Efficient static / dynamic antifouling coating as well as preparation method and application thereof

Abstract

The invention discloses an efficient static / dynamic antifouling coating as well as a preparation method and application thereof, and belongs to the technical field of marine antifouling. The silicon rubber-epoxy resin self-stratification coating with a micron porous structure on the surface is prepared by adopting a template method, and the intelligent nano filler with pH response is loaded to the surface of the porous silicon rubber-epoxy self-stratification coating through capillary acting force, so that the silicon rubber-epoxy self-stratification coating with the pH response intelligent nano filler loaded on the surface is obtained. The coating is the high-efficiency static / dynamic antifouling coating; due to the microphase separation effect between the silicone rubber and the epoxy resin, the epoxy resin enriched at the bottom of the coating improves the interface bonding strength of the epoxy resin anticorrosive primer, and the silicone rubber enriched on the surface of the coating reduces the adhesion of fouling organisms by virtue of the characteristics of low surface energy and low elastic modulus; even if a small amount of fouling organisms are attached, the cuprous oxide antifouling agent can be intelligently released through pH value change, so that the fouling organisms die and are desorbed, and efficient static / dynamic antifouling performance is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of marine antifouling, and particularly relates to an efficient static / dynamic antifouling coating, a preparation method thereof and an application thereof. Background Art

[0002] Marine biofouling refers to the process in which animals, plants or microorganisms in the ocean attach, colonize and grow on the surface of marine structures. Marine biofouling includes four stages: in the first stage, organic substances such as proteins, polysaccharides and lipids, and some inorganic substances will attach to the substrate surface to form a protein film; in the second stage, microorganisms such as bacteria and diatoms attach to the protein film and grow rapidly, and secrete extracellular biopolymers such as proteins and polysaccharides to form a biofilm; in the third stage, seaweed spores and protists attach to the biofilm and grow; in the fourth stage, a large number of large fouling organisms continue to attach and grow to form a serious biofouling layer.

[0003] Marine biofouling will increase the mass and surface roughness of the hull, greatly increasing the resistance of ship navigation. At the same time, due to the usually huge total amount of fouling organisms, the hull weight is greatly increased, resulting in additional fuel consumption for ship navigation. In addition, the attached microorganisms will migrate to other places along with the ship's navigation, posing an impact on the local ecological balance and triggering the risk of alien species invasion. At present, biofouling has become a worldwide problem attracting wide attention due to the extensiveness of its impact and the complexity of prevention and control. According to statistics, the economic loss caused by biofouling globally exceeds 150 billion US dollars every year.

[0004] Therefore, with the in-depth exploration and development of marine resources, the problems brought by biofouling have increasingly attracted people's attention, prompting people to continuously explore and adopt various measures to prevent the attachment and growth of these organisms. Through continuous efforts and exploration by people, a variety of antifouling methods and strategies have been found. Among these methods and strategies, applying antifouling coatings is the method with the lowest cost, the most convenient operation, the most effective and the most common. Antifouling coatings mainly achieve the antifouling purpose by adding antifouling agents such as cuprous oxide, organotin, zinc oxide, etc. to the coatings and gradually releasing them in the marine environment to expel or even kill fouling organisms.

[0005] After long-term research, it has been found that such antifouling coatings can achieve obvious antifouling effects, but they also have some deficiencies. At present, in order to achieve the effect of anti-biofouling for marine structure coatings, the antifouling agent particles are mostly evenly dispersed in the base resin. The antifouling agent in the coating is released into the seawater through physical methods such as "dissolution" and "exudation and diffusion". The effective period of the antifouling agent's action is related to its dissolution and diffusion rate in the seawater environment. In the initial stage of use, the diffusion concentration of the antifouling agent is relatively high, and it can play a good antibacterial role. As the use time extends, the diffusion concentration of the antifouling agent rapidly decreases, the use cycle is short, and it cannot provide long-term anti-biofouling.

[0006] In recent years, low surface energy antifouling coatings have attracted extensive attention from relevant researchers in preventing and controlling marine fouling organisms. Low surface energy antifouling coatings possess excellent dynamic antifouling performance due to their low surface energy and low elastic modulus characteristics on the surface, making it difficult for marine organisms to attach and grow. Even if there are marine organisms on the coating surface, they will desorb under the condition of seawater flow due to the weak bonding effect between the organisms and the coating. However, research has shown that the antifouling period of low surface energy antifouling coatings is relatively short under static seawater conditions. In addition, due to their own low surface energy characteristics, low surface energy antifouling coatings also have problems such as low bonding strength with the substrate.

[0007] Chinese Patent with publication number CN112795307A and application date December 30, 2020 discloses a weather-resistant self-cleaning self-stratifying coating and its preparation method and application. On the basis of a high-temperature cured hydroxyl fluorocarbon resin, a highly active carbon alcohol-terminated polydimethylsiloxane and an epoxy resin are introduced. During the curing process of the coating film, due to the incompatibility and surface energy difference among the epoxy resin, fluorocarbon resin and the silicone chain segment of the carbon alcohol-terminated polydimethylsiloxane, the epoxy resin is enriched in the bottom layer and combines with the metal substrate, the fluorocarbon resin is enriched in the middle layer, and the silicone chain segment of the carbon alcohol-terminated polydimethylsiloxane is enriched on the surface to form a surface silicone layer, forming a three-layer microphase-separated self-stratifying coating. However, the bonding strength of this coating with the substrate is relatively low, and there is a problem of peeling off from the substrate surface when applied in a harsh marine environment.

[0008] Chinese Patent with publication number CN117126578A and application date August 14, 2023 provides a grafted antibacterial molecule-containing silicone polymer / POSS hybrid antifouling coating and its preparation method. The antibacterial groups distributed on the surface of the prepared coating have the characteristics of chemical antifouling and retain the physical antifouling characteristics of the low surface energy of the silicone polymer, significantly enhancing the static antifouling ability of the coating. Moreover, the flexible silicone polymer and the rigid POSS molecule are chemically connected at the molecular level, having relatively high mechanical properties and adhesion. However, in this method, the cost of multi-hydroxyl POSS is relatively high, the preparation process is complex, it is not suitable for large-scale application, and the static antifouling period is relatively short.

[0009] In summary, based on the excellent dynamic antifouling performance of low surface energy antifouling coatings themselves, developing a low surface energy antifouling coating with a simple preparation process, low cost, high bonding strength with the substrate and long-term resistance to marine biofouling is an urgent problem to be solved in the current field of marine antifouling technology. Summary of the Invention

[0010] To solve the problems existing in the prior art, the present invention provides an efficient static / dynamic anti-fouling coating, its preparation method and application, which can significantly improve the bonding strength with the substrate and extend the static anti-fouling period of the coating, so as to meet the anti-fouling requirements of marine structures under static seawater conditions.

[0011] The technical solution of the present invention is as follows:

[0012] One of the purposes of the present invention is to provide a preparation method of an efficient static / dynamic anti-fouling coating. A silicone rubber-epoxy resin self-stratifying coating with a micron-porous structure on the surface is prepared by a template method, and a pH-responsive intelligent nano-filler is loaded onto the surface of the porous silicone rubber-epoxy self-stratifying coating through capillary action to obtain a silicone rubber-epoxy self-stratifying coating with a pH-responsive intelligent nano-filler loaded on the surface, that is, an efficient static / dynamic anti-fouling coating.

[0013] Further, the pH-responsive intelligent nano-filler is a mesoporous silica-coated cuprous oxide nano-filler grafted with a pH-responsive polymer.

[0014] Further, the pH-responsive polymer is poly(2-vinylpyridine)-polymethyl methacrylate.

[0015] Further, it includes the following steps:

[0016] S1. Mix Span 80 and Tween 80 evenly at a mass ratio of 3:1 and stir for 10 - 15 min to prepare a pore-forming agent, and ultrasonically mix for 10 - 30 min;

[0017] S2. Mix Dow Corning 184 silicone rubber and a curing agent evenly at a mass ratio of 10:1 and stir for 1 - 3 h, and add a pore-forming agent with a mass ratio of 10% - 40% relative to the silicone rubber to prepare a silicone rubber precursor;

[0018] S3. Mix bisphenol A epoxy resin, polyamide curing agent and xylene evenly at a mass ratio of 1:1:3 and stir for 1 - 3 h to prepare an epoxy resin precursor;

[0019] S4. Mix the epoxy resin precursor and the silicone rubber precursor evenly at a mass ratio of 3:1 and stir for 2 - 6 h, coat it on the surface of a commercial epoxy resin anti-corrosion primer and cure it to form a silicone rubber-epoxy resin self-stratifying coating, and then soak it in a mixed solution of deionized water and absolute ethanol with a volume ratio of 1:1 at 60 - 70 °C for 12 - 36 h to remove the pore-forming agent, and dry it to form a porous silicone rubber-epoxy self-stratifying coating;

[0020] S5. Add cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate, and cuprous oxide nanoparticles to a mixed solution of anhydrous ethanol and deionized water with a volume ratio of 1:2 according to a mass ratio of 10:5:3:1, and stir for 12 - 24 h. Centrifuge to recover the precipitate product to obtain mesoporous silica-coated cuprous oxide nanocomposite fillers;

[0021] S6. Disperse the mesoporous silica-coated cuprous oxide nanocomposite fillers in anhydrous toluene, and add (3-bromopropyl)trimethoxysilane with a mass fraction of 1% - 5%. Stir for 12 - 24 h to functionalize the surface of the mesoporous silica-coated cuprous oxide nanocomposite fillers with bromoalkyl groups;

[0022] S7. Add poly(2-vinylpyridine)-polymethyl methacrylate to an anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and add the surface bromoalkyl-functionalized mesoporous silica-coated cuprous oxide nanocomposite fillers with a mass fraction of 1% - 5%. Stir for 20 - 60 min and then dry in a vacuum drying oven to obtain intelligent nanocomposite fillers with pH-responsive properties;

[0023] S8. Disperse the pH-responsive intelligent nanocomposite fillers with a mass fraction of 1% - 3% in anhydrous ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating in it for 2 - 6 h. Here, each square centimeter of the porous silicone rubber-epoxy self-stratifying coating is immersed in 10 mL of the anhydrous ethanol solution containing the pH-responsive intelligent nanocomposite fillers to obtain a silicone rubber-epoxy self-stratifying coating with pH-responsive intelligent nanocomposite fillers loaded on its surface, that is, a highly efficient static / dynamic anti-fouling coating.

[0024] Further, in S3, the polyamide curing agent is polyamide 650 or polyamide 651.

[0025] Further, in S4, the curing conditions are curing at 70 - 90 °C for 12 - 24 h.

[0026] Further, in S7, the drying conditions are drying at 100 - 120 °C for 12 - 24 h.

[0027] The second object of the present invention is to provide a highly efficient static / dynamic anti-fouling coating.

[0028] Further, the interfacial bonding strength of the highly efficient static / dynamic anti-fouling coating can reach 4.01 ± 0.22 Mpa.

[0029] The third object of the present invention is to provide an application of the highly efficient static / dynamic anti-fouling coating in the fouling protection of ships, bridges, docks, offshore platforms, and various steel structure projects.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] 1. The present invention innovates for the first time an antifouling coating that can be tightly bonded to the substrate and has high efficient static / dynamic antifouling performance. By utilizing the microphase separation effect between silicone rubber and epoxy resin, the epoxy resin enriched at the bottom of the antifouling coating can have a high interfacial bonding strength with the epoxy resin anticorrosive primer. The interfacial bonding strength tested by the pull-out method can reach 4.01 ± 0.22 Mpa. At the same time, the silicone rubber enriched on the surface of the coating can reduce the attachment of fouling organisms by relying on its own low surface energy and low elastic modulus characteristics, endowing the coating with excellent dynamic antifouling performance. Even if a small amount of fouling organisms attach to the surface of the coating, the pH value change caused by the attachment of fouling organisms on the coating surface can be used to intelligently release cuprous oxide antifouling agent to cause the death of fouling organisms, and the dead fouling organisms can be effectively desorbed from the coating surface through the low surface energy and low elastic modulus characteristics of silicone rubber, realizing high efficient static / dynamic antifouling performance.

[0032] 2. The designed high efficient static / dynamic antifouling coating of the present invention has significant progress compared with the traditional antifouling coating. The static antifouling performance of the coating is evaluated by the method of hanging plate test in the actual sea. After static immersion in seawater for 91 days, the antifouling score can still be greater than 85 points. The dynamic antifouling performance of the coating is evaluated by the rotation method. After static immersion for different times and then being rotated and scoured in seawater, the antifouling score can be greater than 90 points, effectively solving the problem of short static antifouling period of the low surface energy antifouling coating, and realizing high efficient static / dynamic antifouling performance by combining the excellent dynamic antifouling ability of silicone rubber itself;

[0033] 3. The present invention provides a preparation method of the novel high efficient static / dynamic antifouling coating. The raw materials involved in the coating preparation have low cost, and the preparation process is simple, which can realize the low cost of the coating and the simplicity of the preparation process. At the same time, because the preparation method of the present invention significantly improves the bonding strength between the antifouling coating and the substrate and prolongs the static antifouling period of the coating, it can stably play the antifouling performance in seawater for a long time, reducing the additional consumption of coating repair or renewal in the later use, and fully meeting the antifouling requirements of marine structures under static seawater conditions. Description of the Drawings

[0034] Figure 1 It is the surface morphology diagram of the porous silicone rubber - epoxy resin self - stratified coating prepared in Example 1 of the present invention;

[0035] Figure 2 It is the surface morphology diagram of the pH - responsive intelligent nano - filler prepared in Example 1 of the present invention;

[0036] Figure 3 It is the infrared spectrum diagram of the pH - responsive intelligent nano - filler (a) and pH - responsive polymer (b) prepared in Example 1 of the present invention;

[0037] Figure 4This is a graph showing the influence law of different pore former contents on the interfacial bonding strength between the coating and the epoxy resin anticorrosive primer in the performance test of the present invention. Detailed implementation mode

[0038] The following further describes the present invention in conjunction with preferred embodiments. In the ranges disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values; for numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0039] The experimental methods in the following embodiments are all conventional methods unless otherwise specified, and are carried out according to the techniques or conditions described in the literature in this field or according to the product instructions.

[0040] The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels unless otherwise specified.

[0041] Embodiment 1

[0042] This embodiment provides a preparation method for an efficient static / dynamic antifouling coating, including the following steps:

[0043] (1) Stir Span 80 and Tween 80 evenly at a mass ratio of 3:1 for 10 min to prepare a pore former, and ultrasonically mix for 10 min;

[0044] (2) Stir Dow Corning 184 silicone rubber and a curing agent evenly at a mass ratio of 10:1 for 1 h, and add a pore former with a mass ratio of 40% relative to the silicone rubber to prepare a silicone rubber precursor;

[0045] (3) Stir bisphenol A epoxy resin, polyamide 650 and xylene evenly at a mass ratio of 1:1:3 for 1 h to prepare an epoxy resin precursor;

[0046] (4) Stir the epoxy resin precursor and the silicone rubber precursor evenly at a mass ratio of 3:1 for 4 h, coat it on the surface of a commercial epoxy resin anticorrosive primer and cure it at 70 °C for 24 h to form a silicone rubber-epoxy self-stratifying coating, and then soak it in a mixed solution of deionized water and absolute ethanol with a volume ratio of 1:1 at 65 °C for 12 h to remove the pore former, and dry it to form a porous silicone rubber-epoxy self-stratifying coating;

[0047] (5) Add cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate and cuprous oxide nanoparticles in a mass ratio of 10:5:3:1 to a mixed solution of absolute ethanol and deionized water with a volume ratio of 1:2 and stir for 18 h, centrifuge and recover the precipitate product to obtain mesoporous silica-coated cuprous oxide nano-fillers;

[0048] (6) Disperse the mesoporous silica-coated cuprous oxide nanocomposite fillers in anhydrous toluene, add (3-bromopropyl)trimethoxysilane with a mass fraction of 5%, and stir for 18 h to functionalize the surface of the mesoporous silica-coated cuprous oxide nanocomposite fillers with bromoalkyl groups;

[0049] (7) Add the pH-responsive polymer poly(2-vinylpyridine)-polymethyl methacrylate to an anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and add the mesoporous silica-coated cuprous oxide nanocomposite fillers with a surface bromoalkyl functionalization of 1% by mass fraction. After stirring for 40 min, place it in a vacuum drying oven and dry at 100 °C for 12 h to obtain intelligent nanocomposite fillers with pH-responsive properties;

[0050] (8) Disperse the pH-responsive intelligent nanocomposite fillers with a mass fraction of 2% in absolute ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating in it for 4 h to obtain a silicone rubber-epoxy self-stratifying coating with pH-responsive intelligent nanocomposite fillers loaded on the surface, that is, a highly efficient static / dynamic antifouling coating.

[0051] Example 2

[0052] This example provides a preparation method of a highly efficient static / dynamic antifouling coating, including the following steps:

[0053] (1) Uniformly stir Span 80 and Tween 80 at a mass ratio of 3:1 for 15 min to prepare a pore-forming agent, and ultrasonically mix for 30 min;

[0054] (2) Uniformly stir Dow Corning 184 silicone rubber and a curing agent at a mass ratio of 10:1 for 3 h, and add a pore-forming agent with a mass ratio of 10% relative to the silicone rubber to prepare a silicone rubber precursor;

[0055] (3) Uniformly stir bisphenol A epoxy resin, polyamide 651 and xylene at a mass ratio of 1:1:3 for 3 h to prepare an epoxy resin precursor;

[0056] (4) Uniformly stir the epoxy resin precursor and the silicone rubber precursor at a mass ratio of 3:1 for 6 h, coat it on the surface of a commercial epoxy resin anticorrosive primer and cure at 80 °C for 12 h to form a silicone rubber-epoxy self-stratifying coating. Subsequently, soak it in a mixed solution of deionized water and absolute ethanol with a volume ratio of 1:1 at 70 °C for 24 h to remove the pore-forming agent, and dry it to form a porous silicone rubber-epoxy self-stratifying coating;

[0057] (5) Add cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate and cuprous oxide nanoparticles to a mixed solution of absolute ethanol and deionized water with a volume ratio of 1:2 at a mass ratio of 10:5:3:1 and stir for 24 h, and centrifuge to recover the precipitate to obtain mesoporous silica-coated cuprous oxide nanocomposite fillers;

[0058] (6) Disperse the mesoporous silica-coated cuprous oxide nanocomposite fillers in anhydrous toluene, add (3-bromopropyl)trimethoxysilane with a mass fraction of 1%, and stir for 24 h to functionalize the surface of the mesoporous silica-coated cuprous oxide nanocomposite fillers with bromoalkyl groups;

[0059] (7) Add the pH-responsive polymer poly(2-vinylpyridine)-polymethyl methacrylate to an anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and add the mesoporous silica-coated cuprous oxide nanocomposite fillers with a surface bromoalkyl functionalization of 3% by mass fraction. After stirring for 20 min, place it in a vacuum drying oven and dry at 120 °C for 24 h to obtain intelligent nanocomposite fillers with pH-responsive properties;

[0060] (8) Disperse the pH-responsive intelligent nanocomposite fillers with a mass fraction of 3% in absolute ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating in it for 6 h to obtain a silicone rubber-epoxy self-stratifying coating with pH-responsive intelligent nanocomposite fillers loaded on the surface, that is, a highly efficient static / dynamic antifouling coating.

[0061] Example 3

[0062] This example provides a highly efficient static / dynamic antifouling coating, and its preparation method includes the following steps:

[0063] (1) Uniformly stir Span 80 and Tween 80 at a mass ratio of 3:1 for 13 min to prepare a pore-forming agent, and ultrasonically mix for 20 min;

[0064] (2) Uniformly stir Dow Corning 184 silicone rubber and a curing agent at a mass ratio of 10:1 for 2 h, and add a pore-forming agent with a mass ratio of 20% relative to the silicone rubber to prepare a silicone rubber precursor;

[0065] (3) Uniformly stir bisphenol A epoxy resin, polyamide 650 and xylene at a mass ratio of 1:1:3 for 2 h to prepare an epoxy resin precursor;

[0066] (4) Uniformly stir the epoxy resin precursor and the silicone rubber precursor at a mass ratio of 3:1 for 2 h, coat it on the surface of a commercial epoxy resin anticorrosive primer and cure at 90 °C for 18 h to form a silicone rubber-epoxy self-stratifying coating. Subsequently, soak it in a mixed solution of deionized water and absolute ethanol with a volume ratio of 1:1 at 60 °C for 36 h to remove the pore-forming agent, and dry it to form a porous silicone rubber-epoxy self-stratifying coating;

[0067] (5) Add cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate and cuprous oxide nanoparticles to a mixed solution of absolute ethanol and deionized water with a volume ratio of 1:2 at a mass ratio of 10:5:3:1 and stir for 12 h. Centrifuge to recover the precipitate product to obtain mesoporous silica-coated cuprous oxide nanocomposite fillers;

[0068] (6) Disperse the mesoporous silica-coated cuprous oxide nanocomposite filler in anhydrous toluene, add (3-bromopropyl)trimethoxysilane with a mass fraction of 3%, and stir for 12 h to functionalize the surface of the mesoporous silica-coated cuprous oxide nanocomposite filler with bromoalkyl groups;

[0069] (7) Add the pH-responsive polymer poly(2-vinylpyridine)-polymethyl methacrylate to an anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and add the mesoporous silica-coated cuprous oxide nanocomposite filler with a surface bromoalkyl functionalization of 5% by mass fraction. After stirring for 60 min, place it in a vacuum drying oven and dry at 110 °C for 18 h to obtain a smart nanocomposite filler with pH-responsive properties;

[0070] (8) Disperse the pH-responsive smart nanocomposite filler with a mass fraction of 1% in absolute ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating in it for 2 h to obtain a silicone rubber-epoxy self-stratifying coating with pH-responsive smart nanocomposite filler loaded on the surface, that is, a highly efficient static / dynamic antifouling coating.

[0071] Example 4

[0072] This example provides a highly efficient static / dynamic antifouling coating, and its preparation method includes the following steps:

[0073] (1) Uniformly stir Span 80 and Tween 80 at a mass ratio of 3:1 for 12 min to prepare a pore-forming agent, and ultrasonically mix for 25 min;

[0074] (2) Uniformly stir Dow Corning 184 silicone rubber and a curing agent at a mass ratio of 10:1 for 2 h, and add a pore-forming agent with a mass ratio of 30% relative to the silicone rubber to prepare a silicone rubber precursor;

[0075] (3) Uniformly stir bisphenol A epoxy resin, polyamide 651 and xylene at a mass ratio of 1:1:3 for 2 h to prepare an epoxy resin precursor;

[0076] (4) Uniformly stir the epoxy resin precursor and the silicone rubber precursor at a mass ratio of 3:1 for 2 h, coat it on the surface of a commercial epoxy resin anticorrosive primer and cure at 75 °C for 22 h to form a silicone rubber-epoxy self-stratifying coating. Subsequently, soak it in a mixed solution of deionized water and absolute ethanol with a volume ratio of 1:1 at 64 °C for 32 h to remove the pore-forming agent, and dry it to form a porous silicone rubber-epoxy self-stratifying coating;

[0077] (5) Add cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate and cuprous oxide nanoparticles to a mixed solution of absolute ethanol and deionized water with a volume ratio of 1:2 at a mass ratio of 10:5:3:1 and stir for 12 h. Centrifuge to recover the precipitate product to obtain the mesoporous silica-coated cuprous oxide nanocomposite filler;

[0078] (6) Disperse the mesoporous silica-coated cuprous oxide nanocomposite fillers in anhydrous toluene, add (3-bromopropyl)trimethoxysilane with a mass fraction of 3%, and stir for 18 h to functionalize the surface of the mesoporous silica-coated cuprous oxide nanocomposite fillers with bromoalkyl groups;

[0079] (7) Add the pH-responsive polymer poly(2-vinylpyridine)-polymethyl methacrylate to an anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and add the mesoporous silica-coated cuprous oxide nanocomposite fillers with a surface bromoalkyl functionalization of 5% by mass fraction. After stirring for 60 min, place it in a vacuum drying oven and dry at 115 °C for 14 h to obtain intelligent nanocomposite fillers with pH-responsive properties;

[0080] (8) Disperse the pH-responsive intelligent nanocomposite fillers with a mass fraction of 1% in absolute ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating in it for 3 h to obtain a silicone rubber-epoxy self-stratifying coating with pH-responsive intelligent nanocomposite fillers loaded on the surface, that is, a highly efficient static / dynamic antifouling coating.

[0081] Performance Test

[0082] 1. Interface Bonding Strength Test

[0083] Use the pull-out method to test the interface bonding strength between the highly efficient static / dynamic antifouling coatings with different pore-forming agent contents prepared in Examples 1-4 and the epoxy resin anticorrosive primer. At the same time, set EP / PDMS-0 as the control group, and the test results are as Figure 4 shown.

[0084] It can be seen from Figure 4 that when the pore-forming agent content is EP / PDMS-0, the interface bonding strength between the coating and the epoxy resin anticorrosive primer is 4.81 ± 0.52 Mpa; when the pore-forming agent contents are EP / PDMS-10, EP / PDMS-20, EP / PDMS-30, and EP / PDMS-40 respectively, the interface bonding strengths between the coating and the epoxy resin anticorrosive primer are 4.1 ± 0.43 Mpa, 3.98 ± 0.41 Mpa, 3.96 ± 0.36 Mpa, and 3.15 ± 0.22 Mpa respectively, indicating that the highly efficient static / dynamic antifouling coating described in the present invention can show good bonding strength when combined with the substrate compared with the traditional silicone antifouling coating (the interface bonding strength is 1-2 Mpa), and the addition of epoxy resin overcomes the defect that the traditional silicone antifouling coating is easy to fall off.

[0085] 2. Static Antifouling Performance Test

[0086] Disperse 1 g of pH-responsive intelligent nano-fillers in 1 L of artificial seawater, and take samples as Specimens 1 and 2 and adjust their pH values. The concentration of Cu was measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). 2+ The concentrations are shown in Table 1.

[0087] Table 1 Cu release concentrations at different pH values 2+ Release concentration

[0088]

[0089] It can be seen from Table 1 that the pH-responsive polymer P2VP-PMMA on the surface of the synthesized nano-fillers releases Cu at very different concentrations under different pH conditions, achieving rapid release of Cu in an acidic environment. The measured Cu concentration is 14.381 mg / L. In an alkaline environment, the release of Cu is reduced, and the measured Cu concentration is only 0.262 mg / L, indicating its good pH responsiveness. After making it into an antifouling coating, it is expected that when marine fouling organisms attach, the antifouling agent can be rapidly released to kill or drive away the fouling organisms; when there are no marine fouling organisms attached, the release of the antifouling agent can be reduced, thereby extending the service life of the coating. 2+ in an acidic environment, and the measured Cu 2+ concentration is 14.381 mg / L. In an alkaline environment, the release of Cu 2+ is reduced, and the measured Cu 2+ concentration is only 0.262 mg / L, indicating its good pH responsiveness. After making it into an antifouling coating, it is expected that when marine fouling organisms attach, the antifouling agent can be rapidly released to kill or drive away the fouling organisms; when there are no marine fouling organisms attached, the release of the antifouling agent can be reduced, thereby extending the service life of the coating. 2+ 3. Antifouling test

[0090] 3. Antifouling test

[0091] Evaluate the actual sea antifouling performance of the antifouling coating prepared in Example 1 according to GB / T 5370-2007 "Test Method for Submerged Exposure of Antifouling Paint Panels in Shallow Sea". The change trend of the static / dynamic antifouling score is shown in Table 2.

[0092] Table 2 Change trend of static / dynamic antifouling score

[0093]

[0094] As can be seen from Table 2, after 91 days of actual sea hanging plate, the antifouling score of the antifouling coating in Example 1 can still be maintained at 86, showing excellent actual sea antifouling effect. Subsequently, the surface of the coating was dynamically flushed by the rotation method, and the antifouling score of the antifouling coating can be further increased to 90. The prepared antifouling coating has significant static / dynamic antifouling performance as proved by the actual sea antifouling test.

[0095] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied to other related technical fields, shall be similarly included in the patent protection scope of the present invention.

Claims

1. A high-efficiency static / dynamic antifouling coating and a method for preparing the same, characterized in that: A silicone rubber-epoxy self-stratifying coating with a micron-porous structure on the surface is prepared by a template method, and a pH-responsive smart nanofiller is loaded onto the surface of the porous silicone rubber-epoxy self-stratifying coating through capillary force to obtain a silicone rubber-epoxy self-stratifying coating with a pH-responsive smart nanofiller loaded on the surface, i.e., a high-efficiency static / dynamic antifouling coating.

2. According to claim 1, a high-efficiency static / dynamic antifouling coating and a preparation method thereof, characterized in that: The pH-responsive smart nanofiller is a mesoporous silica-coated cuprous oxide nanofiller grafted with a pH-responsive polymer.

3. According to claim 2, a high-efficiency static / dynamic antifouling coating and a preparation method thereof, characterized in that: The pH responsive polymer is poly(2-vinylpyridine)-polymethyl methacrylate.

4. According to claim 3, a high-efficiency static / dynamic antifouling coating and a preparation method thereof, characterized in that: The following steps are involved: S1. Stir Span 80 and Tween 80 at a mass ratio of 3:1 for 10-15 minutes to prepare a pore-forming agent, and then ultrasonically mix for 10-30 minutes; S2, Dow Corning 184 silicone rubber and curing agent are uniformly stirred at a mass ratio of 10:1 for 1-3 hours, and a pore-forming agent is added at a mass ratio of 10%-40% relative to the silicone rubber to prepare a silicone rubber precursor; S3, uniformly stirring bisphenol A epoxy resin, polyamide curing agent and xylene at a mass ratio of 1:1:3 for 1-3 hours to prepare an epoxy resin precursor; S4, uniformly stirring the epoxy resin precursor and the silicone rubber precursor at a mass ratio of 3:1 for 2-6 hours, coating the surface of the commercial epoxy resin anticorrosive primer and curing it to form a silicone rubber-epoxy resin self-stratifying coating, then immersing it in a mixed solution of deionized water and anhydrous ethanol in a volume ratio of 1:1 at 60-70° C. for 12-36 hours to remove the pore-forming agent, and drying it to form a porous silicone rubber-epoxy self-stratifying coating; S5, adding hexadecyl ammonium bromide, ammonia water, ethyl orthosilicate and cuprous oxide nanoparticles in a mass ratio of 10:5:3:1 to a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 1:2, stirring for 12-24 hours, and recovering the precipitated product by centrifugation to obtain mesoporous silica-coated cuprous oxide nanofiller; S6, dispersing the mesoporous silica-coated cuprous oxide nanofiller in anhydrous toluene, adding 1%-5% by mass of (3-bromopropyl)trimethoxysilane, and stirring for 12-24 hours to achieve bromoalkyl functionalization of the surface of the mesoporous silica-coated cuprous oxide nanofiller; S7, adding poly(2-vinylpyridine)-polymethyl methacrylate to anhydrous tetrahydrofuran solution to prepare a reaction solution with a mass concentration of 5.0 mg / mL, and adding 1%-5% by mass fraction of surface bromoalkyl functionalized mesoporous silica-coated cuprous oxide nanofiller, stirring for 20-60 minutes and then drying in a vacuum drying oven to obtain a smart nanofiller with pH response characteristics; S8. Disperse 1%-3% of the mass fraction of pH-responsive smart nanofillers into anhydrous ethanol, and immerse the porous silicone rubber-epoxy self-stratifying coating therein for 2-6 hours, wherein each square centimeter of the porous silicone rubber-epoxy self-stratifying coating is immersed in 10 mL of anhydrous ethanol solution containing the pH-responsive smart nanofillers, to obtain a silicone rubber-epoxy self-stratifying coating with a surface loaded with pH-responsive smart nanofillers, i.e., a high-efficiency static / dynamic antifouling coating.

5. A high-efficiency static / dynamic antifouling coating and preparation method thereof according to claim 4, characterized in that: The polyamide curing agent in S3 is polyamide 650 or polyamide 651.

6. A high-efficiency static / dynamic antifouling coating and preparation method thereof according to claim 4, characterized in that: The curing condition in S4 is curing at 70-90° C. for 12-24 hours.

7. A high-efficiency static / dynamic antifouling coating and preparation method thereof according to claim 4, characterized in that: The drying condition in S7 is drying at 100-120° C. for 12-24 hours.

8. A high-efficiency static / dynamic antifouling coating prepared according to the method of any one of claims 1 to 7.

9. A high-efficiency static / dynamic antifouling coating according to claim 8, characterized in that: The interface bonding strength of the high-efficiency static / dynamic antifouling coating can reach 4.01±0.22Mpa.

10. Use of the high-efficiency static / dynamic antifouling coating according to claim 8 or 9 in the protection against fouling of ships, bridges, docks, offshore platforms and various steel structure projects.

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