A high-adhesion organic silicon marine antifouling and anticorrosion coating, and its preparation method and use

Abstract

The present invention discloses a kind of organosilicon marine antifouling and anticorrosion coating with high adhesion, its preparation method and use, the organosilicon marine antifouling and anticorrosion coating is obtained by coating a composite coating material on the surface of a substrate after light curing; the composite coating material includes dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide, photoinitiator and toluene. The process synthesis conditions provided by the present invention are simple, clean and environmentally friendly, ultraviolet light triggers cross-linking reaction rapidly and effectively, the prepared antifouling and anticorrosion coating has good substrate adhesion, excellent mechanical properties and antifouling and anticorrosion performance, can greatly meet the antifouling performance, substrate adhesion and mechanical strength requirements of organosilicon coatings in marine applications, and has broad application prospects in the field of marine antifouling and anticorrosion coatings.

Description

Technical Field

[0001] The present invention relates to the technical field of marine antifouling and anticorrosion coatings, and in particular to an organosilicon marine antifouling and anticorrosion coating with high adhesion, a preparation method thereof, and uses thereof. Background Art

[0002] Hundreds of thousands of organisms live in the ocean, including a class of marine organisms that grow fixedly on artificial structures (such as ships, docks, and buoys). Fouling organisms attached to underwater surfaces can increase hydrodynamic drag, impair ship maneuverability, increase fuel consumption, clog circulation pipes, and damage equipment, leading to significant economic maintenance costs and environmental safety issues. Furthermore, marine corrosion caused by marine biofouling can cause tiny cracks on the surface, which can gradually lead to large-scale corrosion, reducing surface strength and causing serious safety issues. Therefore, it is crucial to effectively control biofouling and inhibit environmental corrosion on surfaces submerged in the ocean.

[0003] To combat the problem of marine biofouling, a range of technical measures have been adopted, primarily physical methods such as mechanical cleaning, ultrasonic treatment, and ultraviolet irradiation, and chemical methods such as seawater electrolysis and the use of marine antifouling coatings. Mechanical cleaning requires regular deployment of divers using high-pressure water cannons or scrapers equipped with underwater robots to remove biofouling adhering to underwater surfaces. However, this method is time-consuming and labor-intensive, requires frequent maintenance, and can cause significant damage to the substrate. Ultrasonic treatment kills fouling organisms by applying high-frequency sound waves (20-100 Hz). However, due to the need for an external ultrasonic transmitter and energy dissipation issues, it is only suitable for confined spaces such as seawater pipelines. Ultraviolet light irradiation uses the principle that ultraviolet light denatures proteins to kill fouling organisms, but is rarely used due to limitations on irradiation area and distance. Electrolysis of seawater involves electrolyzing chlorides in seawater to produce sodium hypochlorite, which can destroy the cellular tissues of fouling organisms and prevent them from adhering. However, since the ocean is an open system, the sodium hypochlorite generated by electrolysis is infinitely diluted by seawater, rapidly dropping its concentration below the effective concentration. Therefore, this method is also only suitable for confined spaces. Compared with physical antifouling technologies, chemical antifouling technologies offer advantages such as long-term antifouling, significant antifouling effects, and ease of implementation, leading to their wider application. Applying marine antifouling coatings is currently the most effective, economical, simplest, and widely used method.

[0004] Silicone marine antifouling coatings belong to the field of environmentally friendly, foul-releasing antifouling coatings. Based on their low surface free energy and low elastic modulus, they exploit the relative motion between the ship and the seawater to prevent fouling organisms and remove loosely adhered ones, thus holding great promise for application. However, due to the low modulus of PDMS (~1 MPa), it is susceptible to mechanical damage in practical applications. Furthermore, due to its nonpolarity and inertness, PDMS exhibits poor adhesion to substrates. Modification of linear PDMS elastomers with various groups (such as epoxy resin, catechol, polyurethane, urea, and 2uredo-4[1H]-pyrimidine) can improve substrate adhesion and mechanical properties. However, surface modifications induced by these polar groups often compromise antifouling performance. Adding inorganic particles (such as SiO2, nanodiamonds, graphene oxide, and multi-walled carbon nanotubes) to improve substrate adhesion often increases surface roughness, thereby impairing antifouling performance. Therefore, achieving excellent antifouling, substrate adhesion and mechanical properties simultaneously is a major challenge facing silicone antifouling and anticorrosion coatings. Summary of the Invention

[0005] In response to the above-mentioned deficiencies in the prior art, the present invention proposes a highly adhesive organosilicon marine antifouling and anticorrosion coating, a preparation method and use thereof, which overcome the defects of the prior art organosilicon coatings in terms of weak adhesion to the substrate and poor mechanical stability.

[0006] The technical solution adopted to achieve the purpose of the present invention is:

[0007] In a first aspect, the present invention provides an organosilicon marine antifouling and anticorrosion coating with high adhesion, wherein the organosilicon marine antifouling and anticorrosion coating is obtained by coating a composite coating material on the surface of a substrate and subjecting it to light curing;

[0008] The composite coating material comprises dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide, a photoinitiator and toluene.

[0009] Organosilicon marine antifouling coatings belong to the field of environmentally friendly fouling-releasing antifouling coatings. Based on their low surface free energy and low elastic modulus, they utilize the relative motion between the ship and the seawater to prevent and control fouling organisms and remove loosely adhered fouling organisms, thus possessing great application prospects. The present invention cross-links dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, and N-(2,4,6-trichlorophenyl)maleimide through a phototriggered thiol-ene click reaction to produce a highly adhesive organosilicon marine antifouling and anticorrosion coating.

[0010] Dopamine is a major component of adhesive proteins found in a variety of marine organisms. Due to the chemical versatility and affinity diversity of the catechol functional groups in its structure, dopamine possesses unique chemical properties. The catechol structure provides a strong anchoring effect. Dopamine acrylamide acts as a biomimetic anchor to ensure a strong bond between the coating and the substrate, allowing the antifouling and anticorrosion coating to adhere firmly to the substrate. As a new type of organic / inorganic hybrid nanomaterial, thiol-modified hexahedral polysilsesquioxane, with its unique structure combining an internal inorganic rigid structure with external organic groups, effectively improves compatibility with organic substrates. The advantages of the Si-O-Si inorganic core structure give the antifouling and anticorrosion coating excellent mechanical stability. The hydrophobicity of polydimethylsiloxane and the bactericidal properties of N-(2,4,6-trichlorophenyl)maleimide provide the antifouling and anticorrosion coating with excellent antifouling properties.

[0011] The process provided by the present invention has simple synthesis conditions, is clean and environmentally friendly, and the ultraviolet light-induced cross-linking reaction is rapid and effective. The prepared antifouling and anticorrosion coating has good substrate adhesion, excellent mechanical properties and antifouling and anticorrosion properties, and can greatly meet the requirements of marine applications for the antifouling properties, substrate adhesion and mechanical strength of silicone coatings, and has broad application prospects in the field of marine antifouling and anticorrosion coatings.

[0012] As a preferred technical solution of the present invention, the mass ratio of the dopamine acrylamide, the thiol-modified hexahedral polysilsesquioxane, the thiol polydimethylsiloxane, the N-(2,4,6-trichlorophenyl) maleimide and the photoinitiator is (0.5-5):(0.5-5):(10-50):(0.5-2):(1-10), for example, it can be 0.5:0.5:10:0.5:1, 1:1:15: 0.6:2, 1.5:1.5:20:0.7:3, 2:2:25:0.8:4, 2.5:2.5:30:1:5, 3:3:35:1.2:6, 3.5:3.5:40:1.5:7, 4:4:45:1.6:8, 4.5:4.5:50:1.8:9 or 5:5:50:2:10, but are not limited to the listed values, other values ​​not listed within the numerical range are also applicable.

[0013] In some optional examples, the ratio of the total mass of the dopamine acrylamide, the thiol-modified hexahedral polysilsesquioxane, the thiol polydimethylsiloxane, the N-(2,4,6-trichlorophenyl)maleimide and the photoinitiator to the volume of the toluene is (0.0625-0.375) g:1 mL, for example, 0.0625 g:1 mL, 0.08 g:1 mL, 0.1 g:1 mL, 0.12 g:1 mL, 0. 0.14g:1mL, 0.16g:1mL, 0.18g:1mL, 0.2g:1mL, 0.22g:1mL, 0.24g:1mL, 0.26g:1mL, 0.28g:1mL, 0.3g:1mL, 0.32g:1mL, 0.34g:1mL, 0.36g:1mL or 0.375g:1mL, but is not limited to the listed values, other values ​​not listed within the numerical range are also applicable.

[0014] As a preferred technical solution of the present invention, the photoinitiator includes benzoin ethers and / or benzophenones, preferably benzoin dimethyl ether.

[0015] In some optional examples, the material of the substrate includes any one of iron, aluminum, copper or glass.

[0016] In a second aspect, the present invention provides a method for preparing the organosilicon marine antifouling and anticorrosion coating according to the first aspect, the preparation method comprising:

[0017] Dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl)maleimide and a photoinitiator are dissolved in toluene and mixed evenly to obtain a composite coating material. The composite coating material is evenly coated on the surface of a substrate and cured by ultraviolet light to obtain the organic silicone marine antifouling and anticorrosion coating.

[0018] As a preferred technical solution of the present invention, the dopamine acrylamide is prepared by the following method:

[0019] Dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed uniformly to obtain a precursor solution, methacrylic anhydride solution is added dropwise to the precursor solution, and after mixing uniformly, a reaction solution is obtained, an alkali solution is added dropwise to the reaction solution to adjust its pH value, the reaction solution is heated to cause a nucleophilic reaction, and after the reaction is completed, separation and purification are performed to obtain the dopamine acrylamide.

[0020] As a preferred technical solution of the present invention, the mass ratio of the dopamine hydrochloride, the sodium borate, the sodium carbonate, the deionized water and the methacrylic anhydride solution is (1-10):(5-20):(1-10):(100-150):(1-10), for example, it can be 1:5:1:100:1, 2:6:2:105:2, 3:7:3:110:3, 4:8:4:115:4, 5:9:5:120:5, 6:10:6:125:6, 7:12:7:130:7, 8:13:8:135:8, 9:14:9:140:9 or 10:15:10:150:10, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0021] In some optional examples, the methacrylic anhydride solution consists of methacrylic anhydride and an organic solvent, wherein the organic solvent includes any one or a combination of at least two of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

[0022] In some optional examples, the mass fraction of the methacrylic anhydride solution is 90 to 95 wt%, for example, 90 wt%, 90.5 wt%, 91 wt%, 91.5 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 94.5 wt% or 95 wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] In some optional examples, the concentration of the alkali solution is 0.1 to 3.0 mol / L, for example, it can be 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L, 2.0 mol / L, 2.2 mol / L, 2.4 mol / L, 2.6 mol / L, 2.8 mol / L or 3.0 mol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] In some optional examples, alkaline solution is added dropwise to the reaction solution to adjust its pH value to 8-10, for example, it can be 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8 or 10.0, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] In some optional examples, the heating temperature of the nucleophilic reaction of the reaction solution is 25 to 65°C, for example, it can be 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C or 65°C, but is not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, and more preferably 28 to 40°C.

[0026] In some optional examples, the heating time of the nucleophilic reaction of the reaction solution is 6 to 36 hours, for example, it can be 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours or 36 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] In some optional examples, the separation and purification process includes:

[0028] An acid solution is added dropwise to the reaction product obtained by the nucleophilic reaction to adjust its pH value to 1-2, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0; then extraction is performed using ethyl acetate and / or n-hexane as an extractant, preferably a mixture of n-hexane and ethyl acetate in a volume ratio of (0.25-0.65):1 is used as the extractant, for example, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1 or 0.65:1, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0029] As a preferred technical solution of the present invention, the thiol-modified hexahedral polysilsesquioxane is prepared by the following method:

[0030] (3-mercaptopropyl)trimethoxysilane and hydrochloric acid solution are added to methanol for condensation reaction, and after the reaction is completed, the thiol-modified hexahedral polysilsesquioxane is obtained through separation and purification.

[0031] As a preferred technical solution of the present invention, the mass fraction of the hydrochloric acid solution is 35 to 40 wt%, for example, it can be 35 wt%, 35.5 wt%, 36 wt%, 36.5 wt%, 37 wt%, 37.5 wt%, 38 wt%, 38.5 wt%, 39 wt%, 39.5 wt% or 40 wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] In some optional examples, the volume ratio of the (3-mercaptopropyl)trimethoxysilane, the hydrochloric acid solution and the methanol is (1-5):(1-10):(30-80), for example, it can be 1:1:30, 1.5:2:35, 2:3:40, 2.5:4:45, 3:5:50, 3.5:6:60, 4:7:65, 4.5:8:70, 5:9:75 or 5:10:80, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0033] In some optional examples, the temperature of the condensation reaction is 70-120°C, for example, it can be 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In some optional examples, the condensation reaction time is 18 to 30 hours, for example, it can be 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] As a preferred technical solution of the present invention, the ultraviolet light wavelength used in the ultraviolet light curing is 365nm.

[0036] In some optional examples, the power of the ultraviolet light source used for the ultraviolet curing is 1 to 5 W, for example, it can be 1.0 W, 1.5 W, 2.0 W, 2.5 W, 3.0 W, 3.5 W, 4.0 W, 4.5 W or 5.0 W, but it is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0037] In some optional embodiments, the UV curing uses an UV intensity of 0.48 to 2.0 W / cm 2 , for example, it can be 0.48W / cm 2 , 0.5W / cm 2 , 1.0W / cm 2 , 1.1W / cm 2 , 1.2W / cm 2 , 1.3W / cm 2 , 1.4W / cm 2 , 1.5W / cm 2 , 1.6W / cm 2 , 1.7W / cm 2 , 1.8W / cm 2 , 1.9W / cm 2or 2.0W / cm 2 , but is not limited to the listed values. Other values ​​not listed in this numerical range are also applicable, preferably 0.8 to 1.6 W / cm 2 .

[0038] In some optional examples, the UV curing time is 60 to 300 s, for example, it can be 60 s, 70 s, 80 s, 90 s, 100 s, 150 s, 200 s, 250 s or 300 s, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 80 to 300 s.

[0039] In a third aspect, the present invention provides a use of the organic silicon marine antifouling and anticorrosion coating with high adhesion as described in the first aspect, wherein the organic silicon marine antifouling and anticorrosion coating is used for antifouling and anticorrosion of ship hulls.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] Organosilicon marine antifouling coatings belong to the field of environmentally friendly fouling-releasing antifouling coatings. Based on their low surface free energy and low elastic modulus, they utilize the relative motion between the ship and the seawater to prevent and control fouling organisms and remove loosely adhered fouling organisms, thus possessing great application prospects. The present invention cross-links dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, and N-(2,4,6-trichlorophenyl)maleimide through a phototriggered thiol-ene click reaction to produce a highly adhesive organosilicon marine antifouling and anticorrosion coating.

[0042] Dopamine is a major component of adhesive proteins found in a variety of marine organisms. Due to the chemical versatility and affinity diversity of the catechol functional groups in its structure, dopamine possesses unique chemical properties. The catechol structure provides a strong anchoring effect. Dopamine acrylamide acts as a biomimetic anchor to ensure a strong bond between the coating and the substrate, allowing the antifouling and anticorrosion coating to adhere firmly to the substrate. As a new type of organic / inorganic hybrid nanomaterial, thiol-modified hexahedral polysilsesquioxane, with its unique structure combining an internal inorganic rigid structure with external organic groups, effectively improves compatibility with organic substrates. The advantages of the Si-O-Si inorganic core structure give the antifouling and anticorrosion coating excellent mechanical stability. The hydrophobicity of polydimethylsiloxane and the bactericidal properties of N-(2,4,6-trichlorophenyl)maleimide provide the antifouling and anticorrosion coating with excellent antifouling properties.

[0043] The process provided by the present invention has simple synthesis conditions, is clean and environmentally friendly, and the ultraviolet light-induced cross-linking reaction is rapid and effective. The prepared antifouling and anticorrosion coating has good substrate adhesion, excellent mechanical properties and antifouling and anticorrosion properties, and can greatly meet the requirements of marine applications for the antifouling properties, substrate adhesion and mechanical strength of silicone coatings, and has broad application prospects in the field of marine antifouling and anticorrosion coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 A flow chart of the preparation process of the organosilicon marine antifouling and anticorrosive coating provided in Examples 1-9 of the present invention;

[0045] Figure 2 This is the infrared spectrum of the dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane and organosilicon marine antifouling and anticorrosion coating prepared in Example 1 of the present invention:

[0046] Figure 3 This is a surface scanning electron microscope image of the organosilicon marine antifouling and anticorrosion coating prepared in Example 1 of the present invention;

[0047] Figure 4 This is a scanning electron microscope image of a cross section of the organosilicon marine antifouling and anticorrosion coating prepared in Example 1 of the present invention;

[0048] Figure 5 This is a picture of a real sea board test of the organosilicon marine antifouling and anticorrosion coating prepared in Example 1 of the present invention;

[0049] Figure 6 This is a real sea hanging board test picture of the organosilicon marine antifouling and anticorrosion coating prepared in Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0050] In order to fully and clearly describe the technical solution of the present invention, the present invention will be further explained below with reference to the accompanying drawings and embodiments. The embodiments described are only part of the embodiments of the present invention, and the implementation methods of the present invention are not limited thereto.

[0051] Example 1

[0052] This embodiment provides a method for preparing an organosilicon marine antifouling and anticorrosive coating with high adhesion, such as Figure 1 As shown, the preparation method specifically includes the following steps:

[0053] (1) Preparation of dopamine acrylamide: dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed to obtain a precursor solution; 90 wt% methacrylic anhydride solution is added dropwise to the precursor solution, and the mixture is mixed to obtain a reaction solution, wherein the mass ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride solution is 1:5:1:100:1; 0.1 mol / L sodium hydroxide solution is added dropwise to the reaction solution to adjust its pH to 8, and then the reaction solution is heated to 25°C and mixed and stirred for 36 hours to cause a nucleophilic reaction;

[0054] After the reaction is completed, the reaction product is washed twice with 50 mL of ethyl acetate, the solid in the solution is vacuum filtered, the resulting solution is acidified to a pH of 1 with a 6 M hydrochloric acid solution, and the organic layer is extracted three times from the acidified aqueous solution with 50 mL of ethyl acetate; the transparent brown organic layer extracted in ethyl acetate is dried over MgSO4, the solution volume is reduced to 25 mL using a rotary evaporator, the resulting solution is added to 250 mL of n-hexane, and vigorously stirred to precipitate a brown solid, the formed suspension is refrigerated to maximize the size of the formed crystals, the obtained light brown solid is dissolved in 20 mL of ethyl acetate, and then purified by precipitation in 300 mL of n-hexane, and the obtained solid powder is dried in vacuum overnight to obtain dopamine acrylamide;

[0055] (2) Preparation of mercapto-modified hexahedral polysilsesquioxane: (3-mercaptopropyl)trimethoxysilane and a 35 wt% hydrochloric acid solution were added to methanol for condensation reaction, wherein the volume ratio of (3-mercaptopropyl)trimethoxysilane, hydrochloric acid solution, and methanol was 1:1:30, the condensation reaction temperature was 70°C, and the condensation reaction time was 30 h. After the reaction, the mercapto-modified hexahedral polysilsesquioxane was obtained by separation and purification.

[0056] (3) Preparation of organosilicon marine antifouling and anticorrosion coating: dissolving the dopamine acrylamide obtained in step (1), the thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether obtained in step (2) in toluene, wherein the mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether is 0.5:0.5:10:0.5:1, and the total mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether to the volume of toluene is 0.0625 g:1 mL, and mixing them evenly to obtain a composite coating material;

[0057] The composite coating material was evenly applied to the surface of the stainless steel plate and irradiated with ultraviolet light of 365 nm wavelength. The power of the ultraviolet light source was 1 W and the intensity of the ultraviolet light was 0.48 W / cm 2 The irradiation time is 300s, and the organic silicon marine antifouling and anticorrosion coating is obtained after curing.

[0058] The infrared spectra of the dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane and organosilicon marine antifouling and anticorrosion coating prepared in this example are shown in FIG. Figure 2 As shown in the figure, the characteristic peaks of each group in the coating and raw materials are clearly visible, 2557cm -1 The characteristic peak is the stretching vibration peak of -SH, 1259cm -1 The characteristic peak at 1112 cm is the symmetrical deformation vibration absorption peak of Si-(CH3)2. -1 The sharp peak at 690 cm-1 should be the characteristic absorption peak of the Si-O-Si skeleton in the cage-type silsesquioxane, proving the formation of the POSS cage. -1 The characteristic peak at 3189cm is the out-of-plane bending vibration peak of Si-(CH3)2. -1 The stretching vibration peak of -OH is 1653 cm -1 The absorption peak of -NC=O is 1594cm -1 The absorption peak of C=C is 1396cm -1 and 1191cm -1 The absorption peak of benzene ring is at 2557cm -1 The stretching vibration peak of -SH at 1594 cm -1 The C=C absorption peak at 37° disappeared, indicating that a thiol-ene click reaction occurred between -SH and C=C under the initiation of ultraviolet light.

[0059] The surface scanning electron microscope image of the organosilicon marine antifouling and anticorrosion coating prepared in this embodiment is as follows: Figure 3 As shown in the figure, it can be seen that there are 0.1 to 0.8 μm particle protrusions distributed on the coating surface.

[0060] The cross-sectional scanning electron microscope image of the organic silicon marine antifouling and anticorrosion coating prepared in this embodiment is as follows: Figure 4 As shown in the figure, the average thickness of the coating can be measured to be 61.57 μm.

[0061] Example 2

[0062] This embodiment provides a method for preparing an organosilicon marine antifouling and anticorrosion coating with high adhesion, such as Figure 1 As shown, the preparation method specifically includes the following steps:

[0063] (1) Preparation of dopamine acrylamide: dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed to obtain a precursor solution; a 91 wt% methacrylic anhydride solution is added dropwise to the precursor solution, and the mixture is mixed to obtain a reaction solution, wherein the mass ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride solution is 3:10:3:110:3; a 0.5 mol / L sodium hydroxide solution is added dropwise to the reaction solution to adjust its pH to 8.5, and then the reaction solution is heated to 35°C and mixed and stirred for 30 hours to cause a nucleophilic reaction;

[0064] After the reaction is completed, the reaction product is washed twice with 50 mL of ethyl acetate, the solid in the solution is vacuum filtered, the resulting solution is acidified to a pH of 1 with a 6 M hydrochloric acid solution, and the organic layer is extracted three times from the acidified aqueous solution with 50 mL of ethyl acetate; the transparent brown organic layer extracted in ethyl acetate is dried over MgSO4, the solution volume is reduced to 25 mL using a rotary evaporator, the resulting solution is added to 250 mL of n-hexane, and vigorously stirred to precipitate a brown solid, the formed suspension is refrigerated to maximize the size of the formed crystals, the obtained light brown solid is dissolved in 20 mL of ethyl acetate, and then purified by precipitation in 300 mL of n-hexane, and the obtained solid powder is dried in vacuum overnight to obtain dopamine acrylamide;

[0065] (2) Preparation of mercapto-modified hexahedral polysilsesquioxane: (3-mercaptopropyl)trimethoxysilane and a 36 wt% hydrochloric acid solution were added to methanol for condensation reaction, wherein the volume ratio of (3-mercaptopropyl)trimethoxysilane, hydrochloric acid solution, and methanol was 2:3:40, the condensation reaction temperature was 80°C, and the condensation reaction time was 27 h. After the reaction, the mercapto-modified hexahedral polysilsesquioxane was obtained by separation and purification;

[0066] (3) Preparation of organosilicon marine antifouling and anticorrosion coating: dissolving the dopamine acrylamide obtained in step (1), the thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether obtained in step (2) in toluene, wherein the mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether is 1:1:20:0.8:3, and the total mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether to the volume of toluene is 0.1 g:1 mL, and mixing them evenly to obtain a composite coating material;

[0067] The composite coating material was evenly applied to the surface of the stainless steel plate and irradiated with ultraviolet light of 365nm wavelength. The power of the ultraviolet light source was 2W and the intensity of the ultraviolet light was 1W / cm 2 The irradiation time is 240s, and the organic silicon marine antifouling and anticorrosive coating is obtained after curing.

[0068] Example 3

[0069] This embodiment provides a method for preparing an organosilicon marine antifouling and anticorrosion coating with high adhesion, such as Figure 1 As shown, the preparation method specifically includes the following steps:

[0070] (1) Preparation of dopamine acrylamide: dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed to obtain a precursor solution; a 92 wt% methacrylic anhydride solution is added dropwise to the precursor solution, and the mixture is mixed to obtain a reaction solution, wherein the mass ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride solution is 5:15:5:120:5; a 1 mol / L sodium hydroxide solution is added dropwise to the reaction solution to adjust its pH to 9, and then the reaction solution is heated to 45°C and mixed and stirred for 22 hours to cause a nucleophilic reaction;

[0071] After the reaction is completed, the reaction product is washed twice with 50 mL of ethyl acetate, the solid in the solution is vacuum filtered, the resulting solution is acidified to a pH of 1 with a 6 M hydrochloric acid solution, and the organic layer is extracted three times from the acidified aqueous solution with 50 mL of ethyl acetate; the transparent brown organic layer extracted in ethyl acetate is dried over MgSO4, the solution volume is reduced to 25 mL using a rotary evaporator, the resulting solution is added to 250 mL of n-hexane, and vigorously stirred to precipitate a brown solid, the formed suspension is refrigerated to maximize the size of the formed crystals, the obtained light brown solid is dissolved in 20 mL of ethyl acetate, and then purified by precipitation in 300 mL of n-hexane, and the obtained solid powder is dried in vacuum overnight to obtain dopamine acrylamide;

[0072] (2) Preparation of mercapto-modified hexahedral polysilsesquioxane: (3-mercaptopropyl)trimethoxysilane and a 37 wt% hydrochloric acid solution were added to methanol for condensation reaction, wherein the volume ratio of (3-mercaptopropyl)trimethoxysilane, hydrochloric acid solution, and methanol was 3:5:50, the condensation reaction temperature was 90°C, and the condensation reaction time was 24 h. After the reaction, the mercapto-modified hexahedral polysilsesquioxane was obtained by separation and purification;

[0073] (3) Preparation of organosilicon marine antifouling and anticorrosion coating: dopamine acrylamide obtained in step (1), thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether obtained in step (2) are dissolved in toluene, wherein the mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether is 2:2:30:1:5, and the total mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether to the volume of toluene is 0.2 g:1 mL, and the mixture is evenly mixed to obtain a composite coating material;

[0074] The composite coating material was evenly applied to the surface of the aluminum plate and irradiated with ultraviolet light of 365 nm wavelength. The power of the ultraviolet light source was 3 W and the intensity of the ultraviolet light was 1.5 W / cm 2 The irradiation time is 180s, and the organic silicon marine antifouling and anticorrosive coating is obtained after curing.

[0075] Example 4

[0076] This embodiment provides a method for preparing an organosilicon marine antifouling and anticorrosion coating with high adhesion, such as Figure 1 As shown, the preparation method specifically includes the following steps:

[0077] (1) Preparation of dopamine acrylamide: dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed to obtain a precursor solution; a 93 wt% methacrylic anhydride solution is added dropwise to the precursor solution, and the mixture is mixed to obtain a reaction solution, wherein the mass ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride solution is 8:18:8:130:8; a 2 mol / L sodium hydroxide solution is added dropwise to the reaction solution to adjust its pH to 9.5, and then the reaction solution is heated to 55°C and mixed and stirred for 14 hours to cause a nucleophilic reaction;

[0078] After the reaction is completed, the reaction product is washed twice with 50 mL of ethyl acetate, the solid in the solution is vacuum filtered, the resulting solution is acidified to a pH of 1 with a 6 M hydrochloric acid solution, and the organic layer is extracted three times from the acidified aqueous solution with 50 mL of ethyl acetate; the transparent brown organic layer extracted in ethyl acetate is dried over MgSO4, the solution volume is reduced to 25 mL using a rotary evaporator, the resulting solution is added to 250 mL of n-hexane, and vigorously stirred to precipitate a brown solid, the formed suspension is refrigerated to maximize the size of the formed crystals, the obtained light brown solid is dissolved in 20 mL of ethyl acetate, and then purified by precipitation in 300 mL of n-hexane, and the obtained solid powder is dried in vacuum overnight to obtain dopamine acrylamide;

[0079] (2) Preparation of mercapto-modified hexahedral polysilsesquioxane: (3-mercaptopropyl)trimethoxysilane and a 38 wt% hydrochloric acid solution were added to methanol for condensation reaction, wherein the volume ratio of (3-mercaptopropyl)trimethoxysilane, hydrochloric acid solution, and methanol was 4:8:60, the condensation reaction temperature was 100°C, and the condensation reaction time was 21 h. After the reaction, the mercapto-modified hexahedral polysilsesquioxane was obtained by separation and purification.

[0080] (3) Preparation of organosilicon marine antifouling and anticorrosion coating: dissolving the dopamine acrylamide obtained in step (1), the thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether obtained in step (2) in toluene, wherein the mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether is 3:3:40:1.5:8, and the total mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether to the volume of toluene is 0.3 g:1 mL, and mixing them evenly to obtain a composite coating material;

[0081] The composite coating material was evenly applied to the surface of the copper plate and irradiated with ultraviolet light of 365 nm wavelength. The power of the ultraviolet light source was 4 W and the intensity of the ultraviolet light was 1.8 W / cm 2 The irradiation time is 120s, and the organic silicon marine antifouling and anticorrosive coating is obtained after curing.

[0082] Example 5

[0083] This embodiment provides a method for preparing an organosilicon marine antifouling and anticorrosion coating with high adhesion, such as Figure 1 As shown, the preparation method specifically includes the following steps:

[0084] (1) Preparation of dopamine acrylamide: dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed to obtain a precursor solution; a 95 wt% methacrylic anhydride solution is added dropwise to the precursor solution, and the mixture is mixed to obtain a reaction solution, wherein the mass ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride solution is 10:20:10:150:10; a 3.0 mol / L sodium hydroxide solution is added dropwise to the reaction solution to adjust its pH to 10, and then the reaction solution is heated to 65°C and mixed and stirred for 6 hours to cause a nucleophilic reaction;

[0085] After the reaction is completed, the reaction product is washed twice with 50 mL of ethyl acetate, the solid in the solution is vacuum filtered, the resulting solution is acidified to a pH of 1 with a 6 M hydrochloric acid solution, and the organic layer is extracted three times from the acidified aqueous solution with 50 mL of ethyl acetate; the transparent brown organic layer extracted in ethyl acetate is dried over MgSO4, the solution volume is reduced to 25 mL using a rotary evaporator, the resulting solution is added to 250 mL of n-hexane, and vigorously stirred to precipitate a brown solid, the formed suspension is refrigerated to maximize the size of the formed crystals, the obtained light brown solid is dissolved in 20 mL of ethyl acetate, and then purified by precipitation in 300 mL of n-hexane, and the obtained solid powder is dried in vacuum overnight to obtain dopamine acrylamide;

[0086] (2) Preparation of mercapto-modified hexahedral polysilsesquioxane: (3-mercaptopropyl)trimethoxysilane and a 40 wt% hydrochloric acid solution were added to methanol for condensation reaction, wherein the volume ratio of (3-mercaptopropyl)trimethoxysilane, hydrochloric acid solution, and methanol was 5:10:80, the condensation reaction temperature was 120°C, and the condensation reaction time was 18 h. After the reaction, the mercapto-modified hexahedral polysilsesquioxane was obtained by separation and purification;

[0087] (3) Preparation of organosilicon marine antifouling and anticorrosion coating: dissolving the dopamine acrylamide obtained in step (1), the thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether obtained in step (2) in toluene, wherein the mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether is 5:5:50:2:10, and the total mass ratio of dopamine acrylamide, thiol-modified hexahedral polysilsesquioxane, thiol polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide and benzoin dimethyl ether to the volume of toluene is 0.375 g:1 mL, and mixing them evenly to obtain a composite coating material;

[0088] The composite coating material was evenly applied to the surface of the glass plate and irradiated with ultraviolet light of 365 nm wavelength. The power of the ultraviolet light source was 5 W and the intensity of the ultraviolet light was 2.0 W / cm 2 The irradiation time is 60s, and the organic silicon marine antifouling and anticorrosion coating is obtained after curing.

[0089] Example 6

[0090] This embodiment provides a method for preparing a silicone marine antifouling and anticorrosion coating with high adhesion. The difference from Example 1 is that in step (3), the mass ratio of dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl)maleimide and photoinitiator is adjusted to 0.2:0.5:10:0.5:1, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0091] Example 7

[0092] This embodiment provides a method for preparing a silicone marine antifouling and anticorrosive coating with high adhesion. The difference from Example 1 is that in step (3), the mass ratio of dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl)maleimide and photoinitiator is adjusted to 8:0.5:10:0.5:1, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0093] Example 8

[0094] This embodiment provides a method for preparing a highly adhesive organosilicon marine antifouling and anticorrosive coating. The difference from Example 1 is that in step (3), the curing time is adjusted to 50 s, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0095] Example 9

[0096] This embodiment provides a method for preparing a highly adherent organosilicon marine antifouling and anticorrosive coating. The difference from Example 1 is that in step (3), the curing time is adjusted to 350 s, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0097] Comparative Example 1

[0098] This comparative example provides a method for preparing a highly adherent organosilicon marine antifouling and anticorrosive coating. The method differs from Example 1 in that step (2) is omitted, and no mercapto-modified hexahedral polysilsesquioxane is added to the composite coating material in step (3). The other process parameters and operating steps are exactly the same as those in Example 1.

[0099] Comparative Example 2

[0100] This comparative example provides a method for preparing a highly adherent organosilicon marine antifouling and anticorrosion coating. The difference from Example 1 is that N-(2,4,6-trichlorophenyl)maleimide is not added to the composite coating material in step (3), and the other process parameters and operating steps are exactly the same as those in Example 1.

[0101] Comparative Example 3

[0102] This comparative example provides a method for preparing a highly adherent organosilicon marine antifouling and anticorrosive coating. The method differs from Example 1 in that step (2) is omitted, and no mercapto-modified hexahedral polysilsesquioxane and N-(2,4,6-trichlorophenyl)maleimide are added to the composite coating material in step (3). Other process parameters and operating steps are exactly the same as those in Example 1.

[0103] The water contact angle, adhesion, antifouling performance, and anticorrosion performance of the organosilicon marine antifouling and anticorrosion coatings prepared in each embodiment and comparative example were measured. The test method is as follows:

[0104] (1) Water contact angle

[0105] Water contact angles were measured using a contact angle meter (ThetaLite, Bioline Technologies, Sweden) with a 4 μL water droplet volume, 5 to 15 seconds after drop. Five points were randomly selected for each coating surface, and the average of these five measurements was used as the water contact angle value for that coating.

[0106] (2) Adhesion test

[0107] The coating's adhesion to the substrate was tested using a DeFelsko PosiTest AT-A fully automatic digital adhesion tensile tester. According to ASTM D4541, a 2cm diameter cylindrical aluminum ingot was bonded to the coating surface with an epoxy adhesive. The adhesive was cured at room temperature for three days. The coating was then pulled away from the substrate at a stress loading rate of 0.2 MPa / s. The average of five different areas was used as the measurement result.

[0108] (3) Antibacterial test

[0109] Since E. coli is commonly found in the marine environment and daily life, the antibacterial properties of the coatings were evaluated by E. coli. Each coating was immersed in a solution containing 10 ml of bacterial suspension (approximately 10 6 CFU) in a sterile culture dish and cultured at 37°C for 12 hours. After culture, rinse the coating three times with PBS buffer to remove unstable adhering bacteria and discard the rinsing solution. Subsequently, rinse the coating repeatedly to completely separate the attached bacteria and retain the rinsing solution. Spread 200 μL of the rinsing solution evenly on the LB agar culture plate and finally culture it at 37°C for another 18 hours. The antibacterial experiment was repeated three times and the average value was taken. The antibacterial rate was calculated based on the number of colonies on the plate. The antibacterial rate (R b ) is calculated as follows:

[0110]

[0111] Among them, N b and N c Refers to the number of colonies on the plates corresponding to the blank group without coating and the experimental group with coating, respectively.

[0112] (4) Anti-algae test

[0113] Nitzschia closterium was used to evaluate the anti-diatom adhesion performance of the coating. Nitzschia closterium was cultured in F / 2 medium at 25°C with a 12:12 hour light-dark cycle. The glass slide coated with the coating to be tested was placed vertically into the algae solution, so as to minimize the occurrence of diatoms depositing on the coating surface due to gravity, thereby reducing the experimental error. Three parallel experiments were performed for each group of coating samples. After the coating was soaked in the algae solution for one week, it was taken out and gently rinsed with seawater to remove the diatoms that were not firmly adhered to the coating surface. The coating was then immersed in an 80wt% acetone aqueous solution to extract diatom chlorophyll. Finally, the fluorescence intensity was measured using an AMIscience chlorophyll fluorometer, and the anti-algae rate of the sample to be tested was calculated.

[0114] I=(1-X / Y)×100%

[0115] Wherein, I is the diatom inhibition rate; X is the fluorescence intensity of diatoms attached to the test sample; and Y is the fluorescence intensity of diatoms attached to the control sample.

[0116] (5) Actual sea hanging board test

[0117] A 90-day marine field test was conducted from September to December in the Bohai Sea, Tianjin, China (117°46′E, 39°43′N). Coated panels were mounted on stainless steel frames and immersed at a depth of 0.5 m below sea level. Three replicates were used for each coating. After a period of time, the frames were removed and rinsed with natural seawater to remove unstable silt and biofouling. The antifouling performance of the coatings was evaluated and a performance score was obtained according to the national standard GB / T5370-2007, Shallow Sea Immersion Test Method for Antifouling Paint Samples.

[0118] The actual sea board test diagrams of the organosilicon marine antifouling and anticorrosive coatings prepared in Example 1 and Comparative Example 3 are shown as follows: Figure 5 and Figure 6 As shown in the figure, it can be seen that the organic silicon marine antifouling and anticorrosive coating prepared in Comparative Example 3 (such as Figure 6 The surface of the organic silicon marine antifouling and anticorrosive coating (as shown in the figure) was obviously attached with some marine fouling organisms such as tubeworm larvae, diatoms, barnacle larvae, and even a large number of large biofouling organisms such as barnacles and mussels. Under the same test time, the organic silicon marine antifouling and anticorrosive coating prepared in Example 1 (as shown in the figure) was obviously attached with some marine fouling organisms such as tubeworm larvae, diatoms, barnacle larvae, and even a large number of large biofouling organisms such as barnacles and mussels. Figure 5 Only a few diatoms were attached to the surface, and no large, intact organisms were found.

[0119] (6) Corrosion resistance test

[0120] Electrochemical measurements (Tafel polarization curves) were performed in 3.5% NaCl solution at ambient temperature using an electrochemical workstation (CHI660C, CHInstruments, USA). The experiments were performed using a typical three-electrode system, with a metal sheet (exposed area of ​​1 cm) as the working electrode. 2 ), the reference electrode is a saturated calomel electrode (SCE, vs. Ag / AgCl), and the counter electrode is a platinum sheet. All measurements were performed when the open circuit potential (OCP) was stable. The Tafel plot is based on 1mVs -1 The corrosion potential (E corr ) and corrosion current (I corr ).

[0121] The above test results are shown in Table 1.

[0122] Table 1

[0123]

[0124] It can be seen from the test data provided in Table 1 that the organic silicone marine antifouling and anticorrosion coatings prepared in Examples 1-5 of the present invention have high adhesion and antifouling and anticorrosion properties.

[0125] It can be seen from the test data of Example 1, Example 6 and Example 7 that when the addition amount of dopamine acrylamide is too high or too low, the adhesion and antifouling and anticorrosion performance of the antifouling and anticorrosion coating will be affected. This is because the catechol group in dopamine acrylamide can be used as a biomimetic anchor, and produces a strong adsorption effect with the substrate through hydrogen bonding. The excellent adhesion ensures the long-term stability of the antifouling and anticorrosion coating in practical applications, and the performance of the coating can still be maintained during the long-term antifouling and anticorrosion process. However, the excess dopamine acrylamide in the antifouling and anticorrosion coating does not react, thereby affecting the surface energy of the coating and reducing the coating's ability to repel fouling organisms.

[0126] The test data from Examples 1, 8, and 9 demonstrate that both too short and too long curing times can affect the adhesion and anti-fouling and anti-corrosion performance of the anti-fouling and anti-corrosion coatings. This is because too short a curing time results in incomplete reaction of the components in the anti-fouling and anti-corrosion coatings. Unreacted components can easily fall off or adhere to the coating surface during testing, affecting the coating's surface energy and thus reducing the coating's adhesion and anti-fouling and anti-corrosion performance. Continuing to increase the curing time after the components in the anti-fouling and anti-corrosion coating have completed their reaction results in a waste of resources and increased production costs.

[0127] It can be seen from the test data of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 that the compounding of thiol-modified hexahedral polysilsesquioxane and N-(2,4,6-trichlorophenyl)maleimide can greatly improve the adhesion and anti-fouling and anti-corrosion performance of the anti-fouling and anti-corrosion coating. This is because the thiol-modified hexahedral polysilsesquioxane utilizes the advantages of the Si-O-Si inorganic core structure to improve the mechanical strength of the coating, so that the coating is more stable in practical applications and can maintain the integrity of the coating even in harsh environments, thereby improving the adhesion and anti-fouling and anti-corrosion performance of the anti-fouling and anti-corrosion coating.

[0128] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly adhesive organic silicone marine antifouling and anticorrosion coating, characterized in that: The organic silicon marine antifouling and anticorrosive coating is obtained by coating a composite coating material on the surface of a substrate and then light-curing it; The composite coating material comprises dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl) maleimide, a photoinitiator and toluene; The mass ratio of the dopamine acrylamide, the thiol-modified hexahedral polysilsesquioxane, the thiol polydimethylsiloxane, the N-(2,4,6-trichlorophenyl)maleimide and the photoinitiator is (0.5-5):(0.5-5):(10-50):(0.5-2):(1-10); The ratio of the total mass of the dopamine acrylamide, the thiol-modified hexahedral polysilsesquioxane, the thiol polydimethylsiloxane, the N-(2,4,6-trichlorophenyl)maleimide and the photoinitiator to the volume of the toluene is (0.0625~0.375) g:1 mL.

2. The organic silicon marine antifouling and anticorrosion coating with high adhesion according to claim 1, characterized in that: The photoinitiator includes benzoin ethers and / or benzophenones; The material of the substrate includes any one of iron, aluminum, copper or glass.

3. A method for preparing the organic silicon marine antifouling and anticorrosion coating with high adhesion according to any one of claims 1 to 2, characterized in that: The preparation method comprises: Dopamine acrylamide, mercapto-modified hexahedral polysilsesquioxane, mercapto polydimethylsiloxane, N-(2,4,6-trichlorophenyl)maleimide and a photoinitiator are dissolved in toluene and mixed evenly to obtain a composite coating material. The composite coating material is evenly coated on the surface of a substrate and cured by ultraviolet light to obtain the organic silicone marine antifouling and anticorrosion coating.

4. The preparation method according to claim 3, characterized in that The dopamine acrylamide is prepared by the following method: Dopamine hydrochloride, sodium borate, sodium carbonate and deionized water are mixed uniformly to obtain a precursor solution, methacrylic anhydride solution is added dropwise to the precursor solution, and after mixing uniformly, a reaction solution is obtained, an alkali solution is added dropwise to the reaction solution to adjust its pH value, the reaction solution is heated to cause a nucleophilic reaction, and after the reaction is completed, separation and purification are performed to obtain the dopamine acrylamide.

5. The preparation method according to claim 4, characterized in that The mass ratio of the dopamine hydrochloride, the sodium borate, the sodium carbonate, the deionized water and the methacrylic anhydride solution is (1-10):(5-20):(1-10):(100-150):(1-10); The methacrylic anhydride solution is composed of methacrylic anhydride and an organic solvent, wherein the organic solvent includes any one of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, or a combination of at least two thereof; The mass fraction of the methacrylic anhydride solution is 90-95wt%; The concentration of the alkali solution is 0.1~3.0mol / L; Adding alkali solution dropwise to the reaction solution to adjust the pH value thereof to 8-10; The heating temperature of the nucleophilic reaction of the reaction solution is 25~65°C; The heating time of the nucleophilic reaction of the reaction solution is 6 to 36 hours; The separation and purification process comprises: An acid solution is added dropwise to the reaction product obtained by the nucleophilic reaction to adjust the pH value thereof to 1-2, and then extraction is performed using ethyl acetate and / or n-hexane as an extractant.

6. The preparation method according to claim 3, characterized in that The thiol-modified hexahedral polysilsesquioxane is prepared by the following method: (3-mercaptopropyl)trimethoxysilane and hydrochloric acid solution are added to methanol for condensation reaction, and after the reaction is completed, the thiol-modified hexahedral polysilsesquioxane is obtained through separation and purification.

7. The preparation method according to claim 6, characterized in that The mass fraction of the hydrochloric acid solution is 35-40wt%; The volume ratio of the (3-mercaptopropyl)trimethoxysilane, the hydrochloric acid solution and the methanol is (1-5):(1-10):(30-80); The temperature of the condensation reaction is 70-120°C; The condensation reaction time is 18 to 30 hours.

8. The preparation method according to claim 3, characterized in that The ultraviolet light wavelength used in the ultraviolet curing is 365nm; The power of the ultraviolet light source used in the ultraviolet curing is 1~5W; The UV curing process uses a UV light intensity of 0.48-2.0 W / cm 2 ; The curing time of the ultraviolet light curing is 60 to 300 seconds.

9. Use of the highly adhesive organosilicon marine antifouling and anticorrosive coating according to any one of claims 1 to 2, characterized in that: The organic silicon marine antifouling and anticorrosion coating is used for antifouling and anticorrosion of ship hulls.

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