High-solid-content epoxy glass flake heavy anti-corrosion coating for offshore wind power foundation

Abstract

The invention relates to a high-solid-content epoxy glass flake heavy anti-corrosion coating for an offshore wind power foundation, which consists of a component A and a component B, the component A is prepared from raw materials in percentage by weight as follows: 10%-20% of bisphenol A epoxy resin, 20%-40% of modified hydrogenated epoxy resin, 5%-10% of liquid petroleum resin, 1%-2% of a rheological aid, 0.1%-1% of a dispersant, 0.1%-1% of a defoaming agent, 1%-3% of a silane coupling agent, 5%-10% of modified glass flakes, 20%-40% of functional filler and 0-10% of a composite environment-friendly solvent; and the component B is a mixed amine epoxy curing agent. The epoxy glass flake coating disclosed by the invention can be thickly coated at one time, has excellent adhesive force, hardness, wear resistance and impact resistance, is high in drying speed, excellent in chemical corrosion resistance, seawater soaking resistance and cathodic disbonding resistance, and meets the performance requirements of NORSOK M-501: 2022 (edition VII) Surface Treatment and Protective Coating.

Description

Technical Field

[0001] This invention relates to an epoxy coating for heavy-duty corrosion protection in marine engineering, specifically a high-solids-content epoxy glass flake heavy-duty corrosion protection coating for offshore wind power foundations. Background Technology

[0002] The marine environment is a harsh and corrosive environment, placing high demands on anti-corrosion coatings for marine engineering projects, especially for offshore wind power infrastructure located in tidal / splash zones, where the average corrosion rate is 3-10 times higher than that of other engineering equipment and facilities. For offshore wind power foundations, in addition to anti-corrosion performance requirements, higher film thickness, better abrasion resistance, and impact resistance are needed. According to NORSOK M-501:2022 and ISO 12944-9 standards, the design film thickness for anti-corrosion coatings for engineering equipment and facilities in tidal / splash zones is 1000 micrometers, with the following performance requirements: 1. Cyclic aging test ≥4200h, corrosion spread at the marked point is ≤3mm for zinc-rich systems and ≤8mm for non-zinc-rich systems; 2. Resistance to cathodic disbondment ≥4200h, corrosion spread at the scribing point ≤20mm; 3. Impact resistance at 1000 micrometers ≥ 5.6 Joules; 4. Seawater immersion resistance ≥4200h, paint film intact, corrosion spread at the marked area ≤6mm.

[0003] In anti-corrosion coatings, the use of the base resin and curing agent is the most critical. Regarding the base resin formulation, existing technology CN104774527B reports a method for preparing an epoxy glass flake coating for marine tidal / splash zones, which meets the requirements of the old NORSOK M-501:2012 standard. It lacks impact resistance data. Based on experience, low-molecular-weight epoxy resins, bisphenol F epoxy resins, alicyclic amines, and modified phenolic amines exhibit good anti-corrosion performance, but thick coatings generally have poor impact resistance and weather resistance. CN106047065B reports a solvent-free epoxy glass flake coating for steel structures in marine splash zones and its preparation method. Although replacing the epoxy resin with hydrogenated bisphenol A improves weather resistance, the low molecular weight of the resin means that the impact resistance of thick coatings remains unimproved. CN120041056A discloses a solvent-free epoxy heavy-duty anti-corrosion coating, its preparation method and application. Although the main paint and curing agent have been toughened and modified, the salt spray resistance is only 1000 hours. It is mainly used for petrochemical anti-corrosion and is not suitable for heavy-duty anti-corrosion of offshore wind power foundations.

[0004] Therefore, there is an urgent need for an epoxy coating that can be used for heavy-duty corrosion protection of offshore wind power foundations. Summary of the Invention

[0005] The first technical problem to be solved by the present invention is to provide an epoxy glass flake coating for offshore wind power foundations that has high flexibility and impact resistance, high hardness and wear resistance, and high corrosion resistance in a single thick coating.

[0006] The technical solution adopted by the present invention to solve its first technical problem is an epoxy glass flake coating for offshore wind power foundations, which is composed of component A and component B.

[0007] Component A is a mixture of the following raw materials in weight percentages: Bisphenol A epoxy resin 10-20%, modified hydrogenated epoxy resin 20-40%, liquid petroleum resin 5-10%, rheology modifier 1-2%, dispersant 0.1-1%, defoamer 0.1-1%, silane coupling agent 1-3%, modified glass flakes 5-10%, functional filler 20-40%, composite environmentally friendly solvent 0-10%; Component B is a mixed amine epoxy curing agent.

[0008] The mixed amine epoxy curing agent is a mixture of modified polyamide (such as Air Chemical Ancamine 2634), modified aliphatic amine (such as Air Chemical Ancamine 2636), and modified cycloaliphatic amine (such as Air Chemical Ancamine 2280). The weight ratio is 75:10~20:5~15.

[0009] In the epoxy glass flake coating of the present invention, the types of dispersants and defoamers in component A are not limited.

[0010] Preferably, the mass ratio of component A to component B is 100:5-15.

[0011] Preferably, the bisphenol A epoxy resin is composed of E51 epoxy resin and E20 epoxy resin, with a mass ratio of 3-8:1.

[0012] Preferably, the modified hydrogenated epoxy resin is obtained by hydrogenation of E51 epoxy resin followed by an addition reaction with fatty acids.

[0013] Preferably, the liquid petroleum resin is a C9 / C10 phenol-containing unsaturated aromatic hydrocarbon polymer.

[0014] Preferably, the rheology modifier is polyamide wax powder.

[0015] Preferably, the modified glass flakes are glass flakes that have been treated with a silane coupling agent.

[0016] Preferably, the modified functional filler is composed of quartz sand, feldspar powder, and bauxite.

[0017] Preferably, the composite environmentally friendly solvent is a mixture of xylene and one or more of butanol, benzyl alcohol, propylene glycol, propylene glycol ethers, etc., in any proportion.

[0018] The preparation method of component A of the epoxy glass flake coating of the present invention includes the following steps: adding bisphenol A epoxy resin, modified hydrogenated epoxy resin, and liquid petroleum resin to a reactor, and adding a rheology modifier while stirring; raising the temperature to 55-70℃ and holding for 15-30 minutes to fully activate the rheology modifier; lowering the temperature to room temperature; adding a dispersant, defoamer, and functional filler in sequence; increasing the rotation speed to 1000-1500 r / min for high-speed dispersion until the fineness is less than 50 μm; reducing the rotation speed to 500-1000 r / min; adding a silane coupling agent and modified glass flakes while stirring; adjusting the viscosity with a composite environmentally friendly solvent; and continuing to disperse for 15 minutes until uniform, thus obtaining the coating.

[0019] The present invention discloses a method for applying a high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, comprising: uniformly mixing component A and component B at a mass ratio of 100:5-15, filtering the mixture through a 40-120 mesh filter, and then directly applying the mixture to the treated substrate.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention relates to an epoxy glass flake coating with a simple preparation method. It utilizes a modified hydrogenated epoxy resin, where a hydrogenation process saturates the double bonds in the bisphenol A structure with hydrogen atoms, resulting in a more stable molecular structure and better aging resistance. Further modification with fatty acids enhances the resin's flexibility and strength. Finally, it is blended with bisphenol A epoxy resin, achieving both weather resistance and flexibility of the coating film without compromising its anti-corrosion performance. The use of modified glass flakes and functional fillers improves the coating's barrier properties and abrasion resistance, achieving efficient corrosion protection while reducing film loss. The addition of silane coupling agents and liquid petroleum resin further integrates the fillers and resin, improving the density of thick coatings.

[0021] 2. The epoxy glass flake coating of this invention has high solids and low viscosity. Component A dries quickly and has a long adaptability period. It is environmentally friendly with low VOCs, while having good workability and excellent anti-sagging properties. The coating thickness can reach 1000 micrometers in a single application. It is particularly suitable for heavy-duty anti-corrosion applications in marine engineering where thick coatings and high performance requirements are required. Detailed Implementation

[0022] The present invention will now be described in detail through specific embodiments.

[0023] Unless otherwise specified, the raw materials involved in the embodiments of this invention are all commercially available products.

[0024] Example 1 This embodiment describes a high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, consisting of component A and component B. Component A comprises the following raw materials by weight percentage: 15% bisphenol A epoxy resin (E51:E20=4:1), 34% modified hydrogenated epoxy resin (Shanghai Huayi Resin Co., Ltd., 642 modified hydrogenated epoxy resin), 7% liquid petroleum resin, 1.8% polyamide wax powder, 0.2% dispersant, 0.5% defoamer, 1.5% silane coupling agent, 8% modified glass flakes, 27% functional filler (quartz sand:feldspar powder:bauxite=2:2:1), and 5% composite environmentally friendly solvent (xylene:butanol=2:1). Component B comprises the following mixed amine curing agents by weight percentage: 75% 2634 curing agent (Air Chemical Ancamine 2634), 14% 2636 curing agent (Air Chemical Ancamine 2636), and 11% 2280 curing agent (Air Chemical Ancamine 2280).

[0025] The preparation method of component A is as follows: Bisphenol A epoxy resin, modified hydrogenated epoxy resin, and liquid petroleum resin were added to a reactor. While stirring at 500-1000 rpm, a rheology modifier was added. The temperature was raised to 55-70℃ and held for 15-30 minutes to fully activate the rheology modifier. The temperature was then lowered to room temperature, and a dispersant, defoamer, and functional filler were added sequentially. The speed was increased to 1000-1500 rpm for high-speed dispersion until the fineness was less than 50 μm. The speed was then reduced to 500-1000 rpm, and while stirring, a silane coupling agent and modified glass flakes were added. The viscosity was adjusted with a composite environmentally friendly solvent, and dispersion was continued for 15 minutes until uniform. After passing inspection, the mixture was filtered and packaged to obtain component A.

[0026] Preparation and application: Mix component A and component B evenly at a mass ratio of 100:10, filter through a 40-120 mesh filter, and then apply directly to the treated substrate.

[0027] Example 2 This embodiment describes a high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, consisting of component A and component B. Component A comprises the following raw materials by weight percentage: 10% bisphenol A epoxy resin (E51:E20=3:1), 40% modified hydrogenated epoxy resin, 5% liquid petroleum resin, 1% polyamide wax powder, 0.1% dispersant, 0.4% defoamer, 1% silane coupling agent, 6% modified glass flakes, 30% functional filler (quartz sand:feldspar powder:bauxite=2:1:2), and 6.5% composite environmentally friendly solvent (xylene:butanol:propylene glycol methyl ether=3:1:0.5). Component B comprises the following mixed amine curing agents by weight percentage: 75% Ancamine 2634 (Air Chemical), 20% Ancamine 2636 (Air Chemical), and 5% Ancamine 2280 (Air Chemical).

[0028] The preparation method of component A of the epoxy glass flake coating in this embodiment is the same as that in Example 1.

[0029] Preparation and construction: Basically the same as in Example 1, except that the mass ratio of component A to component B is 100:8.

[0030] Example 3 This embodiment describes a high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, consisting of component A and component B. The raw materials of component A, by weight percentage, are: 10% bisphenol A epoxy resin (E51:E20=8:1), 20% modified hydrogenated epoxy resin, 10% liquid petroleum resin, 2% polyamide wax powder, 1% dispersant, 1% defoamer, 3% silane coupling agent, 5% modified glass flakes, 40% functional filler (quartz sand: feldspar powder: bauxite=3:1:1), and 8% composite environmentally friendly solvent (xylene:butanol:propylene glycol methyl ether=3:0.5:1). Component B contains mixed amine curing agents by weight percentage: 75% Ancamine 2634 (Air Chemical), 10% Ancamine 2636 (Air Chemical), and 15% Ancamine 2280 (Air Chemical).

[0031] The preparation method of component A of the epoxy glass flake coating in this embodiment is the same as that in Example 1.

[0032] Preparation and construction: Basically the same as in Example 1, except that the mass ratio of component A to component B is 100:15.

[0033] Example 4 This embodiment describes a high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, consisting of component A and component B. The raw materials of component A, by weight percentage, are: 20% bisphenol A epoxy resin (E51:E20=6:1), 30% modified hydrogenated epoxy resin, 8% liquid petroleum resin, 1.5% polyamide wax powder, 0.5% dispersant, 0.8% defoamer, 2% silane coupling agent, 10% modified glass flakes, 20% functional filler (quartz sand:feldspar powder:bauxite=3:1:1), and 7.2% composite environmentally friendly solvent (xylene:butanol=7:3). Component B contains mixed amine curing agents by weight percentage: 75% 2634 curing agent (Air Chemical Ancamine 2634), 15% 2636 curing agent (Air Chemical Ancamine 2636), and 10% 2280 curing agent (Air Chemical Ancamine 22280).

[0034] The preparation method of component A of the epoxy glass flake coating in this embodiment is the same as that in Example 1.

[0035] Preparation and application: Same as in Example 1, except that the mass ratio of component A to component B is 100:12.

[0036] Comparative Example 1 The difference from Example 1 is that component B does not contain curing agents 2636 and 2280. This results in slower drying and poorer acid resistance, leading to non-compliance.

[0037] Comparative Example 2 The difference from Example 1 is that modified polyamide curing agent 2634 is not added to component B. This results in severe corrosion after cyclic aging and poor resistance to cathodic disbondment.

[0038] Comparative Example 3 The difference from Example 1 is that the modified hydrogenated epoxy resin in component A is replaced with ordinary epoxy resin. This leads to chalking of the paint film after cyclic aging, especially seawater erosion, and excessively rapid paint film loss, resulting in a shortened protective lifespan.

[0039] Comparative Example 4 The difference from Example 1 is that the ratio of E51 to E20 in the bisphenol A epoxy resin of component A is 1:1. This results in a coating that is too thick or has a low solids content, making it difficult to achieve a thick coating in one application.

[0040] According to NORSOK M-501:2022 standard, the coatings prepared in Examples 1 to 4, the coatings prepared in Comparative Examples 1 to 4, and commercially available epoxy glass flake coating products were tested for performance. The results are shown in Tables 1 and 2.

[0041] Table 1 Performance test results of Example 1 and Comparative Example

[0042] Table 2 Performance test results of the examples and commercially available products

[0043] This invention scientifically combines different mixed amines of modified epoxy resin, resulting in a coating film with excellent resistance to cyclic aging, cathodic peeling, and seawater immersion, while also exhibiting impact resistance even after a 1000-micron thick dry film thickness, meeting the latest standard requirements of NORSOK M-501:2022 and ISO 12944-9. The performance test results in Table 1 show that in Comparative Examples 1-4 of this invention, when the mixed amine curing agent was poorly matched, or when the modified resin or resin ratio was incorrect, the performance indicators all failed to meet the standards. The performance test results in Table 2 show that, after different resins and amine curing agents are matched according to the preferred ratio, the performance of all aspects of Examples 1-4 of the present invention is significantly higher than the technical indicators, especially in terms of drying properties, anti-sagging properties, adhesion, cyclic aging, seawater immersion, and cathodic disbondment. The high-solids epoxy glass flake coatings in Examples 1-4 of the present invention have high solids content, do not sag or bubble when coated in a single thick coat, and the paint film has excellent adhesion, hardness, abrasion resistance and impact resistance. They also have fast drying time, resistance to cyclic aging, resistance to seawater immersion and resistance to cathodic disbondment, and meet the performance requirements of NORSOK M-501:2022 (7th edition) "Surface treatment and protective coatings".

[0044] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A high-solids epoxy glass flake heavy-duty anti-corrosion coating for offshore wind power foundations, comprising component A and component B, characterized in that, Component A comprises the following raw materials by weight percentage: 10-20% bisphenol A epoxy resin, 20-40% modified hydrogenated epoxy resin, 5-10% liquid petroleum resin, 1-2% rheology modifier, 0.1-1% dispersant, 0.1-1% defoamer, 1-3% silane coupling agent, 5-10% modified glass flakes, 20-40% functional filler, and 0-10% composite environmentally friendly solvent; Component B is a mixed amine epoxy curing agent.

2. The high-solids epoxy glass flake coating according to claim 1, characterized in that, The bisphenol A epoxy resin is composed of E51 and E20 in a mass ratio of 3-8:

1.

3. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The modified hydrogenated epoxy resin is obtained by reacting E51 epoxy resin with fatty acids after hydrogenation; preferably, the liquid petroleum resin is a C9 / C10 phenol-containing unsaturated aromatic hydrocarbon polymer.

4. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The rheology modifier is polyamide wax powder.

5. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The modified glass flakes are glass flakes that have been surface-treated with a silane coupling agent.

6. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The modified functional filler is a compound of quartz sand, feldspar powder, and bauxite.

7. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The composite environmentally friendly solvent is a mixture of xylene and one or more of butanol, benzyl alcohol, propylene glycol, and propylene glycol ethers in any proportion.

8. The high-solids epoxy glass flake coating according to claim 1 or 2, characterized in that, The mixed amine epoxy curing agent includes a mixture of modified polyamides (such as Air Chemical 2634), modified aliphatic amines (such as Air Chemical 2636), and modified cycloaliphatic amines (such as Air Chemical 2280).

9. The high-solids epoxy glass flake coating according to claim 8, characterized in that, The weight ratio of the epoxy curing agent used in the marine heavy-duty anti-corrosion coating is: 2634:2636:2280 = 75:10~20:5~15.

10. The high-solids epoxy glass flake coating according to claim 1, characterized in that, The mass ratio of component A to component B is 100:5-15.

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