An antifouling and anticorrosion integrated coating with long-acting high adhesion and super-slippery function, and a preparation method and application thereof

Abstract

The application discloses a kind of long-acting high-adhesion, super-slippery function's antifouling anticorrosion integrated coating and its preparation method and application, belong to marine antifouling super-slippery coating material preparation field.The preparation method includes: preparation high-adhesion type epoxy resin precursor, obtain liquid product EGDE-PCA;Preparation high-adhesion, super-slippery integrated epoxy resin precursor, obtain oil liquid product EGDE-PCA / APT-PDMS;EGDE-PCA / APT-PDMS is added to isophorone diamine mixed stirring uniform, coating is carried out on metal material sample, vacuum insulation condition is carried out drying curing reaction, obtains long-acting high-adhesion, super-slippery function's antifouling anticorrosion integrated coating.In early stage of the synthesis reaction, it is not necessary to add organic solvent, and the environmental protection is improved, and the problem that construction process is difficult due to poor fluidity is solved;The coating of the application has super-slippery durability and excellent antifouling anticorrosion effect.

Description

Technical Field

[0001] This invention belongs to the field of marine antifouling and super-slippery coating material preparation, specifically involving an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function, its preparation method and application. Background Technology

[0002] Biofouling in the marine environment is a global challenge facing ships, marine engineering facilities, and underwater equipment. The attachment of organisms such as barnacles, algae, and bacteria not only significantly increases ship drag and energy consumption (energy consumption can increase by 36% for every 10% increase in pollution coverage), but can also accelerate the corrosion of metal structures, threatening the safety and service life of marine equipment. Meanwhile, organotin materials widely used in traditional antifouling and anticorrosion coatings are toxic, seriously harming the marine ecosystem and have been banned by international conventions. Therefore, developing efficient, environmentally friendly, and durable integrated antifouling and anticorrosion coatings has become a research hotspot in marine science and materials engineering.

[0003] Against this backdrop, super-lubricating antifouling coatings, through biomimetic design, construct a dynamic lubrication interface, replacing chemical toxicity with a physical repulsion mechanism, demonstrating significant environmental friendliness. However, traditional super-lubricating coatings face two key bottlenecks: the lubrication layer is easily lost, leading to insufficient antifouling effectiveness, and the coating's adhesion to the substrate is weak. Especially in dynamic marine environments, if the coating cannot form a strong bond with the substrate, it is prone to peeling due to water flow shear or mechanical impact, resulting in a rapid decline in antifouling function. Therefore, how to overcome the mutually exclusive contradiction of "high adhesion - super-lubricity" and achieve synergistic optimization of the two has become a technical barrier that urgently needs to be overcome in this field.

[0004] In recent years, the interdisciplinary innovation of materials science and interface engineering has provided a breakthrough path for this challenge. Through molecular-level structural design, a high-adhesion underlayer is constructed at the substrate interface to enhance the bonding strength, while a dynamic lubrication network is formed on the surface to maintain super-lubricating properties. For example, Chinese patent CN202510213774.0 discloses a high-adhesion transparent self-healing super-lubricating coating and its preparation method. Through the interaction between the coating and the interface groups, a high adhesion effect is obtained, and the super-lubricating performance is achieved through the movement of polydimethylsiloxane chains. Chinese patent CN202411930510.9 discloses a super-lubricating antibacterial coating material and its preparation method and application. The anti-fouling and super-lubricating effects are achieved through the synergistic effect of silver ions and silane chains. The above preparation methods have two shortcomings: (1) the preparation process is relatively complicated, which is not conducive to large-scale application; (2) organic solvents are used in the early synthesis reaction process, which increases the safety risks; (3) the adhesion between the coating and the substrate is limited, and it is impossible to guarantee that the lubricating components exist in the coating substrate for a long time. High-adhesion super-lubricating coatings have gradually moved from laboratory research to engineering applications, but their large-scale promotion still faces challenges such as long-term lubricant stability, adaptability to complex working conditions, and low-cost manufacturing. In the future, through the deep integration of smart responsive materials (such as photothermal controlled-release polymers) and advanced manufacturing technologies (such as 3D-printed microstructures), such coatings are expected to open up broader application scenarios in fields such as corrosion protection of marine equipment, underwater optical devices, and seawater desalination membranes, providing innovative solutions for the sustainable development of the marine economy. Summary of the Invention

[0005] To address the problems of low adhesion strength, poor durability, and inadequate antifouling effect in existing marine antifouling coatings, this invention provides a long-lasting, highly adhesive, and ultra-lubricating integrated antifouling and anti-corrosion coating with spontaneous migration properties and its preparation method. By introducing protocatechuic acid (PCA) into the epoxy resin precursor, the intrinsic adhesion strength and bactericidal effect of the coating are improved. Utilizing the lubricating properties of aminopropyl double-terminated polydimethylsiloxane (APT-PDMS), it is anchored in the epoxy resin precursor as a curing component. During epoxy resin curing, the lubricating substance spontaneously migrates to the coating surface, forming a flexible polymer molecular brush, enhancing the coating's lubrication effect without easy loss, thus achieving long-term coating service and improving antifouling durability. By simplifying the process, a coating with high adhesion strength, excellent ultra-lubricating properties, and antifouling and anti-corrosion effects can be prepared efficiently and conveniently, significantly improving its application performance.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing an integrated antifouling and anticorrosion coating with long-lasting, high-adhesion, and super-slippery functions, comprising the following steps:

[0008] Preparation of high-adhesion epoxy resin precursor:

[0009] p-Toluenesulfonic acid monohydrate ( p EGDE (-TsOH) and protocatechuic acid (PCA) monomers were added to ethylene glycol diglycidyl ether (EGDE), stirred to form a homogeneous solution, and heated under an inert atmosphere to carry out the reaction. After the reaction was completed, organic solvent and water were added for solution extraction, and finally the solvent was evaporated to obtain the liquid product EGDE-PCA.

[0010] Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0011] The liquid product EGDE-PCA was mixed with aminopropyl dual-terminated polydimethylsiloxane (APT-PDMS) and then added to a polar organic solvent. The mixture was stirred and heated to carry out the reaction. After the reaction was completed, the solvent in the liquid mixture was evaporated to obtain the oily liquid product EGDE-PCA / APT-PDMS.

[0012] Preparation of a high-adhesion, ultra-slippery integrated anti-fouling and anti-corrosion coating:

[0013] The oily liquid product EGDE-PCA / APT-PDMS was added to isophorone diamine (IPDA), mixed and stirred evenly. The liquid mixture was then coated onto a metal material sample and dried and cured under vacuum conditions to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super-slip function.

[0014] Furthermore, in the preparation of high-adhesion epoxy resin precursors p The molar ratio of -TsOH, PCA, and EGDE is (0.01-0.05):(0.1-0.5):1;

[0015] Magnetic stirring is used, and the reaction temperature is heated to 80℃-120℃ for 3h-8h.

[0016] Furthermore, in the preparation of the high-adhesion epoxy resin precursor, the organic solvent is dichloromethane or trichloromethane, and the water is deionized water.

[0017] Furthermore, in the preparation of the high-adhesion, super-lubricating integrated epoxy resin precursor, the molar ratio of APT-PDMS to EGDE-PCA is (0.01-0.07):1.

[0018] Furthermore, magnetic stirring was used in the preparation of the high-adhesion, super-lubricating integrated epoxy resin precursor, and the heating reaction temperature was 30℃-80℃ for 3h-5h.

[0019] Furthermore, the polar organic solvent used in the preparation of the high-adhesion, super-lubricating integrated epoxy resin precursor is one of anhydrous ethanol, acetone, ethyl acetate, or tetrahydrofuran.

[0020] Furthermore, in the preparation of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating, the molar ratio of IPDA to EGDE-PCA / APT-PDMS is (0.93-0.99):1.

[0021] Furthermore, ultrasonic stirring is used in the preparation of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating, with a stirring time of 5-15 minutes;

[0022] Vacuum insulation is achieved by using a vacuum oven and evacuating the air for 10-15 minutes.

[0023] The drying and curing reaction temperature is 30℃-80℃, and the time is 12h-36h.

[0024] Secondly, the present invention also provides an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function, which is prepared by the preparation method of the integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function described in the first aspect.

[0025] Thirdly, the present invention also provides an application of the integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function described in the second aspect, used as a super-slippery antifouling and anticorrosion coating for ships, marine engineering facilities and underwater equipment.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. This invention uses EGDE, an epoxy resin precursor with good flowability and high transparency. In the early synthesis reaction, no organic solvents need to be added, which improves environmental friendliness and solves the problem of difficult construction process caused by poor flowability.

[0028] 2. This invention combines a certain proportion of PCA and EGDE, and fixes PCA in epoxy resin by chemical grafting. The catechol structure in PCA can form strong chemical bonds, metallic bonds and other bonds with various substrates, giving epoxy resin excellent intrinsic high adhesion properties and improving the durability of the coating in various applications.

[0029] 3. This invention uses chemical grafting to introduce APT-PDMS into epoxy resin. During the cross-linking and curing process, the lubricating substance will spontaneously migrate to the coating surface to form a layer of PDMS flexible molecular brush, which gives the material super-slip properties, reduces the biofouling rate, and the lubricating substance will not be easily lost, thus improving the super-slip durability of the material.

[0030] 4. The PCA introduced in this invention also has a highly efficient intrinsic bactericidal function, which can kill a variety of marine bacteria and pathogenic bacteria, further inhibiting the formation of biofilm, reducing the biofouling rate, and constructing a dual antifouling system.

[0031] 5. The coating prepared by this invention has high transparency, which meets the requirements of aesthetics, and the raw materials used are low in cost, which provides feasibility for promoting large-scale application in the field of marine engineering. Attached Figure Description

[0032] Figure 1 The flowcharts for the preparation of the antifouling and anticorrosion integrated coatings with long-lasting high adhesion and super-slippery functions in Examples 1 to 10 are shown.

[0033] Among them: 1. EDGE; 2. PCA; 3. p -TsOH; 4. APT-PDMS; 5. IPDA;

[0034] Figure 2 The images are scanning electron microscope (SEM) images of the bottom layer and the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating of Example 1, wherein: (a) is the SEM image of the bottom layer of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating, and (b) is the SEM image of the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating.

[0035] Figure 3 The images show the energy dispersive X-ray spectra (EDS) of the underlayer and surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating in Example 1, where: (a) is the EDS image of the underlayer of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating, and (b) is the EDS image of the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating.

[0036] Figure 4 The images show X-ray photoelectron spectroscopy (XPS) patterns of the contact surface between the high-adhesion, super-slippery integrated antifouling and anticorrosion coating and the substrate, and the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating in Example 1.

[0037] Figure 5 Differential scanning calorimetry (DSC) curves of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating of Example 1 and the control group;

[0038] Figure 6 Thermogravimetric analysis (TGA) curves of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating of Example 1 and the control group are shown.

[0039] Figure 7 Example 1: Scanning electron microscope (SEM) images of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating and a control group after different cycles of rubbing;

[0040] Figure 8Example 1: Colony count diagrams of a high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating, a blank group, and a control group;

[0041] Figure 9 Example 1: Effect diagram of cyclic salt spray test on high adhesion, super slippery integrated antifouling and anticorrosion coating, blank substrate and control group;

[0042] Figure 10 This is a comparison chart of the contact angle and sliding angle of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating of Example 2 and the control group;

[0043] Figure 11 This is a dynamic image of water droplets sliding off the surface of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating in Example 2.

[0044] Figure 12 This is a comparison chart of the contact angle and sliding angle of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating in Example 4 and the control group;

[0045] Figure 13 The image shows a comparison of the contact angle and sliding angle between the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating of Example 5 and the control group. Detailed Implementation

[0046] The technical solutions and effects of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. Experimental methods without specific conditions are generally performed under conventional conditions, such as those described in textbooks and experimental guides, or as recommended by the manufacturer, and are well-known or readily understood by those skilled in the art. The following embodiments are merely preferred embodiments of the present invention and do not limit the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

[0047] A method for preparing an integrated antifouling and anticorrosion coating with long-lasting, high adhesion, and super-slippery properties, such as... Figure 1 As shown, the specific steps include:

[0048] Preparation of high-adhesion epoxy resin precursor:

[0049] Will p -TsOH 3 and PCA 2 monomers were added to EGDE 1. p The molar ratio of -TsOH 3, PCA 2 and EGDE 1 is (0.01-0.05):(0.1-0.5):1. The mixture is magnetically stirred to form a homogeneous solution. The solution is heated to 80℃-120℃ under an inert atmosphere for 3-8 hours. After the reaction is completed, an organic solvent and deionized water are added for solution extraction. The organic solvent is dichloromethane or trichloromethane. Finally, the solvent is evaporated to obtain the liquid product EGDE-PCA.

[0050] Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0051] The liquid product EGDE-PCA was mixed with APT-PDMS 4 and then added to a polar organic solvent. The molar ratio of APT-PDMS 4 to EGDE-PCA was (0.01-0.07):1. The polar organic solvent included one of anhydrous ethanol, acetone, ethyl acetate or tetrahydrofuran. The mixture was stirred and heated to 30℃-80℃ for 3-5 hours. After the reaction was completed, the solvent in the liquid mixture was evaporated by rotary evaporation, and finally the oily liquid product EGDE-PCA / APT-PDMS was obtained.

[0052] Preparation of a high-adhesion, ultra-slippery integrated anti-fouling and anti-corrosion coating:

[0053] The oily liquid product EGDE-PCA / APT-PDMS was added to IPDA 5, with a molar ratio of IPDA 5 to EGDE-PCA / APT-PDMS of (0.93-0.99):1. After mixing, the mixture was ultrasonically stirred for 5-15 minutes to form a homogeneous liquid mixture. The liquid mixture was then coated onto a metal material sample and placed in a vacuum oven for 10-15 minutes after degassing. The sample was then dried and cured at 30-80°C for 12-36 hours to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super-slip properties.

[0054] An integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function is prepared by the above-mentioned preparation method of the integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function.

[0055] An application of the above-mentioned integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function, used as a super-slippery antifouling and anticorrosion coating for ships, marine engineering facilities and underwater equipment.

[0056] EGDE, an epoxy resin precursor, is a low-viscosity, transparent aliphatic epoxy resin with a viscosity between 10 and 100 mPa·s. It has excellent processing properties and, due to its excellent flowability, reduces the use of organic solvents during application. This invention uses this epoxy resin as a matrix to greatly improve environmental performance.

[0057] Protocatechuic acid (PCA) is a substance extracted from ferns. It exhibits varying degrees of antibacterial activity against various pathogenic bacteria, such as Escherichia coli, Staphylococcus aureus, and Salmonella typhi, and also shows some inhibitory effect on common viruses. It is widely used in the medical field. Furthermore, PCA is a dopamine-like substance containing a catechol structure. Dopamine is mainly found in mussels and contains a large amount of catechol, which is key to their ability to firmly adhere to surfaces such as rocks. Scientists have used this property to develop many high-performance biomimetic adhesives. However, dopamine is relatively expensive, increasing costs during use. PCA, on the other hand, is nearly 20 times cheaper than dopamine and also contains catechol groups, enabling it to form strong chemical, covalent, and metallic bonds with various substrate surfaces, making it an ideal material with practical applications.

[0058] Aminopropyl dual-terminated polydimethylsiloxane is a siloxane polymer containing amino functional groups. It combines the flexibility of siloxanes, low surface energy, and reactivity of amino groups. The low surface energy of the siloxane backbone (approximately 20mN / m-22mN / m) makes it easy to spread on the substrate surface, forming a lubricating film and reducing the coefficient of friction. It is widely used in cosmetics, textiles, coatings, adhesives and other fields. The flexibility of the molecular chain makes it play a physical barrier role between metal and plastic interfaces, reducing wear, and is widely used in the lubrication field.

[0059] Example 1

[0060] A method for preparing an integrated antifouling and anticorrosion coating with long-lasting, high adhesion, and super-slippery properties includes the following steps:

[0061] (1) Preparation of high-adhesion epoxy resin precursor:

[0062] 3.91g p -TsOH and 20g of PCA monomer were added to 371g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.01:0.1:1. The mixture was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the mixture was heated to 90°C for 4 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0063] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0064] Take 5g of the liquid product EGDE-PCA obtained in step (1) and mix it with 0.675g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.03. Then add 50mL of anhydrous ethanol solution, stir magnetically and react at 50℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0065] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0066] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.24g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.97:1. After ultrasonic mixing for 5min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate, then put it in a vacuum oven to remove air bubbles for 10min. Finally, after raising the oven to 60℃, react for 12h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0067] Example 2

[0068] (1) Preparation of high-adhesion epoxy resin precursor:

[0069] 1.08g p -TsOH and 15g of PCA monomer were added to 93g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.01:0.33:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 80°C for 5 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0070] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0071] Take 5g of the liquid product EGDE-30%PCA obtained in step (1) and mix it with 0.576g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.01. Then add 50mL of anhydrous ethanol solution, stir magnetically and react at 30℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0072] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0073] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.21g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.99:1. After ultrasonic mixing for 5min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate, then put it in a vacuum oven to remove air bubbles for 10min. Finally, after raising the oven to 50℃, react for 12h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0074] Example 3

[0075] (1) Preparation of high-adhesion epoxy resin precursor:

[0076] 2.55g p -TsOH and 18g of PCA monomer were added to 67g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.03:0.5:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 100°C for 3 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, the product EGDE-PCA was obtained by rotary evaporation.

[0077] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0078] Take 5g of the liquid product EGDE-PCA obtained in step (1) and mix it with 1.125g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.05. Then add 50mL of tetrahydrofuran solution, stir magnetically and react at 40℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0079] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0080] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.19g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.95:1. After ultrasonic mixing for 5min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate, then put it in a vacuum oven to remove air bubbles for 10min. Finally, after raising the oven to 50℃, react for 12h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0081] Example 4

[0082] (1) Preparation of high-adhesion epoxy resin precursor:

[0083] 5.4g p -TsOH and 15g of PCA monomer were added to 93g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.05:0.33:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 110°C for 3 hours. After the reaction was completed, chloroform and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0084] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0085] Take 5g of the liquid product EGDE-30%PCA obtained in step (1) and mix it with 1.125g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.05. Then add 50mL of ethyl acetate solution, stir magnetically and react at 50℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0086] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0087] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.213g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.95:1. After ultrasonic mixing for 10min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate. Then place it in a vacuum oven to remove air bubbles for 15min. Finally, after raising the oven to 40℃, react for 24h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0088] Example 5

[0089] (1) Preparation of high-adhesion epoxy resin precursor:

[0090] 11.71g p -TsOH and 20g of PCA monomer were added to 371g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.03:0.1:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 120°C for 3 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0091] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0092] Take 5g of the liquid product EGDE-PCA obtained in step (1) and mix it with 1.575g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.07. Then add 50mL of acetone solution, stir magnetically and react at 60℃ for 4h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0093] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0094] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.19g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.93:1. After ultrasonic mixing for 15min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate. Then place it in a vacuum oven to remove air bubbles for 15min. Finally, after raising the oven temperature to 30℃, react for 36h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0095] Example 6

[0096] (1) Preparation of high-adhesion epoxy resin precursor:

[0097] 4.25g p -TsOH and 18g of PCA monomer were added to 67g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.05:0.5:1. The mixture was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the mixture was heated to 80°C for 6 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0098] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0099] Take 5g of the liquid product EGDE-PCA obtained in step (1) and mix it with 1.575g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.07. Then add 50mL of acetone solution, stir magnetically and react at 60℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0100] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0101] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.19g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.93:1. After ultrasonic mixing for 10min, the liquid mixture is brushed onto a 5cm×5cm low carbon steel plate. Then, it is placed in a vacuum oven to remove air bubbles for 10min. Finally, the oven is heated to 50℃ and reacted for 24h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0102] Example 7

[0103] (1) Preparation of high-adhesion epoxy resin precursor:

[0104] 3.91g p 20g of TsOH and PCA monomers were added to 371g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.01:0.1:1. The mixture was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the mixture was heated to 90°C for 4 hours. After the reaction was completed, dichloromethane and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0105] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0106] Take 5g of the liquid product EGDE-10%PCA obtained in step (1) and mix it with 1.125g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.05. Then add 50mL of ethanol solution, stir magnetically and react at 80℃ for 4h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0107] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0108] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.19g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.95:1. After ultrasonic mixing for 15min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate. Then place it in a vacuum oven to remove air bubbles for 15min. Finally, after raising the oven to 80℃, react for 12h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0109] Example 8

[0110] (1) Preparation of high-adhesion epoxy resin precursor:

[0111] 11.73g p -TsOH g and PCA monomer 20 g were added to 371 g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.03:0.1:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 80°C for 6 hours. After the reaction was completed, chloroform and deionized water were added to extract the solution. Finally, the product EGDE-PCA was obtained by rotary evaporation.

[0112] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0113] Take 5g of the liquid product EGDE-10%PCA obtained in step (1) and mix it with 1.575g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.03. Then add 50mL of ethanol solution, stir magnetically and react at 80℃ for 4h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0114] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0115] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.213g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.95:1. After ultrasonic mixing for 15min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate. Then place it in a vacuum oven to remove air bubbles for 15min. Finally, after raising the oven temperature to 60℃, react for 24h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0116] Example 9

[0117] (1) Preparation of high-adhesion epoxy resin precursor:

[0118] 0.85g p -TsOH and 18g of PCA monomer were added to 67g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.01:0.5:1. The mixture was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the mixture was heated to 90°C for 5 hours. After the reaction was completed, chloroform and deionized water were added to extract the solution. Finally, rotary evaporation was used to obtain the product EGDE-PCA.

[0119] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0120] Take 5g of the liquid product EGDE-50%PCA obtained in step (1) and mix it with 1.114g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.06. Then add 50mL of ethanol solution, stir magnetically and react at 80℃ for 3h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0121] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0122] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.178g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.96:1. After ultrasonic mixing for 15min, brush the liquid mixture onto a 5cm×5cm low carbon steel plate, then put it into a vacuum oven to remove air bubbles for 15min. Finally, after raising the oven to 60℃, react for 24h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0123] Example 10

[0124] (1) Preparation of high-adhesion epoxy resin precursor:

[0125] 0.85g p -TsOH and 18g of PCA monomer were added to 67g of EGDE. p The molar ratio of -TsOH, PCA and EGDE was 0.01:0.5:1. The solution was magnetically stirred to form a homogeneous solution. Nitrogen gas was introduced and the solution was heated to 80°C for 8 hours. After the reaction was completed, chloroform and deionized water were added to extract the solution. Finally, the product EGDE-PCA was obtained by rotary evaporation.

[0126] (2) Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor:

[0127] Take 5g of the liquid product EGDE-PCA obtained in step (1) and mix it with 1.432g of APT-PDMS. The molar ratio of EGDE-PCA to APT-PDMS is 1:0.07. Then add 50mL of ethyl acetate solution, stir magnetically and react at 60℃ for 5h. After the reaction is completed, evaporate the solvent from the liquid mixture to finally obtain the product EGDE-PCA / APT-PDMS.

[0128] (3) Preparation of a high-adhesion, super-slippery integrated antifouling and anticorrosion coating:

[0129] Take 5g of the oily liquid product EGDE-PCA / APT-PDMS obtained in step (2) and add it to 1.164g of IPDA. The molar ratio of IPDA to EGDE-PCA / APT-PDMS is 0.93:1. After ultrasonic mixing for 10min, the liquid mixture is brushed onto a 5cm×5cm low carbon steel plate. Then, it is placed in a vacuum oven to remove air bubbles for 15min. Finally, the oven is heated to 40℃ and reacted for 36h to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

[0130] Performance Analysis:

[0131] (1) Morphological and elemental composition analysis:

[0132] Morphological and elemental analyses were performed on the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 1 and its contact surface with the low-carbon steel substrate, such as... Figure 2 As shown, after peeling from the low-carbon steel substrate, the bottom surface of the coating is rough and uneven, while the surface of the coating is smooth and flat. This indicates that the lubricating components in the coating are concentrated on the surface. Figure 3 As shown, the C, O, and Si elements are uniformly distributed on the coating bottom and coating surface after being peeled off from the low-carbon steel substrate, while the Si element content on the coating surface is much higher than that on the coating bottom, further indicating that the lubricating component APT-PDMS is concentrated on the coating surface.

[0133] (2) X-ray photoelectron spectroscopy analysis:

[0134] X-ray photoelectron spectroscopy was performed on the surface of the high-adhesion, super-slippery integrated antifouling and anti-corrosion coating prepared in Example 1 and its contact surface with the low-carbon steel substrate. Figure 4 As shown in the XPS full spectrum, it can be seen that the coating surface and its contact surface with the substrate both show the positions of C, N, O and Si peaks. In particular, the peak intensity of Si on the coating surface is significantly greater than that at the interface between the coating and the substrate, which further illustrates that the lubricating component APT-PDMS can spontaneously migrate to the surface of the coating during the crosslinking and curing process.

[0135] (3) Differential scanning calorimetry:

[0136] Differential scanning calorimetry (DSC) analysis was performed on the high-adhesion, super-slippery integrated antifouling and anti-corrosion coating prepared in Example 1, and the results were compared with a control group. The difference between control group 1-1 and Example 1 was that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 1-2 and Example 1 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 5 As shown, the glass transition temperature of the control group 1-1 was only 23.23℃. After the introduction of PCA, the glass transition temperature was significantly increased to 31.86℃. This is because the rigid structure in PCA made a positive contribution to the increase of the glass transition temperature of the coating. The glass transition temperature of the high adhesion, super-lubricating integrated antifouling and anticorrosion coating of the present invention reached 34.28℃. This is because the increase in molecular weight after the introduction of APT-PDMS further increased the glass transition temperature. This indicates that the high adhesion, super-lubricating integrated antifouling and anticorrosion coating of the present invention has good rigidity and heat resistance. The lubricating components in the coating are not easily destroyed, thus allowing it to exist more stably in harsh environments.

[0137] (4) Thermogravimetric analysis:

[0138] Thermogravimetric analysis was performed on the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 1, and compared with the control group. The difference between control group 1-1 and Example 1 is that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients; the difference between control group 1-2 and Example 1 is that EGDE-PCA was prepared, mixed and stirred with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 6 The thermogravimetric curves shown indicate that, compared to the control group 1-1 without any active ingredients, the initial degradation temperature of the coating in control group 1-2 decreased after the introduction of PCA. This is because, during the heating process, the diphenol structure in PCA accelerates the oxidative decomposition of the system, and the contribution of oxidative decomposition to the system is greater than the contribution of the rigid structure to the support system. In contrast, the initial degradation temperature of the high-adhesion, super-lubricating integrated antifouling and anticorrosion coating of the present invention is better than that of control group 1-1. This is because the introduction of APT-PDMS increases the molecular weight, which, in synergy with the rigid structure, increases the initial degradation temperature of the system. This demonstrates that the high-adhesion, super-lubricating integrated antifouling and anticorrosion coating of the present invention has good thermal stability and is the cornerstone and guarantee for maintaining long-term super-lubricating properties under high temperature or thermal fluctuation environments.

[0139] (5) Abrasion resistance analysis:

[0140] The high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating prepared in Example 1 was subjected to tribological tests. The coating surface was cyclically rubbed with steel wool for 0, 500, 1000, 2000, and 3000 cycles, respectively, and compared with a control group. The difference between control group 1-1 and Example 1 was that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 1-2 and Example 1 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 7 As shown, scratches appeared on the coating surface after 500 cycles of cyclic friction in control group 1-1, and more scratches appeared on the coating surface after 1000 cycles of cyclic friction in control group 1-2. This is because the introduction of PCA increased the stiffness of the system and improved the wear resistance of the coating. However, after 3000 cycles, the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating of this invention only had slight scratches on the coating surface. This is because the further introduction of APT-PDMS made the coating surface smoother and had better wear resistance.

[0141] (6) Antibacterial performance analysis:

[0142] The antibacterial properties of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 1 were analyzed. The resistance of the coating to four typical bacteria—Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Bacillus thuringiensis—was tested using the colony counting method, and compared with the blank group and control group. The difference between control group 1-1 and Example 1 was that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 1-2 and Example 1 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 8 As shown, compared with the blank group, the control group 1-1 has a limited antibacterial effect. After the introduction of PCA, the antibacterial effect of the control group 1-2 is significantly enhanced. This is because the catechol structure in PCA has a suitable bactericidal effect. The high adhesion and super-slippery integrated antifouling and anticorrosion coating of the present invention shows a very good antibacterial effect, indicating that the introduction of the lubricating component APT-PDMS can block the adhesion of fouling organisms on the coating surface, thereby improving the antifouling and antibacterial ability.

[0143] (7) Analysis of corrosion resistance:

[0144] The anti-corrosion performance of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating prepared in Example 1 was analyzed using the cyclic salt spray method. A 3.5 wt.% sodium chloride solution was used to place the coated tinplate sample into a cyclic salt spray chamber. The sample surface was monitored periodically (10 days, 20 days, and 30 days), and compared with a blank substrate and a control group. Figure 9 As shown, after 10 days in a circulating salt spray chamber, the cross-shaped area on the surface of the blank substrate (tinplate) was covered with rust. The cross-shaped area on the surface of the control group 1-1 coating sample showed slight corrosion, while the corrosion of the control group 1-2 coating sample was even less severe. After 20 days in a circulating salt spray chamber, obvious corrosion marks appeared on the control group 1-1, and corrosion marks also began to appear on the control group 1-2 coating sample. After 30 days in a circulating salt spray chamber, the cross-shaped area on the control group 1-1 and control group 1-2 coating samples was covered with rust, while no corrosion marks were observed on the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating of the present invention. This indicates that the coating surface of the present invention has excellent hydrophobicity, which can isolate most of the water mist invasion and significantly improve the anti-corrosion performance.

[0145] (8) Optical performance analysis:

[0146] Optical performance analysis was performed on the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 2. Coating thicknesses were controlled at 60 μm, 120 μm, 180 μm, and 240 μm, with three parallel experiments conducted at each thickness. The average ultraviolet transmittance in the visible light range was recorded and compared with the control group. The difference between control group 2-1 and Example 2 was that EGDE and IPDA were directly mixed and brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 2-2 and Example 2 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The transmittance of the control group and Example 2 is shown in Table 1.

[0147] The optical properties of the high-adhesion, super-slippery integrated antifouling and anti-corrosion coating prepared in Example 4 were analyzed. Coating thicknesses were controlled at 60 μm, 120 μm, 180 μm, and 240 μm, with three parallel experiments performed at each thickness. The average ultraviolet transmittance in the visible light range was recorded and compared with the control group. The difference between control group 4-1 and Example 4 was that EGDE and IPDA were directly mixed and brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 4-2 and Example 4 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The transmittance of the control group and Example 4 is shown in Table 1.

[0148] Optical performance analysis was performed on the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 5. Coating thicknesses were controlled at 60 μm, 120 μm, 180 μm, and 240 μm, with three parallel experiments conducted at each thickness. The average ultraviolet transmittance in the visible light range was recorded and compared with the control group. The difference between control group 5-1 and Example 5 was that EGDE and IPDA were directly mixed and brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 5-2 and Example 5 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The transmittance of the control group and Example 5 is shown in Table 1.

[0149] Table 1. Optical performance analysis of Examples 2, 4, and 5: transmittance

[0150]

[0151] According to the data in Table 1, the UV transmittance in the visible light range of control groups 2-1, 4-1, and 5-1 remained around 90% with increasing thickness. After the addition of PCA, the transmittance of control groups 2-2, 4-2, and 5-2 decreased, and the transmittance showed a decreasing trend with increasing coating thickness. Although the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in this invention continued to introduce APT-PDMS, the transmittance was still maintained above 84.72%, indicating that the high-adhesion, super-slippery integrated antifouling and anticorrosion coating has high transparency and can meet the requirements of aesthetics.

[0152] (9) Adhesion strength analysis:

[0153] The adhesion strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 2 was analyzed. The lap shear strength and pull-out strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating on low-carbon steel plate were tested. The coating thickness was 500 μm. Three parallel experiments were conducted, and the average values ​​of shear strength and pull-out strength were recorded and compared with the control group. The difference between control group 2-1 and Example 2 was that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 2-2 and Example 2 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The adhesion strength of the control group and Example 2 are shown in Table 2.

[0154] The adhesion strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 4 was analyzed. The lap shear strength and pull-out strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating on low-carbon steel plate were tested. The coating thickness was 500 μm. Three parallel experiments were conducted, and the average values ​​of shear strength and pull-out strength were recorded and compared with the control group. The difference between control group 4-1 and Example 4 was that EGDE and IPDA were directly mixed and brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 4-2 and Example 4 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The adhesion strength of the control group and Example 4 is shown in Table 2.

[0155] The adhesion strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 5 was analyzed. The lap shear strength and pull-out strength of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating on low-carbon steel plate were tested. The coating thickness was 500 μm. Three parallel experiments were conducted, and the average values ​​of shear strength and pull-out strength were recorded and compared with the control group. The difference between control group 5-1 and Example 5 was that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients. The difference between control group 5-2 and Example 5 was that EGDE-PCA was prepared, mixed with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. The adhesion strength of the control group and Example 5 is shown in Table 2.

[0156] Table 2. Adhesion performance analysis of Examples 2, 4 and 5: transmittance

[0157]

[0158] According to the data in Table 2, the control groups 2-2, 4-2, and 5-2 with PCA introduced showed the best adhesion strength, with shear strength increased by 210.71%, 250%, and 250.26% respectively compared to the control groups 2-1, 4-1, and 5-1. However, the adhesion strength of Examples 2, 4, and 5 was slightly lower than that of the control groups 2-2, 4-2, and 5-2 due to the introduction of the lubricating component APT-PDMS. This is because lubrication and adhesion strength are mutually exclusive properties. However, the adhesion strength of the high-adhesion, super-lubricating integrated antifouling and anticorrosion coating prepared by the present invention did not decrease significantly, and the shear strength and pull-out strength remained above 11 MPa. During the curing process, the lubricating component of the high-adhesion, super-lubricating integrated antifouling and anticorrosion coating of the present invention spontaneously migrates to the coating surface, and the catechol structure spontaneously forms a strong bond with the substrate, so they do not affect each other. Therefore, it can maintain good adhesion strength.

[0159] (10) Infiltrative analysis:

[0160] The wettability of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 2 was analyzed, and the contact angle and sliding angle were tested and compared with the control group. The difference between control group 2-1 and Example 2 is that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients; the difference between control group 2-2 and Example 2 is that EGDE-PCA was prepared, mixed and stirred with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 10 As shown, the contact angles of control groups 2-1 and 2-2 gradually increased and the sliding angles gradually decreased compared to Example 2, indicating that the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating of the present invention has good hydrophobic effects. The sliding behavior of water droplets on the surface of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 2 was dynamically recorded, as shown... Figure 11 As shown, at an inclination angle of 4.5°, water droplets slide off the surface of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating within 15 seconds, indicating that the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating of the present invention has excellent lubrication ability.

[0161] The wettability of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 4 was analyzed, and the contact angle and sliding angle were tested and compared with the control group. The difference between control group 4-1 and Example 4 is that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients; the difference between control group 4-2 and Example 4 is that EGDE-PCA was prepared, mixed and stirred with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 12 As shown, the contact angle of control group 4-1, control group 4-2 and Example 4 gradually increased and the sliding angle gradually decreased, indicating that the surface of the high adhesion, super slippery integrated antifouling and anticorrosion coating of the present invention has a good hydrophobic effect.

[0162] The wettability of the high-adhesion, super-slippery integrated antifouling and anticorrosion coating prepared in Example 5 was analyzed, and the contact angle and sliding angle were tested and compared with the control group. The difference between control group 5-1 and Example 5 is that EGDE and IPDA were directly mixed and stirred before being brushed onto a 5cm × 5cm low-carbon steel plate, resulting in an EGDE / IPDA coating without any added active ingredients; the difference between control group 5-2 and Example 5 is that EGDE-PCA was prepared, mixed and stirred with IPDA, and then brushed onto a 5cm × 5cm low-carbon steel plate. Figure 13As shown, the contact angle of control group 5-1, control group 5-2 and Example 5 gradually increased and the sliding angle gradually decreased, indicating that the surface of the high adhesion, super slippery integrated antifouling and anticorrosion coating of the present invention has a good hydrophobic effect.

Claims

1. A method for preparing an integrated antifouling and anticorrosion coating with long-lasting, high adhesion, and super-slippery functions, characterized in that, Includes the following steps: Preparation of high-adhesion epoxy resin precursor: p-Toluenesulfonic acid monohydrate p -TsOH and protocatechuic acid (PCA) monomers were added to ethylene glycol diglycidyl ether (EGDE) and stirred to form a homogeneous solution. p The molar ratio of -TsOH, PCA and EGDE was (0.01-0.05):(0.1-0.5):

1. The reaction was carried out under an inert atmosphere and heated. After the reaction was completed, organic solvent and water were added for solution extraction. Finally, the solvent was evaporated to obtain the liquid product EGDE-PCA. Preparation of high-adhesion, super-lubricating integrated epoxy resin precursor: The liquid product EGDE-PCA was mixed with aminopropyl dual-terminated polydimethylsiloxane APT-PDMS and then added to a polar organic solvent. The molar ratio of APT-PDMS to EGDE-PCA was (0.01-0.07):

1. The mixture was stirred and heated to carry out the reaction. After the reaction was completed, the solvent in the liquid mixture was evaporated to obtain the oily liquid product EGDE-PCA / APT-PDMS. Preparation of a high-adhesion, ultra-slippery integrated anti-fouling and anti-corrosion coating: The oily liquid product EGDE-PCA / APT-PDMS was added to isophorone diamine IPDA, with a molar ratio of IPDA to EGDE-PCA / APT-PDMS of (0.93-0.99):

1. After mixing and stirring evenly, the liquid mixture was coated onto a metal material sample and dried and cured under vacuum heat preservation conditions to obtain a slightly yellow transparent solid epoxy resin coating, which is an integrated anti-fouling and anti-corrosion coating with long-lasting high adhesion and super slippery function.

2. The method for preparing an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 1, characterized in that, In the preparation of the high-adhesion epoxy resin precursor, magnetic stirring was used, and the heating reaction temperature was 80℃-120℃ for 3h-8h.

3. The method for preparing an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 1, characterized in that, In the preparation of the high-adhesion epoxy resin precursor, the organic solvent is dichloromethane or trichloromethane, and the water is deionized water.

4. The method for preparing an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 1, characterized in that, The preparation of the high-adhesion, super-lubricating integrated epoxy resin precursor was carried out by magnetic stirring, with the heating reaction temperature at 30℃-80℃ and the time at 3h-5h.

5. The method for preparing an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 1, characterized in that, The preparation of the high-adhesion, super-lubricating integrated epoxy resin precursor uses one of the following polar organic solvents: anhydrous ethanol, acetone, ethyl acetate, or tetrahydrofuran.

6. The method for preparing an integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 1, characterized in that, Ultrasonic stirring was used in the preparation of the high-adhesion, super-slippery integrated anti-fouling and anti-corrosion coating, with a stirring time of 5-15 minutes; Vacuum insulation is achieved by using a vacuum oven and evacuating the air for 10-15 minutes. The drying and curing reaction temperature is 30℃-80℃, and the time is 12h-36h.

7. A long-lasting, highly adhesive, and ultra-slippery integrated anti-fouling and anti-corrosion coating, characterized in that, The coating is prepared using the method described in any one of claims 1-6, which provides an integrated antifouling and anticorrosion coating with long-lasting, high adhesion, and super-slippery properties.

8. The application of the integrated antifouling and anticorrosion coating with long-lasting high adhesion and super-slippery function as described in claim 7, characterized in that, Super-slippery antifouling and anti-corrosion coating used for ships, marine engineering facilities and underwater equipment.

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