Anti-rust and anti-corrosion coating for ships and preparation method thereof

Abstract

The invention provides an anti-rust and anti-corrosion coating for ships and a preparation method thereof. The anti-rust and anti-corrosion coating for the ship is prepared from the following components in percentage by mass: 40 to 70 percent of epoxy emulsion, 10 to 20 percent of polyether amine curing agent, 5 to 10 percent of styryl POSS polymer, 10 to 15 percent of anti-rust filler, 10 to 40 percent of deionized water and 1 to 3 percent of additive. The added styryl POSS polymer and the epoxy emulsion are subjected to a grafting reaction to form covalent bonding, the grafting action enables the styryl POSS polymer to serve as a catenary to be combined with the epoxy emulsion, the obdurability of the coating is enhanced, the epoxy emulsion and the polyether amine curing agent are combined to act together, and the coating has the good anti-corrosion effect. The marine paint has the advantages that the marine paint is adsorbed on all oxide substrates of a ship through static electricity and a donor-acceptor interaction mechanism, so that a coating layer formed by the marine paint can fully cover the surface of the ship, a uniform and compact protective layer is formed, oxygen and molecules can be effectively isolated, and the anti-corrosion and anti-rust effects are further improved.

Description

Technical Field

[0001] The invention relates to the technical field of ship coatings, in particular to an anti-rust and anti-corrosion coating for ships and a preparation method thereof. Background Art

[0002] As we all know, ships have been in an extremely harsh marine environment since they were launched, and the hull plates are generally made of steel. Long-term immersion in seawater is prone to electrochemical corrosion. In addition, the hull will collide with the seawater due to the forward power of the ship during navigation, resulting in strong fluid dynamics in the seawater, which will have a huge impact on the underwater hull coating. After the coating is damaged, pitting will occur, further aggravating the electrochemical corrosion of the hull. When the ship is docked, the fender will cause certain wear on the outer shell coating near the waterline of the ship's side, which will aggravate the oxidation of iron elements and cause corrosion. Therefore, the coating used for ships needs to have not only excellent anti-rust and anti-corrosion properties, but also high wear resistance and toughness. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention provides an anti-rust and anti-corrosion coating for ships and a preparation method thereof, which solves the problems raised in the above-mentioned background technology by compounding styrene-based POSS polymer, epoxy emulsion and polyetheramine curing agent to form a three-dimensional network structure.

[0004] To achieve the above objectives, the present invention is implemented through the following technical solutions: According to a first aspect of the present invention, there is provided an anti-rust and anti-corrosion coating for ships, comprising, by mass percentage, 40-70% of epoxy emulsion, 10-20% of polyetheramine curing agent, 5-10% of styrene-based POSS polymer, 10-15% of anti-rust filler, 10-40% of deionized water and 1-3% of additives; Wherein, the structural formula of the styrene-based POSS polymer is as shown in Formula I: Formula I; In formula I, the R group is selected from amino and alkyl groups.

[0005] The styrene group in the styrene-based POSS polymer of the present invention can undergo a grafting reaction with the epoxy emulsion, so that the styrene-based POSS polymer is grafted with the epoxy emulsion as a hanging chain, and the cage-type polysilsesquioxane in the styrene-based POSS polymer can fill the surface gaps of the ship steel material. At the same time, since the "cage" structure of the cage-type polysilsesquioxane in the styrene-based POSS polymer is elastic, the toughness of the coating and the structural stability and compactness of the coating can be enhanced; the epoxy emulsion and the polyetheramine curing agent work together to be adsorbed on all oxide matrices of the ship through electrostatic and donor-acceptor interaction mechanisms, so as to achieve full coverage of the ship surface and form a dense coating, which can effectively improve the anti-corrosion and anti-rust effects.

[0006] Preferably, the anti-rust filler is selected from at least one of graphene oxide, aluminum tripolyphosphate, zinc phosphate, chromium phosphate or zinc phosphoborate.

[0007] The anti-rust filler added to the coating of the present invention can be dispersed in a three-dimensional network structure formed by compounding styrene-based POSS polymer, epoxy emulsion and polyetheramine curing agent, thereby increasing the anti-corrosion effect of the coating material.

[0008] Preferably, the epoxy emulsion is selected from at least one of E20 emulsion, E35 emulsion, E44 emulsion or E51 emulsion.

[0009] Preferably, the auxiliary agent is selected from at least one of a leveling agent, a defoaming agent, an antioxidant, a thickener, a preservative and a mildewcide.

[0010] The additives added in the present invention include a leveling agent that can improve the fluidity of the coating, avoid unevenness on the coating surface, and make the coating surface smooth; a defoamer that can avoid bubbles generated during the construction process, prevent pinholes and bubbles from appearing on the coating, and improve the density and uniformity of the coating; an antioxidant that can avoid discoloration and aging on the coating surface; a thickener that can increase the viscosity of the coating and reduce the phenomenon of film sagging; a preservative that can inhibit the growth of microorganisms in the coating and prevent the coating from spoiling and deteriorating; and a mildew inhibitor that can prevent the coating from breeding bacteria in a humid environment. The present invention can increase the service life of the marine coating by reasonably selecting the above-mentioned additives.

[0011] Preferably, the composition comprises, by mass percentage, 50-60% of epoxy emulsion, 10-11% of polyetheramine curing agent, 5-8% of styrene-based POSS polymer, 12-13% of rust-proof filler, 20-28% of deionized water and 1-2% of auxiliary agent.

[0012] According to a second aspect of the present invention, there is provided a method for preparing an anti-rust and anti-corrosion coating for ships, comprising the following steps: firstly, an anti-rust filler, an additive and water are stirred, ground and dispersed to obtain an aqueous slurry; then, an epoxy emulsion, a polyetheramine curing agent and a styrene-based POSS polymer are added to the aqueous slurry, and stirred evenly to obtain the anti-rust and anti-corrosion coating for ships.

[0013] Preferably, the preparation method of the styrene-based POSS polymer is: Azobisisobutyronitrile is added to tetrahydrofuran containing silanol and trichlorosilane to carry out a free radical polymerization reaction to obtain the styrene-based POSS polymer.

[0014] Preferably, the mass ratio of the silanol to trichlorosilane is 1:1 to 1.5; The amount of the initiator added is 0.1-1 wt % of the silicon triol.

[0015] Preferably, the temperature of the free radical polymerization reaction is 45-60° C., and the time of the free radical polymerization reaction is 12-24 hours.

[0016] Preferably, the fineness of the aqueous slurry obtained by grinding and dispersion is ≤15 μm.

[0017] The present invention provides an anti-rust and anti-corrosion coating for ships and a preparation method thereof. The coating has the following beneficial effects: (1) This scheme provides an anti-rust and anti-corrosion coating for ships. The added styrene-based POSS polymer undergoes a grafting reaction with the epoxy emulsion to form a covalent bond. This grafting reaction allows the styrene-based POSS polymer to combine with the epoxy emulsion as a hanging chain, thereby enhancing the strength and toughness of the coating. The introduction of the styrene group provides additional cross-linking points, thereby improving the structural stability and density of the coating, thereby improving the anti-corrosion and anti-rust effects.

[0018] (2) This scheme provides an anti-rust and anti-corrosion coating for ships. The cage-type polysilsesquioxane structure in the styrene-based POSS polymer has excellent filling properties and can penetrate and fill the tiny gaps on the surface of the ship's steel materials. It can reduce the pores and defects inside the coating, improve the density of the coating, and effectively block the penetration of seawater and corrosive media, thereby enhancing the anti-corrosion and anti-rust effects.

[0019] (3) The present invention provides an anti-rust and anti-corrosion coating for ships. Since the "cage" structure of the cage-type polybis(2-hydroxyethyl)siloxane in the styrene-based POSS polymer is elastic, the coating has better elasticity and durability, and can effectively reduce the risk of cracking and peeling.

[0020] (4) The present invention provides an anti-rust and anti-corrosion coating for ships. The epoxy emulsion and the polyetheramine curing agent work together to be adsorbed on all oxide matrices of the ship through electrostatic and donor-acceptor interaction mechanisms, so that the coating formed by the ship coating can achieve full coverage of the ship surface, forming a uniform and dense protective layer that can effectively isolate oxygen and is molecules, thereby improving the anti-corrosion and anti-rust performance of the ship coating. DETAILED DESCRIPTION

[0021] In order to better illustrate the content of the present invention, a detailed description is given below in conjunction with specific embodiments.

[0022] An anti-rust and anti-corrosion coating for ships, comprising, by mass percentage, 40-70% of epoxy emulsion, 10-20% of polyetheramine curing agent, 5-10% of styrene-based POSS polymer, 10-15% of anti-rust filler, 10-40% of deionized water and 1-3% of auxiliary agent; Wherein, the structural formula of the styrene-based POSS polymer is as shown in Formula I: Formula I; In formula I, the R group is selected from amino and alkyl groups.

[0023] In a specific embodiment, the preparation method of the anti-rust and anti-corrosion coating for ships is as follows: (1) Preparation of styrene-based POSS polymer: Silanetriol and trichlorosilane are dissolved in tetrahydrofuran, and then azobisisobutyronitrile is added to carry out free radical polymerization at 45-60°C for 12-24 hours. After vacuum distillation and solvent removal, a styrene-based POSS polymer is obtained; (2) Mixing the anti-rust filler, the additive and water, stirring, dispersing and grinding to obtain an aqueous slurry with a fineness of ≤15 μm; (3) Add epoxy emulsion, polyetheramine curing agent and styrene-based POSS polymer to the water-based adhesive and stir evenly to obtain an anti-rust and anti-corrosion coating for ships.

[0024] The epoxy emulsion in the present invention is selected from E20 emulsion, E35 emulsion, E44 emulsion and E51 emulsion produced by Guangzhou Epoxy Material Technology Co., Ltd.; the polyetheramine curing agent is selected from the polyetheramine T403 curing agent of Jinan Linyan Mandy New Materials Co., Ltd.; the leveling agent is selected from the BYK3441 leveling agent of Guangzhou Si Tuyuan Chemical Co., Ltd.; the defoaming agent is selected from the BYK024 defoaming agent of German BYK Chemical Company; the antioxidant is selected from the 5067 oxidant of Tianjin Lianlong New Materials Co., Ltd.; the thickener is selected from the PA-800 thickener of Zhejiang Fenghong New Materials Co., Ltd.; the preservative and mildewproof agent are both selected from the OTW series of Guangzhou Jiankai Biological Co., Ltd.

[0025] Example 1 Calculated by mass percentage, it includes 64% E44 epoxy emulsion, 10% polyetheramine curing agent, 5% styrene-based POSS polymer, 10% graphene oxide, 10% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0026] The specific preparation method is: (1) Dissolve 1 kg of silanol and 1 kg of trichlorosilane in excess tetrahydrofuran, mix well, add 100 g of azobisisobutyronitrile, and perform free radical polymerization at 60 ° C for 18 hours. After vacuum distillation and solvent removal, obtain a styrene-based POSS polymer; (2) adding graphene oxide, 5067 oxidant, BYK024 defoamer and BYK3441 leveling agent into deionized water, stirring, dispersing and grinding to obtain an aqueous slurry with a fineness of ≤15 μm; (3) Add E44 epoxy emulsion, polyetheramine curing agent and styrene-based POSS polymer to the aqueous slurry and stir evenly to obtain an anti-rust and anti-corrosion coating for ships.

[0027] Example 2 Calculated by mass percentage, it includes 50% E51 epoxy emulsion, 10% polyetheramine curing agent, 7% styrene-based POSS polymer, 12% graphene oxide, 20% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0028] Example 3 Calculated by mass percentage, it includes 64% E51 epoxy emulsion, 10% polyetheramine curing agent, 5% styrene-based POSS polymer, 10% graphene oxide, 10% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0029] Example 4 Calculated by mass percentage, it includes 52.6% E44 epoxy emulsion, 15% polyetheramine curing agent, 8% styrene-based POSS polymer, 5% aluminum tripolyphosphate, 6% zinc phosphate, 20% deionized water, 0.3% BYK3441 leveling agent, 0.5% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0030] Example 5 Calculated by mass percentage, it includes 52% E51 epoxy emulsion, 10% polyetheramine curing agent, 5% styrene-based POSS polymer, 12% graphene oxide, 20% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0031] Comparative Example 1 Calculated by mass percentage, it includes 69% E51 epoxy emulsion, 10% polyetheramine curing agent, 10% graphene oxide, 10% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0032] Comparative Example 2 Calculated by mass percentage, it includes 74% E51 epoxy emulsion, 5% styrene-based POSS polymer, 10% graphene oxide, 10% deionized water, 0.2% BYK3441 leveling agent, 0.2% BYK024 defoaming agent, 0.3% 5067 oxidant, 0.2% preservative and 0.1% mildew inhibitor.

[0033] The determination method and evaluation method of the anticorrosion and antimildew coatings for ships prepared in the above Examples 1 to 5 and Comparative Examples 1 to 2 are as follows: (1) Adhesion: A grid cutter was used to cut 100 small squares in the horizontal and vertical directions. 3M600 tape was used to stick to the grids. The 3M600 tape was quickly pulled up to test the shedding area. The shedding area of ​​each embodiment is shown in Table 1.

[0034] Table 1

[0035] According to the data in Table 1, the anti-corrosion and anti-mildew coatings for ships prepared in Examples 1 to 5 have a coating with higher viscosity and higher structural stability formed on the surface of ship steel materials and are not easy to fall off.

[0036] (2) Toughness: The coatings formed on the surface of ship steel materials by the anticorrosion and mildew-proof coatings prepared in Examples 1 to 5 and the Vickers hardness test after immersion in 3.5% NaCl solution for 20 days were tested respectively, as shown in Table 2: Table 2

[0037] From the data in Table 2, it can be seen that the hardness of the coatings formed in Examples 1 to 5 decreased slightly after being soaked in salt water for 20 days. This is because the concentration of epoxy resin in the coating was relatively reduced due to water penetration, and the three-dimensional network structure in the coating was loose, resulting in a decrease in hardness. However, compared with Comparative Examples 1 and 2, the initial hardness and the hardness after soaking in salt water for 20 days were better.

[0038] (3) Corrosion and salt resistance test: According to the experimental methods and requirements in national standards GB / T1771 and GB / T26323, the salt spray resistance and filiform corrosion resistance of the surface coating of ship steel materials were tested. The test results are shown in Table 3; Table 3

[0039] According to the data in Table 3, the three-dimensional network structure is constructed through the synergistic effect of epoxy emulsion, polyetheramine curing agent and styrene-based POSS polymer, which can significantly improve the salt spray resistance of the coating and have a significant inhibitory effect on the occurrence of filamentous corrosion.

[0040] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An anti-rust and anti-corrosion coating for ships, characterized in that: The composition comprises, by mass percentage, 40-70% of epoxy emulsion, 10-20% of polyetheramine curing agent, 5-10% of styrene-based POSS polymer, 10-15% of anti-rust filler, 10-40% of deionized water and 1-3% of additives; Wherein, the structural formula of the styrene-based POSS polymer is as shown in Formula I: Formula I; In formula I, the R group is selected from amino and alkyl groups.

2. The anti-rust and anti-corrosion coating for ships according to claim 1, characterized in that: The anti-rust filler is selected from at least one of graphene oxide, aluminum tripolyphosphate, zinc phosphate, chromium phosphate or zinc phosphoborate.

3. The anti-rust and anti-corrosion coating for ships according to claim 1, characterized in that: The epoxy emulsion is selected from at least one of E20 emulsion, E35 emulsion, E44 emulsion or E51 emulsion.

4. The anti-rust and anti-corrosion coating for ships according to claim 1, characterized in that: The auxiliary agent is selected from at least one of a leveling agent, a defoaming agent, an antioxidant, a thickener, a preservative and a mildewproof agent.

5. The anti-rust and anti-corrosion coating for ships according to claim 1, characterized in that: The composition comprises, by mass percentage, 50-60% of epoxy emulsion, 10-11% of polyetheramine curing agent, 5-8% of styrene-based POSS polymer, 12-13% of anti-rust filler, 20-28% of deionized water and 1-2% of auxiliary agent.

6. A method for preparing the anti-rust and anti-corrosion coating for ships according to any one of claims 1 to 5, characterized in that: The following steps are involved: Firstly, the anti-rust filler, the auxiliary agent and water are stirred, ground and dispersed to obtain an aqueous slurry; then epoxy emulsion, polyetheramine curing agent and styrene-based POSS polymer are added to the aqueous slurry, and stirred evenly to obtain the anti-rust and anti-corrosion coating for ships.

7. The method for preparing an anti-rust and anti-corrosion coating for ships according to claim 6, characterized in that: The preparation method of the styrene-based POSS polymer is: Azobisisobutyronitrile is added to tetrahydrofuran containing silanol and trichlorosilane to carry out a free radical polymerization reaction to obtain the styrene-based POSS polymer.

8. The method for preparing an anti-rust and anti-corrosion coating for ships according to claim 7, characterized in that: The mass ratio of the silicon triol to trichlorosilane is 1:1-1.5; The amount of the initiator added is 0.1-1 wt % of the silicon triol.

9. The method for preparing an anti-rust and anti-corrosion coating for ships according to claim 7, characterized in that: The temperature of the free radical polymerization reaction is 45-60° C., and the time of the free radical polymerization reaction is 12-24 hours.

10. The method for preparing an anti-rust and anti-corrosion coating for ships according to claim 6, characterized in that: The fineness of the aqueous slurry obtained by grinding and dispersion is ≤15μm.

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