High wear-resistant epoxy anticorrosive coating material and preparation method thereof

Abstract

The application discloses a kind of high wear-resistant epoxy anticorrosive coating materials and preparation method, belong to the technical field of concrete coating protection of submarine tunnel, coating material includes 60-80 parts epoxy resin, 14-18 parts scale ceramic micro powder composite filler, 8-16 parts modified amine curing agent.Composite filler contains scale ceramic micro powder, nano ZrO2, modified bentonite, zinc phosphate by composite coupling agent pretreatment;Modified amine curing agent contains polyether amine, hydrogenated cashew phenol, benzyl alcohol and KH-560.The composite filler is mixed with epoxy resin by stage dispersion, and modified amine curing agent is stirred and dispersed, and is cured at room temperature after coating or spraying.The application realizes room temperature rapid curing by the synergistic effect of composite coupling agent and hydrogenated cashew phenol, combined with the performance optimization of multiple filler multiple protection and curing agent, so that the coating has high wear resistance, long-term anticorrosion and excellent anti-aging performance, effectively solves the pain points such as existing coating anticorrosion performance antagonism and complex construction.

Description

Technical Field

[0001] This invention relates to the field of concrete coating protection technology for submarine tunnels, and in particular to a high wear-resistant epoxy anti-corrosion coating material and its preparation method. Background Technology

[0002] With the rapid development of my country's transportation infrastructure and marine engineering technology, the construction scale of long-distance, large-diameter, and high-water-pressure underwater shield tunnel projects continues to expand. The design reference life of concrete segments for submarine tunnels needs to be 100 years or more, but the service environment is harsh. They need to withstand mechanical loads and face multiple erosions such as seawater erosion, microbial corrosion, and temperature fluctuations. In addition, the porous nature of concrete itself can easily lead to steel corrosion and segment deterioration, shortening the service life. Therefore, there is an urgent need for high-performance protective coating materials.

[0003] Currently, epoxy resin coatings are a commonly used material for the protection of concrete segments in subsea tunnels due to their excellent adhesion and chemical stability. However, conventional epoxy coatings struggle to balance wear resistance and corrosion resistance, making them prone to failure under mechanical wear. Furthermore, they lack sufficient resistance to microbial corrosion and aging, leading to problems such as powdering, blistering, and peeling after long-term service. From the perspective of curing agents, traditional amine curing agents have high crosslinking density and high internal stress, resulting in poor toughness and low crack resistance after curing. Most amine curing agents require high temperatures for full curing, which is insufficient to meet the room-temperature curing requirements of subsea tunnel construction. Regarding filler modification, single nanofillers or ordinary ceramic fillers are prone to agglomeration, failing to simultaneously improve the coating's strength, toughness, and wear resistance. Multi-component filler blends suffer from poor interfacial compatibility and uneven dispersion, further hindering performance improvement.

[0004] Therefore, there is an urgent need to develop an epoxy coating material that combines high wear resistance, long-lasting corrosion protection, and excellent anti-aging properties. This material must meet the construction requirements of rapid curing at room temperature and low surface treatment compatibility, while solving the technical pain points of existing coatings such as difficulty in balancing wear resistance and toughness, short anti-corrosion life, and high construction difficulty. Summary of the Invention

[0005] To address the challenges of achieving both wear resistance and corrosion resistance in existing epoxy anti-corrosion coatings, as well as the poor toughness and aging resistance of curing agents, a flake ceramic micropowder composite filler was developed. The flake ceramic has a flake diameter of 10-50 μm and a thickness of 1-5 μm.

[0006] S2. Add polyetheramine, hydrogenated cashew nut phenol and benzyl alcohol to the reaction vessel in sequence, stir and mix at 55-65℃ for 25-35 min, slowly add silane coupling agent KH-560, raise the temperature to 70-75℃ and continue the reaction for 1.5-2 h to obtain modified amine curing agent.

[0007] S3. Add epoxy resin and the flake ceramic micro powder composite filler to the reactor, disperse at 1400-1600 rpm for 30-50 min, and then disperse at 1100-1300 rpm for 15-25 min.

[0008] S4. Add the modified amine curing agent to the mixture obtained in step S3 and disperse it at 600-800 rpm for 5-10 min;

[0009] S5. Apply or spray the material obtained in step S4 onto the surface of the substrate and cure at 22-28℃ for 24-48 hours.

[0010] In a preferred embodiment of the present invention, in step S1, the composite coupling agent includes silane coupling agent KH-560 and titanate coupling agent;

[0011] The titanate coupling agent is a monoalkoxy type titanate coupling agent, selected from one or more of isopropoxytriisostearoyl titanate and isopropoxytris(dioctylpyrophosphate)titanate.

[0012] In a preferred embodiment of the present invention, step S1, the pretreatment of the composite coupling agent includes:

[0013] Flake ceramic micro powder and nano ZrO2 are added to a composite coupling agent, stirred at 55-65℃ for 0.5-2h, allowed to stand for 0.2-1h, filtered, and dried at 75-85℃ for 1-3h.

[0014] The mass ratio of silane coupling agent KH-560 to titanate coupling agent in the composite coupling agent is 1:0.5-1.5;

[0015] The total amount of the composite coupling agent is 2-3% of the mass of the flake ceramic micro powder and 3-4% of the mass of the nano ZrO2.

[0016] In a preferred embodiment of the present invention, in step S1, the mass fraction of the flake ceramic powder is 55-80%, the mass fraction of nano ZrO2 is 12-18%, the mass fraction of modified bentonite is 15-25%, and the mass fraction of zinc phosphate is 2-6%.

[0017] In a preferred embodiment of the present invention, in step S1, the size of the nano ZrO2 is 2-8 nm, and the particle size D50 of the zinc phosphate is 15-20 μm.

[0018] In a preferred embodiment of the present invention, in step S1, the modified bentonite is prepared by:

[0019] Octadecyltrimethylammonium bromide was added to a bentonite solution, heated and stirred at 75-85°C for 0.5-1.5 h, washed with ethanol, and then vacuum dried at 55-65°C.

[0020] In a preferred embodiment of the present invention, in step S2, the modified amine curing agent comprises, by weight, 35-50 parts polyetheramine, 30-45 parts hydrogenated cashew nut shell powder, 10-15 parts benzyl alcohol, and 5-8 parts silane coupling agent KH-560.

[0021] In a preferred embodiment of the present invention, in step S2, the hydrogenated cashew nut shell is prepared by:

[0022] Preheated and dehydrated cashew phenols were dissolved in isopropanol and diluted. 2-4% nickel-based catalyst was added, and the reaction was carried out at 160-200℃ for 1.5-2.5 hours. During the reaction, the volume ratio of hydrogen to cashew phenols was controlled at 280-320:1.

[0023] In a preferred embodiment of the present invention, in step S4, the thickness of the cured coating is 200-1000 μm.

[0024] In a preferred embodiment of the present invention, a high wear-resistant epoxy anti-corrosion coating material comprises, by weight, 60-80 parts epoxy resin, 14-18 parts flake ceramic micro powder composite filler, and 8-16 parts modified amine curing agent.

[0025] This invention addresses the shortcomings of the prior art and has the following beneficial effects:

[0026] This invention strengthens the interfacial bonding strength between inorganic fillers and organic epoxy groups through the synergistic effect of a composite coupling agent and hydrogenated cashew nut shell powder, while simultaneously constructing a continuous and stable hydrophobic barrier to effectively prevent corrosive media from penetrating through interfacial gaps. The hydrogenation treatment eliminates the unsaturated double bonds of cashew nut shell powder, which, combined with the interfacial stabilizing effect of the composite coupling agent, significantly improves the anti-aging performance of the coating. This solves the problems of weak interfacial bonding, easy detachment of the hydrophobic layer, and insufficient anti-aging ability in the prior art, achieving long-term protection of the coating under harsh working conditions. It can also effectively inhibit marine microbial corrosion and prevent premature coating failure.

[0027] The modified amine curing agent of this invention is precisely matched with the modification effect of the composite coupling agent, enabling rapid and full curing of the coating without high temperature conditions. At the same time, it significantly reduces the surface treatment requirements of the concrete substrate, making it suitable for the humid, low-temperature, and space-constrained construction environment of submarine tunnels. Compared with the shortcomings of traditional amine curing agents, such as low curing efficiency and stringent substrate treatment requirements of conventional epoxy coatings, it significantly improves on-site construction efficiency and reduces quality risks caused by complex construction procedures.

[0028] This invention lays a crucial foundation for the performance of multi-component composite fillers through the interfacial bridging effect of composite coupling agents and hydrogenated cashew nut shells. This allows the functions of the flake-shaped wear-resistant skeleton of flake ceramic micropowder, the interstitial filling of nano-ZrO2, the toughness adjustment of modified bentonite, and the active corrosion protection of zinc phosphate to be fully released. This improves the comprehensive performance of the coating, such as wear resistance and resistance to alternating high and low temperatures, while achieving the dual goals of high wear resistance and long-term corrosion protection. This meets the complex and demanding service conditions of concrete segments in submarine tunnels and provides reliable protection for the long-term safe service of the structure. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 This is a process flow diagram of the preparation method of the present invention. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein. Therefore, the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0033] Unless otherwise specified in the following examples, all raw materials were commercially available or prepared using conventional methods in the art. These included ethanol (Sinopharm Chemical Reagent Co., Ltd., purity ≥96%), isopropanol (Sinopharm Chemical Reagent Co., Ltd., purity ≥99.7%), silane coupling agent KH-560 (γ-glycidyl etheroxypropyltrimethoxysilane, Sinopharm Chemical Reagent Co., Ltd., purity ≥98.0%), isopropoxytriisostearoyl titanate (Hubei Rishengchang New Material Technology Co., Ltd., purity 99%), isopropoxytris(dioctyl pyrophosphate) titanate (Hubei Chenghai Chemical Co., Ltd., purity 99%), benzyl alcohol (Sinopharm Chemical Reagent Co., Ltd., purity ≥99.0%), zinc phosphate (Zn3(PO4)2, Shanghai Yuanye Biotechnology Co., Ltd.), and alumina-supported nickel catalyst. (Shanghai Hanlu New Material Technology Co., Ltd., 40-45wt%), Epoxy Resin E44 (Nantong Xingchen Synthetic Materials Co., Ltd., epoxy equivalent 210-244g / eq, viscosity 6000-10000mPa∙s), Epoxy Resin E51 (Nantong Xingchen Synthetic Materials Co., Ltd., epoxy equivalent 180-200g / eq, viscosity 10000-18000mPa∙s), Cashew Phenol (Fuyong Biotechnology Co., Ltd.), Nano ZrO2 (Zhejiang Chongchuan New Material Technology Co., Ltd., purity 99.9%), Polyetheramine (D230, D400, Sinopharm Chemical Reagent Co., Ltd.), Octadecyltrimethylammonium bromide (Sinopharm Chemical Reagent Co., Ltd., purity 99%).

[0034] like Figure 1 As shown, a high-wear-resistant epoxy anti-corrosion coating material and its preparation method are disclosed. The coating material comprises the following components by weight: 60-80 parts epoxy resin, 14-18 parts flake ceramic micro powder composite filler, and 8-16 parts modified amine curing agent. The preparation method includes the following steps:

[0035] S1. Pretreated flake ceramic micro powder, nano ZrO2, modified bentonite, and zinc phosphate are mixed and ball-milled for 2-4 hours to obtain flake ceramic micro powder composite filler.

[0036] S2. Add polyetheramine, hydrogenated cashew nut phenol and benzyl alcohol to the reaction vessel in sequence, stir and mix at 55-65℃ for 25-35 min, slowly add silane coupling agent KH-560, raise the temperature to 70-75℃ and continue the reaction for 1.5-2 h to obtain modified amine curing agent.

[0037] S3. Add epoxy resin and flake ceramic micro powder composite filler to the reactor and disperse at 1400-1600 rpm for 30-50 min, then disperse at 1100-1300 rpm for 15-25 min.

[0038] S4. Add the modified amine curing agent to the mixture obtained in step S3 and disperse it at 600-800 rpm for 5-10 min.

[0039] S5. Apply or spray the material obtained in step S4 onto the surface of the substrate and cure at 22-28℃ for 24-48 hours.

[0040] Specifically, step S1 is the preparation of flake ceramic micro powder composite filler. By pretreating with composite coupling agent and synergistically proportioning with multi-component fillers, the uniformity of filler dispersion and interfacial compatibility are ensured, and the structural foundation for the wear resistance and corrosion resistance of the coating is laid.

[0041] Before ball milling, flake ceramic micro powder and nano ZrO2 need to be pretreated with a composite coupling agent. Specifically, silane coupling agent KH-560 and titanate coupling agent are mixed evenly at a mass ratio of 1:0.5-1.5, dissolved in an ethanol-water aqueous solution with a volume ratio of 2-4:1, flake ceramic micro powder and nano ZrO2 are added, and the mixture is stirred continuously at 55-65℃ for 0.5-2 hours. After stirring, the mixture is allowed to stand for 0.2-1 hours, the solid material is collected by filtration, and then dried in an oven at 75-85℃ for 1-3 hours to complete the pretreatment.

[0042] The flake ceramic powder used has a diameter of 10-50μm and a thickness of 1-5μm. It has a plate-like intercalation structure, in which the SiO2 phase accounts for about 46.5% by mass, the Al2O3 phase accounts for about 39.5% by mass, and the remainder is an alkali-resistant glass phase, i.e., the SiO2-Al2O3 composite phase. Specifically, using 46.5% quartz powder and 39.5% alumina powder as core raw materials, and 8% borax and 6% soda ash as fluxing agents, the mixture is dried at 105-110℃ to remove water and then mixed evenly. It is then placed in a melting furnace and melted at a constant temperature of 1550-1600℃ for 2-3 hours. The melt is then quenched by a high-pressure cold water flow of 0.3-0.5MPa to form thin-sheet ceramic fragments. These fragments are then coarsely crushed by a jaw crusher and dry mechanically separated by a planetary ball mill. Subsequently, using water as the medium and zirconia balls as the grinding media, the mixture is wet-milled at 300-350rpm for 4-6 hours with a material-to-water ratio of 1:1.5-2 and a ball-to-material ratio of 5:1. After vacuum filtration, the slurry is dried at a low temperature of 75-85℃. The SiO2 and Al2O3 phases of the flake ceramic micropowder are chemically bonded and uniformly distributed in the flake matrix. The surface is rich in hydroxyl functional groups, which can undergo condensation reaction with silane coupling agent KH-560 / titanium ester coupling agent to achieve surface activation. After ball milling, they can be arranged in parallel orientation in the coating to form a dense physical barrier layer.

[0043] Among them, the titanate coupling agent is a monoalkoxy type titanate coupling agent, selected from one or more of isopropoxytriisostearoyl titanate and isopropoxytris(dioctylpyrophosphoryloxy) titanate; the total amount of composite coupling agent is controlled to be 2-3% of the mass of flake ceramic micro powder and 3-4% of the mass of nano ZrO2, and the size of nano ZrO2 is 2-8 nm.

[0044] Furthermore, during the pretreatment process, the silane coupling agent KH-560 first hydrolyzes to generate silanol groups, which then undergo a dehydration condensation reaction with the hydroxyl groups on the surface of the flake ceramic micropowder and nano ZrO2 to form stable covalent bonds, achieving the first interfacial anchoring between the filler and the resin matrix. The alkoxy group of the titanate coupling agent undergoes a coordination complexation reaction with the hydroxyl groups on the filler surface, forming a second anchoring. Simultaneously, the long-chain alkyl group at the other end of the titanate coupling agent can form a physical entanglement with the hydrophobic long chain of hydrogenated cashew phenol in the subsequent modified amine curing agent. The synergistic effect of dual anchoring and long-chain entanglement enables the composite coupling agent to be firmly fixed on the filler surface and form a tight bond with the cross-linking network of the curing agent, eliminating interfacial gaps between the flake ceramic layers, fundamentally avoiding the risk of interlayer delamination, and effectively inhibiting filler agglomeration.

[0045] Specifically, the preparation of modified bentonite includes: adding octadecyltrimethylammonium bromide to a bentonite solution, stirring at 75-85℃ for 0.5-1.5 h, washing three times with ethanol after stirring, and then vacuum drying at 55-65℃. The organic cations in octadecyltrimethylammonium bromide undergo a displacement reaction with the inorganic cations between the bentonite layers, significantly improving its compatibility with epoxy resin, thereby regulating the balance between the toughness and hardness of the coating.

[0046] Furthermore, the flake ceramic micro powder and nano ZrO2 pretreated with the composite coupling agent are mixed with modified bentonite and zinc phosphate in the following proportions: flake ceramic micro powder mass fraction 55-80%, nano ZrO2 mass fraction 12-18%, modified bentonite mass fraction 15-25%, and zinc phosphate mass fraction 2-6%, wherein the particle size D50 of zinc phosphate is 15-20μm. The above mixture was placed in a ball mill and ball-milled for 2-4 hours. The mechanical force during the ball milling process caused the filler components to be evenly dispersed, allowing the flake-like structure of the ceramic micropowder to maintain its directional arrangement and forming a physical barrier basis for the intercalation of the flakes. Nano ZrO2 fully filled the gaps between the flake-like ceramic micropowder layers, making up for the local protective gaps of the simple flake structure. Zinc phosphate particles were evenly distributed in the filler system, providing a material basis for the subsequent formation of a passivation film on the substrate surface and the realization of electrochemical active corrosion protection. Modified bentonite dissociated into nanosheets during ball milling and formed chemical bonds with other fillers and resins through covalent bonds or hydrogen bonds. This not only blocked the crack propagation path but also played a role in interfacial bonding regulation, resulting in a flake-like ceramic micropowder composite filler with stable performance and no gaps at the interface.

[0047] Furthermore, step S2 aims to prepare a modified amine curing agent that combines flexibility, toughening, hydrophobicity, corrosion resistance, and room temperature curing properties. The composition of the curing agent is designed to meet the interfacial bonding requirements of the flake ceramic micropowder composite filler.

[0048] Further, polyetheramine, hydrogenated cashew nut shell powder, and benzyl alcohol are added to the reaction vessel in sequence and stirred at 55-65℃ for 25-35 minutes. Silane coupling agent KH-560 is slowly added dropwise. After the addition is complete, the reaction system is heated to 70-75℃ and the reaction is continued for 1.5-2 hours to obtain a viscous liquid modified amine curing agent.

[0049] Specifically, by weight, the modified amine curing agent consists of: 35-50 parts polyetheramine, 30-45 parts hydrogenated cashew nut phenol, 10-15 parts benzyl alcohol, and 5-8 parts silane coupling agent KH-560.

[0050] The polyetheramine is selected from one or more of polyetheramine D230 and polyetheramine D400.

[0051] Specifically, the preparation process of hydrogenated cashew nut phenol is as follows: preheated and dehydrated cashew nut phenol is dissolved in isopropanol and diluted. 2-4% of the mass of cashew nut phenol is added to the diluted solution, and the mixture is placed in a reactor. Hydrogen gas is introduced and the volume ratio of hydrogen gas to cashew nut phenol is maintained at 280-320:1. The reaction is carried out at 160-200℃ for 1.5-2.5 hours to eliminate the unsaturated double bonds in the cashew nut phenol molecule.

[0052] Specifically, the ether bonds in the polyetheramine molecular chain provide a flexible foundation for the curing agent, effectively reducing the internal stress of the curing system; the long-chain alkyl groups of hydrogenated cashew phenol not only interweave between the polyetheramine molecular chains to further alleviate internal stress, but also entangle with the long-chain alkyl groups of the composite coupling agent to form a continuous hydrophobic barrier, improving the corrosion resistance of the coating; benzyl alcohol improves the fluidity of the entire reaction system, exposing more crosslinking sites to catalyze the curing reaction; the silane coupling agent KH-560 participates in the crosslinking reaction, and the epoxy groups reserved at the ends of its molecules can further combine with the composite coupling agent groups on the surface of the filler, strengthening the interfacial compatibility between the curing agent and the filler, so that the filler, curing agent and resin form an integrated network.

[0053] Furthermore, step S3 involves the mixing and dispersion of epoxy resin and flake ceramic micro powder composite filler.

[0054] Specifically, epoxy resin and the flake ceramic micropowder composite filler obtained in step S1 are added to a reactor, and a homogenizer is started to disperse the composite filler at a high speed of 1400-1600 rpm for 30-50 minutes. The high-speed shear force effectively breaks down the agglomerates of the composite filler in the epoxy resin, while guiding the flake ceramic micropowder to initially show a directional alignment trend. Then, the composite filler is dispersed at a speed of 1100-1300 rpm for 15-25 minutes to further refine the particle size of the filler, while avoiding the high-speed shear force from damaging the flaky structure of the flake ceramic micropowder. This allows the composite filler to be uniformly dispersed in the epoxy resin matrix, and the directional alignment of the flake ceramic micropowder forms a dense basic structure, laying the foundation for the subsequent cross-linking reaction with the curing agent and the protective performance of the coating.

[0055] The epoxy resin is a bisphenol A type epoxy resin, which can be selected from one or more of E51 and E44.

[0056] Furthermore, step S4 involves mixing the modified amine curing agent with the resin filler.

[0057] Specifically, the modified amine curing agent synthesized in step S2 is added to the mixture obtained in step S3, and the homogenizer speed is adjusted to a low speed range of 600-800 rpm, and dispersion is continued for 5-10 minutes. The purpose of low-speed dispersion is to avoid destroying the parallel arrangement structure of the flake ceramic powder in the epoxy resin matrix, while ensuring that the modified amine curing agent molecules are in full contact with and uniformly mixed with the resin filler system.

[0058] Furthermore, the coating and curing in step S5 aim to form a coating with both high wear resistance and long-lasting corrosion resistance. The mixture obtained in step S4 is applied to the substrate surface by scraping or spraying. After coating, the substrate is placed in a room temperature environment of 22-28℃ for 24-48 hours to cure, and the film thickness of the coating is 200-1000μm.

[0059] Specifically, during the curing process, the modified amine curing agent undergoes a ring-opening crosslinking reaction with the epoxy resin to form a stable three-dimensional network structure. The flake ceramic micropowder maintains a parallel arrangement in the coating, and through the bifunctional group bridge constructed by the composite coupling agent, it forms a tight bond with the curing agent network without interface gaps, enhancing the physical barrier effect. Nano ZrO2 fills the tiny gaps between the flake layers, improving the structural density and compensating for the insufficient local wear resistance caused by simple SiO2 and Al2O3 modification. Zinc phosphate forms a passivation film on the substrate surface through the electrochemical reaction of zinc ions and phosphate ions, achieving electrochemical active corrosion protection and compensating for the lack of passive protection of epoxy resin. Modified bentonite dissociates into nanoscale sheets in the epoxy resin, and forms a chemical bond with the resin and filler through covalent bonds or hydrogen bonds, enhancing the interfacial adhesion, blocking the crack propagation path, and regulating the balance of coating toughness and hardness. The long-chain alkyl groups of hydrogenated cashew phenol are tightly entangled with the long-chain alkyl groups in the composite coupling agent, forming a continuous and stable hydrophobic barrier in the three-dimensional network structure, blocking the penetration path of corrosive media. Therefore, by coating and curing at room temperature, a coating with high wear resistance, long-lasting corrosion resistance, anti-aging and anti-peeling properties can be formed. It can effectively resist the penetration of corrosive media, microbial erosion, mechanical friction and temperature changes in the submarine tunnel environment, and provide reliable protection for the long-term safe service of concrete segments.

[0060] Specifically, the aforementioned high wear-resistant epoxy anti-corrosion coating material can be applied to the protection of concrete segments in submarine tunnels.

[0061] Example 1: A high wear-resistant epoxy anti-corrosion coating material and its preparation method. By mass, the coating material includes 70 parts epoxy resin, 14 parts flake ceramic micro powder composite filler, and 16 parts modified amine curing agent.

[0062] Step S1: First, pretreat the flake ceramic powder and nano ZrO2 with a composite coupling agent. Mix KH-560 silane coupling agent (mass ratio 1:1) with isopropoxytriisostearoyl titanate coupling agent until homogeneous, then dissolve in an ethanol-water aqueous solution (volume ratio 3:1). The total amount of composite coupling agent is controlled to be 3% of the mass of the flake ceramic powder and 4% of the mass of the nano ZrO2. Add the flake ceramic powder and nano ZrO2 to the prepared coupling agent solution and stir continuously at 60℃ for 1 hour. After stirring, let stand for 30 minutes, filter to collect the solid material, and place it in an oven to dry at 80℃ for 2 hours to complete the pretreatment. Add octadecyltrimethylammonium bromide to the bentonite solution, heat and stir at 80℃ for 1 hour, wash three times with ethanol, and then vacuum dry at 60℃ to obtain modified bentonite. Pretreated flake ceramic powder, nano ZrO2, modified bentonite, and zinc phosphate were mixed in a certain proportion, wherein the mass fraction of flake ceramic powder was 65%, the mass fraction of nano ZrO2 was 14%, the mass fraction of modified bentonite was 15%, and the mass fraction of zinc phosphate was 6%. The mixed material was placed in a ball mill and ball-milled for 3 hours to obtain flake ceramic powder composite filler.

[0063] Step S2: Dissolve preheated and dehydrated cashew phenol in isopropanol and dilute. Add 3% (by weight of cashew phenol) of alumina-supported nickel catalyst to the diluted solution. Place the mixture in a reactor, introduce hydrogen gas, and maintain a hydrogen to cashew phenol volume ratio of 300:1. React at 180°C for 2 hours to obtain hydrogenated cashew phenol. Take 44 parts by weight of polyetheramine D230, 36 parts of hydrogenated cashew phenol, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560. Add polyetheramine D230, hydrogenated cashew phenol, and benzyl alcohol sequentially to the reactor and stir at 60°C for 30 minutes. Slowly add silane coupling agent KH-560 dropwise. After the addition is complete, raise the temperature of the reaction system to 70°C and continue the reaction for 2 hours to obtain a viscous liquid modified amine curing agent.

[0064] Step S3: Add 70 parts of epoxy resin E51 and the flake ceramic micro powder composite filler obtained in step S1 to the reactor, start the homogenizer and disperse at a high speed of 1500 rpm for 40 min, then adjust the homogenizer speed to 1200 rpm and continue to disperse for 20 min.

[0065] Step S4: Add the modified amine curing agent synthesized in step S2 to the mixture obtained in step S3, adjust the homogenizer speed to a low speed range of 700 rpm, and continue to disperse for 10 min.

[0066] Step S5: Apply the mixture obtained in step S4 to the surface of the substrate by spraying, and cure it at 25°C for 36 hours to obtain a high wear-resistant epoxy anti-corrosion coating with a film thickness of 200-1000μm.

[0067] Example 2: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 18 parts flake ceramic micro powder composite filler, and 12 parts modified amine curing agent by mass.

[0068] The preparation method and the parameters and specifications of each raw material in this embodiment are completely consistent with those in Example 1, except that the mass ratio of the flake ceramic micro powder composite filler and the modified amine curing agent is different.

[0069] Example 3: A high wear-resistant epoxy anti-corrosion coating material and its preparation method. By mass, the coating material includes 70 parts epoxy resin, 14 parts flake ceramic micro powder composite filler, and 16 parts modified amine curing agent.

[0070] Compared with Example 1, in this embodiment, the mass ratio of KH-560 silane coupling agent to isopropoxytriisostearoyl titanate coupling agent in step S1 is 1:0.5, and the remaining steps and processes are completely consistent with Example 1.

[0071] Example 4: A high wear-resistant epoxy anti-corrosion coating material and its preparation method. By mass, the coating material includes 70 parts epoxy resin, 14 parts flake ceramic micro powder composite filler, and 16 parts modified amine curing agent.

[0072] Compared with Example 1, in this embodiment, the mass ratio of KH-560 silane coupling agent to isopropoxytriisostearoyl titanate coupling agent in step S1 is 1:1.5, and the remaining steps and processes are completely consistent with Example 1.

[0073] Example 5: A high wear-resistant epoxy anti-corrosion coating material and its preparation method. By mass, the coating material includes 70 parts epoxy resin, 14 parts flake ceramic micro powder composite filler, and 16 parts modified amine curing agent.

[0074] Compared with Example 1, in step S2 of this embodiment, 50 parts by weight of polyetheramine D230, 30 parts of hydrogenated cashew nut shell powder, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560 are taken. The remaining steps and processes are completely consistent with those of Example 1.

[0075] Example 6: A high wear-resistant epoxy anti-corrosion coating material and its preparation method. By mass, the coating material includes 70 parts epoxy resin, 14 parts flake ceramic micro powder composite filler, and 16 parts modified amine curing agent.

[0076] Compared with Example 1, in step S2 of this embodiment, 35 parts by weight of polyetheramine D230, 45 parts of hydrogenated cashew nut phenol, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560 are taken. The remaining steps and processes are completely consistent with those of Example 1.

[0077] Comparative Example 1: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0078] Compared with Example 1, this comparative example replaces the flake ceramic powder with equal amounts of nano-SiO2 and nano-Al2O3 particles, while the remaining steps and processes are the same. Based on the fact that the flake ceramic powder contains 46.5% SiO2 and 39.5% Al2O3, the mass ratio of nano-SiO2 to nano-Al2O3 particles is 1:1.18.

[0079] Step S1: First, pretreat nano-SiO2, nano-Al2O3, and nano-ZrO2 with a composite coupling agent. Mix KH-560 silane coupling agent (mass ratio 1:1) with isopropoxytriisostearoyl titanate coupling agent until homogeneous, then dissolve in an ethanol-water aqueous solution (volume ratio 3:1). The total amount of composite coupling agent is controlled to be 3% of the mass of nano-SiO2 and nano-Al2O3 particles and 4% of the mass of nano-ZrO2. Add nano-SiO2, nano-Al2O3, and nano-ZrO2 to the prepared coupling agent solution and stir continuously at 60℃ for 1 hour. After stirring, let stand for 30 minutes, filter to collect the solid material, and place it in an oven to dry at 80℃ for 2 hours to complete the pretreatment. Add octadecyltrimethylammonium bromide to the bentonite solution, heat and stir at 80℃ for 1 hour, wash three times with ethanol, and then vacuum dry at 60℃ to obtain modified bentonite. Pretreated nano-SiO2, nano-Al2O3, and nano-ZrO2 were mixed with modified bentonite and zinc phosphate in a certain proportion, wherein the mass fractions of nano-SiO2 and nano-Al2O3 were 65%, nano-ZrO2 was 14%, modified bentonite was 15%, and zinc phosphate was 6%. The mixed material was then ball-milled in a ball mill for 3 hours to obtain the composite filler.

[0080] Step S2: Dissolve preheated and dehydrated cashew phenol in isopropanol and dilute. Add 3% (by weight of cashew phenol) of alumina-supported nickel catalyst to the diluted solution. Place the mixture in a reactor, introduce hydrogen gas, and maintain a hydrogen to cashew phenol volume ratio of 300:1. React at 180°C for 2 hours to obtain hydrogenated cashew phenol. Take 44 parts by weight of polyetheramine D230, 36 parts of hydrogenated cashew phenol, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560. Add polyetheramine D230, hydrogenated cashew phenol, and benzyl alcohol sequentially to the reactor and stir at 60°C for 30 minutes. Slowly add silane coupling agent KH-560 dropwise. After the addition is complete, raise the temperature of the reaction system to 70°C and continue the reaction for 2 hours to obtain a viscous liquid modified amine curing agent.

[0081] Step S3: Add 70 parts of epoxy resin E51 and the composite filler obtained in step S1 to the reactor, start the homogenizer and disperse at a high speed of 1500 rpm for 40 min, then adjust the homogenizer speed to 1200 rpm and continue to disperse for 20 min.

[0082] Step S4: Add the modified amine curing agent synthesized in step S2 to the mixture obtained in step S3, adjust the homogenizer speed to a low speed range of 700 rpm, and continue to disperse for 10 min.

[0083] Step S5: Apply the mixture obtained in step S4 to the surface of the substrate by spraying, and cure it at 25°C for 36 hours to obtain a high wear-resistant epoxy anti-corrosion coating with a film thickness of 200-1000μm.

[0084] Comparative Example 2: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass.

[0085] Compared with Example 1, the composite filler in this comparative example does not contain flake ceramic powder. The mass fractions of each component are 40% nano ZrO2, 42% modified bentonite, and 18% zinc phosphate. The remaining process parameters are exactly the same as those in Example 1.

[0086] Step S1: First, pretreat the nano-ZrO2 with a composite coupling agent. Mix KH-560 silane coupling agent (mass ratio 1:1) and isopropoxytriisostearoyl titanate coupling agent evenly, and dissolve them in an ethanol-water aqueous solution with a volume ratio of 3:1. The total amount of the composite coupling agent is controlled to be 4% of the mass of the nano-ZrO2. Add the nano-ZrO2 to the prepared coupling agent solution and stir continuously at 60℃ for 1 hour. After stirring, let it stand for 30 minutes, filter to collect the solid material, and place it in an oven to dry at 80℃ for 2 hours to complete the pretreatment. Add octadecyltrimethylammonium bromide to the bentonite solution, heat and stir at 80℃ for 1 hour, wash three times with ethanol, and then vacuum dry at 60℃ to obtain modified bentonite. Pretreated nano-ZrO2 was mixed with modified bentonite and zinc phosphate in a certain proportion, wherein the mass fraction of nano-ZrO2 was 40%, the mass fraction of modified bentonite was 42%, and the mass fraction of zinc phosphate was 18%. The mixed material was placed in a ball mill and ball-milled for 3 hours to obtain the composite filler.

[0087] Step S2: Dissolve preheated and dehydrated cashew phenol in isopropanol and dilute. Add 3% (by weight of cashew phenol) of alumina-supported nickel catalyst to the diluted solution. Place the mixture in a reactor, introduce hydrogen gas, and maintain a hydrogen-to-cashew phenol volume ratio of 300:1. React at 180°C for 2 hours to obtain hydrogenated cashew phenol. Take 44 parts by weight of polyetheramine D230, 36 parts of hydrogenated cashew phenol, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560. Specifically, add polyetheramine D230, hydrogenated cashew phenol, and benzyl alcohol sequentially to the reactor and stir at 60°C for 30 minutes. Slowly add silane coupling agent KH-560 dropwise. After the addition is complete, raise the temperature of the reaction system to 70°C and continue the reaction for 2 hours to obtain a viscous liquid modified amine curing agent.

[0088] Step S3: Add 70 parts of epoxy resin E51 and the composite filler obtained in step S1 to the reactor, start the homogenizer and disperse at a high speed of 1500 rpm for 40 min, then adjust the homogenizer speed to 1200 rpm and continue to disperse for 20 min.

[0089] Step S4: Add the modified amine curing agent synthesized in step S2 to the mixture obtained in step S3, adjust the homogenizer speed to a low speed range of 700 rpm, and continue to disperse for 10 min.

[0090] Step S5: Apply the mixture obtained in step S4 to the surface of the substrate by spraying, and cure it at 25°C for 36 hours to obtain a high wear-resistant epoxy anti-corrosion coating with a film thickness of 200-1000μm.

[0091] Comparative Example 3: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass.

[0092] Compared with Example 1, this comparative example does not contain nano ZrO2 in the composite filler. The mass fraction of each component is 76% flake ceramic micro powder, 17% modified bentonite, and 7% zinc phosphate. The remaining steps and process parameters are the same as in Example 1.

[0093] Comparative Example 4: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass.

[0094] Compared with Example 1, in step S1, the composite filler does not contain zinc phosphate, and the mass fractions of each component are 69% flake ceramic powder, 15% nano ZrO2, and 16% modified bentonite. The remaining steps and process parameters are the same as in Example 1.

[0095] Comparative Example 5: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0096] Compared with Example 1, in step S1, the composite filler does not contain modified bentonite, and the mass fractions of each component are 76.5% flake ceramic powder, 16.5% nano ZrO2, and 7% zinc phosphate. The remaining steps and process parameters are the same as in Example 1.

[0097] Comparative Example 6: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0098] Compared with Example 1, in step S2, the modified amine curing agent in this comparative example does not contain benzyl alcohol. 50 parts by weight of polyetheramine D230, 41 parts of hydrogenated cashew nut phenol, and 9 parts of silane coupling agent KH-560 are used. The remaining steps and process parameters are the same as in Example 1.

[0099] Comparative Example 7: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0100] Compared with Example 1, in step S2, the modified amine curing agent in this comparative example does not contain hydrogenated cashew phenol. 69 parts by weight of polyetheramine D230, 19 parts by weight of benzyl alcohol, and 12 parts by weight of silane coupling agent KH-560 are used. The remaining steps and process parameters are the same as in Example 1.

[0101] Comparative Example 8: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0102] Compared with Example 1, in step S2, the modified amine curing agent used was unhydrogenated cashew phenol, and 44 parts by weight of polyetheramine D230, 36 parts of ordinary cashew phenol, 12 parts of benzyl alcohol, and 8 parts of silane coupling agent KH-560 were used. The remaining steps and process parameters were the same as in Example 1.

[0103] Comparative Example 9: A method for preparing a high wear-resistant epoxy anti-corrosion coating material, wherein the coating material comprises 70 parts epoxy resin, 14 parts composite filler, and 16 parts modified amine curing agent by mass components.

[0104] Compared with Example 1, in step S1, the flake ceramic powder and nano ZrO2 were pretreated only with silane coupling agent KH-560, while the remaining steps and process parameters were the same as in Example 1. Specifically, step S1 is as follows:

[0105] Flake ceramic micropowder and nano ZrO2 were pretreated with a coupling agent. KH-560 silane coupling agent was dissolved in an ethanol-water aqueous solution with a volume ratio of 3:1. The flake ceramic micropowder and nano ZrO2 were added, stirred at 60℃ for 1 hour, allowed to stand for 30 minutes, filtered, and dried at 80℃ for 2 hours to complete the pretreatment. Octadecyltrimethylammonium bromide was added to a bentonite solution, heated and stirred at 80℃ for 1 hour, washed three times with ethanol, and then vacuum dried at 60℃ to obtain modified bentonite. The pretreated flake ceramic micropowder, nano ZrO2, modified bentonite, and zinc phosphate were mixed in a specific ratio, with the flake ceramic micropowder mass fraction being 65%, nano ZrO2 mass fraction being 14%, modified bentonite mass fraction being 15%, and zinc phosphate mass fraction being 6%. The mixed material was ball-milled for 3 hours to obtain the flake ceramic micropowder composite filler.

[0106] Experimental Example 1: Performance tests were conducted on Examples 1-6 and Comparative Examples 7-9, including interfacial pull-out adhesion, water contact angle, gloss retention rate under xenon lamp aging, and electrochemical impedance modulus.

[0107] For interfacial pull-out adhesion, the pull-out strength of the coating to the concrete substrate was tested according to GB / T5210-2006 "Paints and Varnishes - Pull-out Adhesion Test". The static water contact angle of the coating surface was measured using a contact angle meter, and the average value of three different measuring points was taken. According to GB / T1865-2009 "Paints and Varnishes - Artificial Climate Aging and Artificial Radiation Exposure to Filtered Xenon Arc Radiation", after aging for 1000 hours, the 60° gloss of the coating was tested, and the gloss retention rate was calculated. Using an electrochemical workstation, the coating was immersed in 3.5% NaCl solution for 6 months, and the impedance modulus in the low-frequency region (0.01Hz) was tested to reflect the coating's resistance to the penetration of corrosive media.

[0108] The test results are shown in Table 1.

[0109] Table 1 Coating performance test results

[0110]

[0111] As shown in Table 1, the ratio of KH-560 to isopropoxytriisostearoyl titanate differs in Examples 1, 3, and 4. The interfacial pull-out adhesion of Example 1 is 5.2 MPa, while that of Examples 3 and 4 decreases to 4.8 MPa and 4.7 MPa, respectively. The 1:1 ratio in Example 1 achieves complementarity between the covalent anchoring of the silane coupling agent and the coordination complexation anchoring of the titanate coupling agent, constructing a strong filler-matrix interfacial bond structure. Insufficient titanate content leads to insufficient hydrophobic long link branch density, while excessive content causes coupling agent agglomeration and decreased filler modification uniformity, both of which directly weaken the interfacial bond strength. Meanwhile, the ratio of the composite coupling agent determines the uniformity of the distribution of hydrophobic long chains on the filler surface, simultaneously affecting the fundamental performance of water contact angle, gloss retention rate, and electrochemical impedance modulus. In Examples 1, 3, and 4, the water contact angle decreased from 115° to 110° and 108°, respectively; the gloss retention rate decreased from 88% to 85% and 83%, respectively; and the electrochemical impedance modulus decreased from 1.5 × 10⁻⁶ to 1.5 × 10⁻⁶. 9 Ω・cm 2 1.2×10 9 Ω・cm, 1.1×10 9 Ω・cm 2 .

[0112] Examples 1, 5, and 6 use different amounts of hydrogenated cashew nut shell extract: 36 parts in Example 1, 30 parts in Example 5, and 45 parts in Example 6. Example 1 has the best water contact angle and electrochemical impedance modulus, while Example 5 has the best values ​​of 112° and 1.3 × 10⁻⁶, respectively. 9 Ω・cm 2 Example 6 reduced to 109°, 1.0 × 10 9 Ω・cm 2 Example 1 shows that the amount of hydrogenated cashew phenol used optimizes the entanglement density between the long-chain alkyl groups of hydrogenated cashew phenol and the hydrophobic long chains of the composite coupling agent, forming a dense and continuous hydrophobic barrier. The integrity of the hydrophobic barrier determines the water contact angle and electrochemical impedance modulus. In Example 5, insufficient long-chain alkyl density resulted in micro-gaps in the hydrophobic barrier. In Example 6, excessive long-chain alkyl groups interspersed between the polyetheramine molecular chains reduced the curing crosslinking density, leading to a decrease in the density of the hydrophobic barrier. Both of these factors degrade the hydrophobicity and corrosion resistance of the coating. Therefore, the amount of hydrogenated cashew phenol used affects the water contact angle and electrochemical impedance modulus. Simultaneously, the long-chain entanglement effect and changes in crosslinking density indirectly affect the interfacial pull-out adhesion and gloss retention rate. In Examples 1, 5, and 6, the interfacial pull-out adhesion decreased from 5.2 MPa to 4.9 MPa and 4.6 MPa, respectively, and the gloss retention rate decreased from 88% to 86% and 82%, respectively.

[0113] Example 2 involves adjusting the overall composition ratio of the coating. Compared to Example 1, only the ratio of filler to curing agent differs. Its interfacial pull-out adhesion is 5.0 MPa, water contact angle is 113°, gloss retention is 87%, and electrochemical impedance modulus is 1.4 × 10⁻⁶. 9 Ω・cm 2 Therefore, within a reasonable scope, this invention has flexible implementation capabilities and is suitable for large-scale production under different process requirements.

[0114] Comparative Example 7, without the addition of hydrogenated cashew nut shellac, could not form long-chain entanglements with the composite coupling agent, resulting in a lack of hydrophobic barrier; its water contact angle was only 82° and its electrochemical impedance modulus was only 8.2 × 10⁻⁶. 6 Ω・cm 2 This indicates that hydrogenated cashew nut shell powder plays an important role in the hydrophobicity and corrosion resistance of the coating. Comparative Example 8 uses unhydrogenated cashew nut shell powder, which can form temporary long-chain entanglement with the composite coupling agent, resulting in an interfacial pull-out adhesion of 5.1 MPa, close to the level of Example 1. However, the unsaturated double bonds in the unhydrogenated cashew nut shell powder molecule are easily oxidized and broken, resulting in a gloss retention rate of only 51% and a significant deterioration in the coating's anti-aging properties. Comparative Example 9 uses a single KH-560 coupling agent, which lacks the coordination complexation effect of titanate esters and cannot construct a strong filler-matrix interfacial bond structure. Its interfacial pull-out adhesion is only 2.6 MPa, indicating that the combined use of composite coupling agents is beneficial to improving the interfacial bond strength of the coating.

[0115] Experimental Example 2: Performance tests were conducted on Example 1 and Comparative Examples 1-6, including erosion and abrasion resistance, resistance to high and low temperature alternation, and room temperature curing degree.

[0116] Specifically, for the erosion abrasion resistance weight loss rate, a simplified jet erosion test was used. Seawater containing sand (0.5mm particle size) was used to scour the coating at a flow rate of 5m / s. After 100 hours of erosion, the coating was weighed, and the weight loss rate was calculated as: Weight loss rate = (mass before erosion - mass after erosion) / mass before erosion × 100%. For high and low temperature alternation resistance, the coating was cycled in the range of -20-60℃, with a low temperature cycle of 4 hours, a room temperature transition of 1 hour, and a high temperature cycle of 4 hours. Cracks and peeling were observed in the coating, and the number of defect-free cycles was recorded. For room temperature curing degree, differential scanning calorimetry (DSC) was used to test the actual heat of reaction after curing at 25℃ for 24 hours. This was compared with the heat of reaction after complete curing, and the degree of curing was calculated as: Degree of curing = (actual heat of reaction / heat of reaction after complete curing) × 100%. The test results are shown in Table 2.

[0117] Table 2 Coating performance test results

[0118]

[0119] As shown in Table 2, in terms of erosion and wear loss rate, the 0.07% of Example 1 is much lower than that of Comparative Example 1 (2.10% with SiO2 and Al2O3 replacing flake ceramics), Comparative Example 2 (3.30% without flake ceramics), and Comparative Example 5 (0.13% without modified bentonite). This difference is inseparable from the synergistic effect of the composite coupling agent and hydrogenated cashew nut shell powder. The composite coupling agent and hydrogenated cashew nut shell powder achieve a strong bond between the filler and the organic matrix, allowing the multi-component filler to fully perform its function.

[0120] Specifically, the parallel arrangement of the flake-like structure of the ceramic micropowder forms a rigid wear-resistant skeleton, while nano-ZrO2 fills the gaps between the flakes to prevent localized wear concentration. The nano-sheets of the dissociated modified bentonite play a bonding and regulating role between the filler and the matrix, alleviating stress concentration during the wear process. In contrast, in Comparative Example 1, the nanoparticles lack the directional protection of the flake-like structure and are prone to agglomeration. Comparative Example 2 loses its core wear-resistant skeleton due to the absence of flake ceramics, and Comparative Example 5 suffers from easy peeling of the filler-matrix interface due to the lack of modified bentonite. None of these examples can achieve a "rigid and flexible" wear-resistant effect.

[0121] In terms of resistance to high and low temperature cycling, Example 1's 50 crack-free cycles were significantly better than Comparative Example 5's 20 cycles, Comparative Example 2's 15 cycles, and Comparative Example 1's 25 cycles. This is because the composite coupling agent and the hydrogenated cashew phenol core synergistically eliminated the interfacial voids between the filler and the matrix, preventing stress concentration at the interface during temperature cycling. Furthermore, the modified bentonite nanosheets further blocked the crack propagation path, while the rigid support of the flake ceramics and nano-ZrO2 resisted the volume shrinkage stress caused by temperature changes. The synergy of these three factors allowed the coating to maintain structural integrity during extreme temperature cycling. Without modified bentonite, cracks easily propagate along the filler-matrix interface. Without flake ceramics or when particles are used instead, the coating's resistance to volume changes decreased significantly, leading to a sharp reduction in the number of cycles.

[0122] Regarding the degree of curing at room temperature, Example 1 achieved 93%, which is higher than the 67% of Comparative Example 6 without benzyl alcohol. This is because benzyl alcohol not only improves the fluidity of the system and exposes more crosslinking sites, but also forms a synergistic effect with the modified amine curing agent. The long-chain alkyl group of hydrogenated cashew phenol has reduced the internal stress of the curing system, and the silane coupling agent KH-560 enhances the interfacial compatibility between the curing agent and the filler. Furthermore, benzyl alcohol further optimizes the curing reaction environment, allowing the ring-opening crosslinking reaction between the curing agent and the epoxy resin to be more complete. Without benzyl alcohol, the system has poor fluidity, and the crosslinking sites are difficult to contact fully. Even with interfacial synergy, efficient room temperature curing cannot be achieved, ultimately leading to a significant reduction in the degree of curing.

[0123] The zinc phosphate-free comparative example 4 exhibited an erosion wear weight loss rate of 0.09% and resistance to 50 cycles of high and low temperature alternation, similar to Example 1. However, electrochemical impedance spectroscopy (EIS) was also performed on it, and its impedance modulus after 6 months was only 5.8 × 10⁻⁶. 8 Ω・cm2 This is significantly lower than the 1.5 × 10⁻⁶ in Example 1. 9 Ω・cm 2 The core reason is that Comparative Example 4 lacks the active corrosion protection supplement of zinc phosphate. Zinc phosphate can form a passivation film on the substrate surface and actively inhibit steel corrosion through the electrochemical reaction of zinc ions and phosphate ions. It forms a dual synergy of delaying penetration and actively inhibiting corrosion with passive protection. However, Comparative Example 4 lacks this active protection component, making it difficult to resist the continuous penetration of corrosive media during long-term service, which ultimately leads to a significant reduction in corrosion protection life. This also confirms the indispensability of zinc phosphate as an electrochemical active corrosion protection component in multi-element fillers, as well as the complementary value of auxiliary synergy and core synergy.

[0124] Based on the preferred embodiments of the present invention described above, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method for preparing a high wear-resistant epoxy anti-corrosion coating material, characterized in that, Includes the following steps: S1. Pretreated flake ceramic micro powder, nano ZrO2, modified bentonite, and zinc phosphate are mixed and ball-milled for 2-4 hours to obtain flake ceramic micro powder composite filler; wherein, the flake diameter of the flake ceramic is 10-50 μm and the thickness is 1-5 μm; the composite coupling agent includes silane coupling agent KH-560 and titanate coupling agent; S2. Add polyetheramine, hydrogenated cashew nut phenol and benzyl alcohol to the reaction vessel in sequence, stir and mix at 55-65℃ for 25-35 min, slowly add silane coupling agent KH-560, raise the temperature to 70-75℃ and continue the reaction for 1.5-2 h to obtain modified amine curing agent. S3. Add epoxy resin and the flake ceramic micro powder composite filler to the reactor, disperse at 1400-1600 rpm for 30-50 min, and then disperse at 1100-1300 rpm for 15-25 min. S4. Add the modified amine curing agent to the mixture obtained in step S3 and disperse it at 600-800 rpm for 5-10 min; S5. Apply or spray the material obtained in step S4 onto the surface of the substrate and cure at 22-28℃ for 24-48 hours.

2. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S1, the titanate coupling agent is a monoalkoxy type titanate coupling agent, selected from one or more of isopropoxytriisostearoyl titanate and isopropoxytris(dioctylpyrophosphate)titanate.

3. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S1, the pretreatment of the composite coupling agent includes: Flake ceramic micro powder and nano ZrO2 are added to a composite coupling agent, stirred at 55-65℃ for 0.5-2h, allowed to stand for 0.2-1h, filtered, and dried at 75-85℃ for 1-3h. The mass ratio of silane coupling agent KH-560 to titanate coupling agent in the composite coupling agent is 1:0.5-1.5; The total amount of the composite coupling agent is 2-3% of the mass of the flake ceramic micro powder and 3-4% of the mass of the nano ZrO2.

4. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S1, the mass fraction of the flake ceramic powder is 55-80%, the mass fraction of nano ZrO2 is 12-18%, the mass fraction of modified bentonite is 15-25%, the mass fraction of zinc phosphate is 2-6%, and the sum of all components is 100%.

5. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S1, the size of the nano ZrO2 is 2-8 nm, and the particle size D50 of the zinc phosphate is 15-20 μm.

6. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S1, the modified bentonite is prepared as follows: Octadecyltrimethylammonium bromide was added to a bentonite solution, heated and stirred at 75-85°C for 0.5-1.5 h, washed with ethanol, and then vacuum dried at 55-65°C.

7. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S2, the modified amine curing agent comprises, by weight, 35-50 parts polyetheramine, 30-45 parts hydrogenated cashew nut shell powder, 10-15 parts benzyl alcohol, and 5-8 parts silane coupling agent KH-560.

8. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S2, the hydrogenated cashew phenol is prepared as follows: Preheated and dehydrated cashew phenols were dissolved in isopropanol and diluted. 2-4% nickel-based catalyst was added, and the reaction was carried out at 160-200℃ for 1.5-2.5 hours. During the reaction, the volume ratio of hydrogen to cashew phenols was controlled at 280-320:

1.

9. The method for preparing a high wear-resistant epoxy anti-corrosion coating material according to claim 1, characterized in that: In step S4, the thickness of the cured coating is 200-1000 μm.

10. A high wear-resistant epoxy anti-corrosion coating material, characterized in that: By weight, it includes 60-80 parts epoxy resin, 14-18 parts flake ceramic micro powder composite filler, and 8-16 parts modified amine curing agent.

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