three times, and then rotary evaporated to remove the solvent to obtain a polyepoxy monomer;

[0036] Step S2: 18g of styrene, 10g of butyl acrylate, 4g of methyl methacrylate, 3g of butyl methacrylate, 2g of trifluoroethyl methacrylate, 1g of a polyepoxy monomer, 0.5g of hydroxyethyl acrylate, 0.2g of a compound emulsifier and 60mL of deionized water were added to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and the mixture was stirred and reacted at a temperature of 25°C and a stirring rate of 200r / min for 30min. After that, 0.3g of a compound initiator was added under the condition of heating to 70°C and stirring was continued for 30min. After that, the mixture was heated to 90°C and stirring was continued for 2h. After the reaction was completed, the reaction product was cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier was a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator was a mixture of isopropyl benzene hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0037] Step S3: 20mmol 1-octylimidazole, 10mmol 2,6-bis(bromomethyl)naphthalene and 80mL anhydrous toluene were added to a three-necked flask equipped with an agitator, a thermometer and an air guide tube, and nitrogen protection was introduced. The mixture was stirred at 25°C and a stirring rate of 200r / min for 30min, and then the mixture was heated to 110°C and the stirring reaction was continued for 10h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The product was then added to anhydrous tetrahydrofuran, allowed to stand for 2h, and then centrifuged. The precipitate was washed twice with anhydrous acetone, and then placed in a vacuum drying oven and dried at 40°C for 4h to obtain a naphthalene ring bisimidazole salt.

[0038] Step S4: Weigh 55 parts of anticorrosive cross-linked emulsion, 0.2 parts of naphthalene ring bisimidazole salt, 2 parts of propylene glycol methyl ether, 0.3 parts of zinc phosphate, 0.5 parts of wetting agent, 0.1 parts of defoaming agent, 5.5 parts of barium sulfate, 2 parts of titanium dioxide, 0.3 parts of cross-linking agent, 0.2 parts of thickener and 0.1 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting dispersant and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0039] Step S5: Add the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix for 30 minutes at a temperature of 25°C and a stirring rate of 800 r / min to obtain a bottom-and-top integrated anti-corrosion coating.

[0040] Example 2:

[0041] This embodiment is a method for preparing a bottom-to-top integrated anti-corrosion coating, comprising the following steps:

[0042] Step S1: 10 mmol of resveratrol, 140 mmol of epichlorohydrin, and 1 g of tetrabutylammonium bromide were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 250 r / min for 15 minutes, and then the temperature was raised to 92° C. and the stirring reaction was continued for 7 hours. The temperature was then lowered to 62° C. and 75 mL of a 25% sodium hydroxide solution was added and the stirring reaction was continued for 5.5 hours. After the reaction was completed, the reaction product was cooled to room temperature, washed with distilled water 4 times, and then the solvent was removed by rotary evaporation to obtain a polyepoxy monomer;

[0043] Step S2: 20g of styrene, 11g of butyl acrylate, 5g of methyl methacrylate, 4g of butyl methacrylate, 5g of trifluoroethyl methacrylate, 4g of a polyepoxy monomer, 1g of hydroxyethyl acrylate, 0.3g of a compound emulsifier and 65mL of deionized water were added to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and the mixture was stirred and reacted at a temperature of 28°C and a stirring rate of 250r / min for 35min. After that, 0.4g of a compound initiator was added under the condition of raising the temperature to 72°C and continuing to stir and react for 35min. After that, the mixture was raised to 92°C and continued to stir and react for 3h. After the reaction, the reaction product was cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier was a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator was a mixture of isopropyl hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0044] Step S3: 20mmol 1-octylimidazole, 10mmol 2,6-bis(bromomethyl)naphthalene and 85mL anhydrous toluene are added to a three-necked flask equipped with an agitator, a thermometer and an air guide tube, and nitrogen protection is introduced. The reaction is stirred at 28°C and a stirring rate of 250r / min for 35min, and then the temperature is raised to 115°C and the stirring reaction is continued for 12h. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation. The product is then added to anhydrous tetrahydrofuran, and then allowed to stand for 2.5h. The product is then centrifuged and washed twice with anhydrous acetone. The precipitate is then placed in a vacuum drying oven and dried at 42°C for 5h to obtain a naphthalene ring bisimidazole salt.

[0045] Step S4: Weigh 60 parts of anticorrosive cross-linked emulsion, 0.8 parts of naphthalene ring bisimidazole salt, 3 parts of propylene glycol methyl ether, 0.4 parts of zinc phosphate, 0.6 parts of wetting agent, 0.2 parts of defoaming agent, 7.5 parts of barium sulfate, 4 parts of titanium dioxide, 0.7 parts of cross-linking agent, 0.3 parts of thickener and 0.2 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting dispersant and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0046] Step S5: Add the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix for 35 minutes at a temperature of 28° C. and a stirring rate of 900 r / min to obtain a bottom-to-top integrated anti-corrosion coating.

[0047] Example 3:

[0048] This embodiment is a method for preparing a bottom-to-top integrated anti-corrosion coating, comprising the following steps:

[0049] Step S1: 10 mmol of resveratrol, 150 mmol of epichlorohydrin, and 1.2 g of tetrabutylammonium bromide were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 20 minutes, and then the temperature was raised to 95° C. and the stirring reaction was continued for 8 hours. The temperature was then lowered to 65° C. and 80 mL of a 30% by mass sodium hydroxide solution was added and the stirring reaction was continued for 6 hours. After the reaction was completed, the reaction product was cooled to room temperature, washed with distilled water 5 times, and then rotary evaporated to remove the solvent to obtain a polyepoxy monomer;

[0050] Step S2: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 8g of trifluoroethyl methacrylate, 7g of a polyepoxy monomer, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water were added to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and the mixture was stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator was added under the condition of heating to 75°C and the stirring reaction was continued for 40min. After that, the mixture was heated to 95°C and the stirring reaction was continued for 4h. After the reaction was completed, the reaction product was cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier was a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator was a mixture of isopropyl benzene hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0051] Step S3: 20mmol 1-octylimidazole, 10mmol 2,6-bis(bromomethyl)naphthalene and 90mL anhydrous toluene were added to a three-necked flask equipped with an agitator, a thermometer and an air guide tube, and nitrogen protection was introduced. The reaction was stirred at 30°C and a stirring rate of 300r / min for 40min, and then the temperature was raised to 120°C and the stirring reaction was continued for 15h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation. The product was then added to anhydrous tetrahydrofuran, and then allowed to stand for 3h. The product was then centrifuged and washed 3 times with anhydrous acetone. The precipitate was then placed in a vacuum drying oven and dried at 45°C for 6h to obtain a naphthalene ring bisimidazole salt.

[0052] Step S4: Weigh 65 parts of anticorrosive cross-linked emulsion, 1.4 parts of naphthalene ring bisimidazole salt, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting dispersant and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0053] Step S5: Add the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix at a temperature of 30°C and a stirring rate of 1000 r / min for 40 minutes to obtain a bottom-to-top integrated anti-corrosion coating.

[0054] Comparative Example 1:

[0055] This comparative example is a method for preparing a bottom-and-top integrated anti-corrosion coating, comprising the following steps:

[0056] Step S1: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water are added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture is stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator is added under the condition of heating to 75°C and the stirring reaction is continued for 40min, and then the mixture is heated to 95°C and the stirring reaction is continued for 4h. After the reaction is completed, the reaction product is cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier is a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator is a mixture of isopropyl hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0057] Step S2: Weigh 65 parts of anti-corrosion cross-linked emulsion, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting and dispersing agent and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0058] Step S3: Add the anti-corrosion cross-linked emulsion, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix at a temperature of 30° C. and a stirring rate of 1000 r / min for 40 minutes to obtain a bottom-to-top integrated anti-corrosion coating.

[0059] Comparative Example 2:

[0060] This comparative example is a method for preparing a bottom-and-top integrated anti-corrosion coating, comprising the following steps:

[0061] Step S1: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 8g of trifluoroethyl methacrylate, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water are added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture is stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator is added under the condition of heating to 75°C and the stirring reaction is continued for 40min, and then the mixture is heated to 95°C and the stirring reaction is continued for 4h. After the reaction is completed, the reaction product is cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier is a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator is a mixture of isopropyl hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0062] Step S2: Weigh 65 parts of anti-corrosion cross-linked emulsion, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting and dispersing agent and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0063] Step S3: Add the anti-corrosion cross-linked emulsion, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix at a temperature of 30° C. and a stirring rate of 1000 r / min for 40 minutes to obtain a bottom-to-top integrated anti-corrosion coating.

[0064] Comparative Example 3:

[0065] This comparative example is a method for preparing a bottom-and-top integrated anti-corrosion coating, comprising the following steps:

[0066] Step S1: 10 mmol of resveratrol, 150 mmol of epichlorohydrin, and 1.2 g of tetrabutylammonium bromide were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 20 minutes, and then the temperature was raised to 95° C. and the stirring reaction was continued for 8 hours. The temperature was then lowered to 65° C. and 80 mL of a 30% by mass sodium hydroxide solution was added and the stirring reaction was continued for 6 hours. After the reaction was completed, the reaction product was cooled to room temperature, washed with distilled water 5 times, and then rotary evaporated to remove the solvent to obtain a polyepoxy monomer;

[0067] Step S2: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 7g of a polyepoxy monomer, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water were added to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and the mixture was stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator was added under the condition of heating to 75°C and stirring was continued for 40min, and then the mixture was heated to 95°C and stirring was continued for 4h. After the reaction, the reaction product was cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier was a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator was a mixture of isopropyl hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0068] Step S3: Weigh 65 parts of anti-corrosion cross-linked emulsion, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting and dispersing agent and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0069] Step S4: adding the anti-corrosion cross-linked emulsion, propylene glycol methyl ether, zinc phosphate, a wetting agent, a defoaming agent, barium sulfate, titanium dioxide, a cross-linking agent, a thickener and an antioxidant into a mixer, stirring and mixing for 40 minutes at a temperature of 30° C. and a stirring rate of 1000 r / min to obtain a bottom-to-top integrated anti-corrosion coating.

[0070] Comparative Example 4:

[0071] This comparative example is a method for preparing a bottom-and-top integrated anti-corrosion coating, comprising the following steps:

[0072] Step S1: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water are added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture is stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator is added under the condition of heating to 75°C and the stirring reaction is continued for 40min, and then the mixture is heated to 95°C and the stirring reaction is continued for 4h. After the reaction is completed, the reaction product is cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier is a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator is a mixture of isopropyl hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0073] Step S2: 20mmol 1-octylimidazole, 10mmol 2,6-bis(bromomethyl)naphthalene and 90mL anhydrous toluene are added to a three-necked flask equipped with an agitator, a thermometer and an air guide tube, and nitrogen protection is introduced. The reaction is stirred at 30°C and a stirring rate of 300r / min for 40min, and then the temperature is raised to 120°C and the stirring reaction is continued for 15h. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation. The product is then added to anhydrous tetrahydrofuran, and then allowed to stand for 3h. The precipitate is then centrifuged and washed 3 times with anhydrous acetone. The precipitate is then placed in a vacuum drying oven and dried at 45°C for 6h to obtain a naphthalene ring bisimidazole salt.

[0074] Step S3: Weigh 65 parts of anticorrosive cross-linked emulsion, 1.4 parts of naphthalene ring bisimidazole salt, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting dispersant and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0075] Step S4: adding the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stirring and mixing for 40 minutes at a temperature of 30°C and a stirring rate of 1000 r / min to obtain a bottom-to-top integrated anti-corrosion coating.

[0076] Comparative Example 5:

[0077] This comparative example is a method for preparing a bottom-and-top integrated anti-corrosion coating, comprising the following steps:

[0078] Step S1: 10 mmol of resveratrol, 150 mmol of epichlorohydrin, and 1.2 g of tetrabutylammonium bromide were added to a three-necked flask equipped with a stirrer, a thermometer, and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 20 minutes, and then the temperature was raised to 95° C. and the stirring reaction was continued for 8 hours. The temperature was then lowered to 65° C. and 80 mL of a 30% by mass sodium hydroxide solution was added and the stirring reaction was continued for 6 hours. After the reaction was completed, the reaction product was cooled to room temperature, washed with distilled water 5 times, and then rotary evaporated to remove the solvent to obtain a polyepoxy monomer;

[0079] Step S2: 22g of styrene, 12g of butyl acrylate, 6g of methyl methacrylate, 5g of butyl methacrylate, 8g of trifluoroethyl methacrylate, 7g of a polyepoxy monomer, 1.5g of hydroxyethyl acrylate, 0.4g of a compound emulsifier and 70mL of deionized water were added to a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, and the mixture was stirred and reacted at a temperature of 30°C and a stirring rate of 300r / min for 40min. After that, 0.5g of a compound initiator was added under the condition of heating to 75°C and the stirring reaction was continued for 40min. After that, the mixture was heated to 95°C and the stirring reaction was continued for 4h. After the reaction was completed, the reaction product was cooled to room temperature to obtain an anti-corrosion cross-linked emulsion; the compound emulsifier was a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:1; the compound initiator was a mixture of isopropyl benzene hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:1;

[0080] Step S3: Weigh 65 parts of anti-corrosion cross-linked emulsion, 4 parts of propylene glycol methyl ether, 0.5 parts of zinc phosphate, 0.7 parts of wetting agent, 0.3 parts of defoaming agent, 9.5 parts of barium sulfate, 6 parts of titanium dioxide, 1.1 parts of cross-linking agent, 0.4 parts of thickener and 0.3 parts of antioxidant according to weight parts, and set aside; the wetting agent is a mixture of VOK-490 wetting and dispersing agent and tego4100 wetting agent in a mass ratio of 1:1; the defoaming agent is BYK-1790 defoaming agent; the cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionic acid); the thickener is sodium carboxymethyl cellulose; the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1;

[0081] Step S4: adding the anti-corrosion cross-linked emulsion, propylene glycol methyl ether, zinc phosphate, a wetting agent, a defoaming agent, barium sulfate, titanium dioxide, a cross-linking agent, a thickener and an antioxidant into a mixer, stirring and mixing for 40 minutes at a temperature of 30° C. and a stirring rate of 1000 r / min to obtain a bottom-to-top integrated anti-corrosion coating.

[0082] A bottom-to-top anti-corrosion coating of Examples 1-3 and Comparative Examples 1-5 was sprayed onto the surface of a clean tinplate to form an anti-corrosion coating with a thickness of 50±2 μm. Performance tests were then conducted, and the test results are shown in the following table:

[0083]

[0084] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-5, it can be seen that the bottom-and-top integrated anti-corrosion coating of the present application has excellent anti-corrosion performance.

[0085] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0086] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the scope of protection of the present invention.

Claims

1. A bottom-to-top anti-corrosion coating, characterized in that: It comprises the following components in parts by weight: 55-65 parts of anticorrosive cross-linked emulsion, 0.2-1.4 parts of naphthalene ring bisimidazole salt, 2-4 parts of propylene glycol methyl ether, 0.3-0.5 parts of zinc phosphate, 0.5-0.7 parts of wetting agent, 0.1-0.3 parts of defoaming agent, 5.5-9.5 parts of barium sulfate, 2-6 parts of titanium dioxide, 0.3-1.1 parts of cross-linking agent, 0.2-0.4 parts of thickener and 0.1-0.3 parts of antioxidant; Wherein, the anticorrosive cross-linked emulsion is prepared by the following steps: Step a1: stirring resveratrol, epichlorohydrin and tetrabutylammonium bromide to react, then adding sodium hydroxide solution and continuing to stir the reaction. After the reaction is completed, the reaction product is cooled, washed, and rotary evaporated to obtain a polyepoxy monomer; Step a2: Styrene, butyl acrylate, methyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate, polyepoxy monomer, hydroxyethyl acrylate, compound emulsifier and deionized water are stirred and reacted, and then a compound initiator is added and the stirring reaction is continued. After the reaction is completed, the reaction product is cooled to room temperature to obtain an anti-corrosion cross-linked emulsion.

2. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The usage ratio of the resveratrol, epichlorohydrin, tetrabutylammonium bromide and sodium hydroxide solution in step a1 is 10 mmol: 130-150 mmol: 0.8-1.2 g: 70-80 mL.

3. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The mass fraction of the sodium hydroxide solution in step a1 is 20-30%.

4. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The amount ratio of the styrene, butyl acrylate, methyl methacrylate, butyl methacrylate, trifluoroethyl methacrylate, polyepoxy monomer, hydroxyethyl acrylate, compound emulsifier, deionized water and compound initiator in step a2 is 18-22g: 10-12g: 4-6g: 3-5g: 2-8g: 1-7g: 0.5-1.5g: 0.2-0.4g: 60-70mL: 0.3-0.5g.

5. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The compound emulsifier in step a2 is a mixture of emulsifier OP-10 and emulsifier TO-9 in a mass ratio of 1:

1.

6. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The composite initiator in step a2 is a mixture of cumene hydroperoxide and dibenzoyl peroxide in a mass ratio of 1:

1.

7. The bottom-to-top integrated anti-corrosion coating according to claim 1, characterized in that: The naphthalene ring bisimidazolium salt is prepared by the following steps: 1-Octyl imidazole, 2,6-bis(bromomethyl)naphthalene and anhydrous toluene are stirred for reaction. After the reaction, the reaction product is cooled, then rotary evaporated, and then added to anhydrous tetrahydrofuran. The product is then allowed to stand and centrifuged. The precipitate is washed and dried to obtain a naphthalene ring bisimidazole salt.

8. The bottom-to-top integrated anti-corrosion coating according to claim 7, characterized in that: The usage ratio of the 1-octylimidazole, 2,6-bis(bromomethyl)naphthalene and anhydrous toluene is 20 mmol:10 mmol:80-90 mL.

9. A method for preparing a bottom-and-top integrated anti-corrosion coating, characterized in that: The following steps are involved: Step 1: Weigh 55-65 parts of anticorrosive cross-linked emulsion, 0.2-1.4 parts of naphthalene ring bisimidazolium salt, 2-4 parts of propylene glycol methyl ether, 0.3-0.5 parts of zinc phosphate, 0.5-0.7 parts of wetting agent, 0.1-0.3 parts of defoaming agent, 5.5-9.5 parts of barium sulfate, 2-6 parts of titanium dioxide, 0.3-1.1 parts of cross-linking agent, 0.2-0.4 parts of thickener and 0.1-0.3 parts of antioxidant according to weight parts, and set aside; Step 2: Add the anti-corrosion cross-linked emulsion, naphthalene ring bisimidazole salt, propylene glycol methyl ether, zinc phosphate, wetting agent, defoaming agent, barium sulfate, titanium dioxide, cross-linking agent, thickener and antioxidant into a mixer, stir and mix for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 800-1000r / min to obtain a bottom-to-top integrated anti-corrosion coating.

10. The method for preparing a bottom-to-top integrated anti-corrosion coating according to claim 9, characterized in that: The wetting agent is a mixture of VOK-490 wetting and dispersing agent and Tego4100 wetting agent in a mass ratio of 1:1; The defoamer is BYK-1790 defoamer; The cross-linking agent is pentaerythritol tetrakis(3-mercaptopropionate); The thickener is sodium carboxymethyl cellulose; The antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1.

Images