Antifouling coating composition as well as preparation method and application thereof

Abstract

The invention provides an antifouling coating composition as well as a preparation method and application thereof. The antifouling coating composition comprises hydroxyl-terminated polysiloxane as shown in a formula I, a compound as shown in a formula II and / or a formula III, a cross-linking agent as shown in a formula IV and a catalyst, wherein E comprises amino, an epoxy group, phenyl, furan ring, hydroxyl or sulfydryl, M comprises Cu, Zn or Ag, A comprises unsubstituted or substituted C1-C6 alkyl, B comprises a hydrolyzable group, D comprises amino, epoxy group, glycidyl ether group, hydroxyl or sulfydryl, 3 < = p: q < = infinity, 0 < = m < = 2, 0 < = n < = 2, 0 < = x < = 2, and 1 < = y < = 6. The antifouling coating composition provided by the invention can be used for forming an antifouling coating with the advantages of strong intrinsic dynamic and static antifouling capability, excellent mechanical property, scouring resistance, corrosion resistance, long service life and the like on the surface of the marine facility, and the marine facility is well protected.

Description

Technical Field

[0001] The present application specifically relates to an antifouling coating composition, a preparation method thereof and applications. Background Art

[0002] Ships, oil platforms, buoys, and other facilities submerged in seawater for extended periods often harbor marine microorganisms, animals, and plants, which often attach, grow, and reproduce on their surfaces, causing damage. Biofouling, particularly on ships and other facilities, can increase their weight and frictional resistance during navigation, leading to reduced speed and increased energy consumption.

[0003] The current method for preventing marine organisms from attaching and growing on the surface of marine facilities is mainly to add antifouling coatings to the surface of marine facilities. Traditional antifouling coatings mainly prevent biofouling by adding biotoxic substances such as inorganic or organic fungicides to repel or kill marine organisms. However, these biotoxic substances are easily released into seawater, which will not only cause the antifouling coating to fail quickly, but also cause pollution to the marine environment. In recent years, researchers have proposed a type of silicone-based antifouling coating, which can effectively prevent the attachment of marine organisms due to its low surface energy characteristics. Although this type of silicone antifouling coating has advantages such as environmental friendliness, its static antifouling ability is poor. Summary of the Invention

[0004] The main purpose of this application is to provide an antifouling coating composition, a preparation method and application thereof, thereby overcoming the defects of the prior art.

[0005] To achieve the above-mentioned invention objectives, the technical solutions adopted in this application include: The first aspect of the present application provides an antifouling coating composition, comprising a hydroxyl-terminated polysiloxane of formula I, a compound of formula II and / or formula III, a crosslinking agent of formula IV, and a catalyst in a mass ratio of a:b:c:d, 60≤a≤85, 0<b≤20, 0<c≤10, 0.01≤d≤5; ; ; ;

[0006] Wherein, E comprises an amino group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group or a thiol group, M comprises Cu, Zn or Ag, A is selected from an unsubstituted or substituted C1-C6 alkyl group, B comprises a hydrolyzable group, D comprises an amino group, an epoxy group, a glycidyl ether group, a hydroxyl group or a thiol group, p, q, m, n, x, y are all integers, and 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6.

[0007] The second aspect of the present application provides a method for preparing the antifouling coating composition, which comprises: In a protective atmosphere, tetramethyltetravinylsilane and octamethylcyclotetrasiloxane are mixed and subjected to an addition reaction to obtain a hydroxyl-terminated polysiloxane represented by formula I; At least the hydroxyl-terminated polysiloxane is uniformly mixed with the compound represented by formula II and / or formula III, the crosslinking agent represented by formula IV and a catalyst to prepare the antifouling coating composition.

[0008] The third aspect of the present application provides an antifouling coating, which is formed from the antifouling coating composition.

[0009] The fourth aspect of the present application provides a protective structure, comprising a protective coating covering the surface of a substrate, wherein the protective coating comprises the antifouling coating.

[0010] A fifth aspect of the present application provides an object, at least a portion of the surface of which is covered with the antifouling coating.

[0011] The sixth aspect of the present application provides use of the antifouling coating composition or the antifouling coating in antifouling the surface of an object, especially in antifouling the surface of a marine facility.

[0012] The seventh aspect of the present application provides a method for antifouling the surface of an object, comprising: applying the antifouling coating composition on at least a portion of the surface of the object to form an antifouling coating.

[0013] Compared with the prior art, the antifouling coating composition provided in the present application is prepared by combining a hydroxyl-terminated polysiloxane with a compound represented by Formula II and / or Formula III and a silane-based crosslinker containing a hydrolyzable group. When forming the antifouling coating, the hydroxyl groups provided by the polysiloxane can be used to react with the carboxyl groups, amino groups or oxime groups provided by the compound represented by Formula II and / or Formula III and the amino groups, epoxy groups, glycidyl ether groups, hydroxyl groups or thiol groups provided by the crosslinker represented by Formula IV, so that the antifouling coating has both excellent mechanical properties and intrinsic dynamic antifouling ability. At the same time, the electrically neutral hydrophilic structure and / or antibacterial function E group provided by the hydroxyl-terminated polysiloxane represented by Formula I is utilized to exhibit good, long-lasting and stable anti-plankton adhesion performance and anti-surface colonization and fouling organisms, thereby achieving intrinsic static antifouling. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in this application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0015] Figure 1 These are photos of actual sea specimens of the antifouling coating samples in Examples 1, 4, 6, and 8 of the present invention and Comparative Examples 1-5; Figure 2 This is a graph showing the anti-biofilm adhesion performance results of the antifouling coating samples in Examples 2, 8, 11, 13-16 and Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0016] In order to fully understand the purpose, technical content and features of this application, the invention scheme and implementation process are described in detail below in combination with specific implementation methods and drawings.

[0017] Some embodiments of the present application provide an antifouling coating composition comprising a hydroxyl-terminated polysiloxane of formula I, a compound of formula II and / or formula III, a crosslinking agent of formula IV, and a catalyst in a mass ratio of a:b:c:d, 60≤a≤85, 0<b≤20, 0<c≤10, 0.01≤d≤5; ; ; ; ; Wherein, E comprises an amino group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group or a thiol group, M comprises Cu, Zn or Ag, A is selected from an unsubstituted or substituted C1-C6 alkyl group, B comprises a hydrolyzable group, D comprises an amino group, an epoxy group, a glycidyl ether group, a hydroxyl group or a thiol group, p, q, m, n, x, y are all integers, and 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6.

[0018] In one embodiment, the hydroxyl-terminated polysiloxane includes an addition reaction product of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane and / or a click reaction product of the addition reaction product and a compound having a thiol group, wherein in the addition reaction system, the tetramethyltetravinylsilane accounts for 0-30% of the molar weight of octamethylcyclotetrasiloxane.

[0019] In one embodiment, the weight average molecular weight of the hydroxyl-terminated polysiloxane is 30,000 to 100,000, preferably 30,000 to 50,000.

[0020] Furthermore, the raw materials for the hydroxyl-terminated polysiloxane click reaction (i.e., the aforementioned compound having a thiol group) include 2-mercaptoethylamine, 2-phenylethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptofuran, 3-mercapto-1-propanol, etc., preferably 2-mercaptoethylamine, 2-methyl-3-mercaptofuran, etc., but not limited to these.

[0021] In one embodiment, the hydrolyzable group of the crosslinking agent represented by Formula IV includes an alkoxy group. In some cases, it may also be an oxime group. For example, the crosslinking agent represented by Formula IV may include, but is not limited to, one or more combinations of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and ethyl orthosilicate condensates.

[0022] In a more preferred embodiment, 65≤a≤75, 5<b≤15, 2<c≤5, 0.05≤d≤4. In the present application, excessive use of the hydroxyl-terminated polysiloxane will increase the brittleness of the paint film and cause cracks, while too little will affect the intrinsic antifouling properties of the coating. Excessive use of the compound represented by Formula II and / or Formula III will easily cause phase separation in the coating, while too little will also be detrimental to the intrinsic antifouling properties of the coating. Excessive use of the crosslinking agent represented by Formula IV will increase the rigidity of the paint film and make it prone to cracking, while too little will reduce the strength of the paint film and make it prone to deformation. Excessive use of the catalyst will cause the coating to crosslink too quickly, generating bubbles in the paint film, while too little will result in incomplete curing.

[0023] In the present application, the catalyst can be selected from transition metal compounds, metal salts and organometallic compounds of various metals, such as organometallic compounds of tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium, titanium, boron and zirconium, preferably organotin compounds, organobismuth compounds, organotitanium compounds, organozirconium compounds, organohafnium compounds, titanates or zirconates, etc. Typical catalysts include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin dineodecanoate, dibutyltin dimethoxy, dibutyltin dibenzoate, dibutyltin acetylacetonate, dibutyltin acetylacetonate, alkyl dibutyltin acetylacetonate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin 2-ethylhexanoate, dioctyltin 2-ethylhexanoate, dioctyltin 2-ethylhexanoate, dibutyltin 2-ethylhexanoate, dibutyltin 2-methyl ... Tin, dioctyltin dineodecanoate, dioctyltin dimethoxy, dioctyltin dibenzoate, dioctyltin acetylacetonate, dioctyltin acetylacetonate, dioctyltin alkyl acetylacetonate, dimethyltin dibutyrate, dimethyltin bisneodecanoate, dimethyltin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin octanoate, tin stearate, iron stearate, iron 2-ethylhexanoate, lead octanoate, lead 2-ethyloctanoate, 2-ethylhexanoate Cobalt phosphate, cobalt naphthenate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc stearate, metal trifluoromethanesulfonate, triethyltin tartrate, stannous octoate, methylphenyltin trioctanoate, isobutyltin triceroate, bismuth 2-ethylhexanoate, bismuth octoate, bismuth neodecanoate, titanium naphthenate, zirconium naphthenate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, triethanolamine titanate, tetra(isopropylene oxide) Titanate, titanium tetrabutoxide, titanium tetrapropoxide, titanium tetraisopropoxide, tetrabutyl zirconate, tetra(2-ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropyleneoxy)-zirconate, zirconium tetrabutoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, and chelated titanate, such as diisopropyl bis(acetylacetonate) titanate, diisopropyl bis(ethylacetylacetonate) titanate, and diisopropyl bis(ethylacetoacetate) titanium diisopropoxide. In the present application, the catalyst is preferably dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, or dioctyltin dilaurate, but is not limited thereto.

[0024] In one embodiment, the antifouling coating composition may further comprise a combination of one or more of a solvent, a filler, and an auxiliary agent. The auxiliary agent may include a combination of one or more of a reinforcing agent, a thixotropic agent, a thickener, an anti-settling agent, a dehydrating agent, a dispersant, a wetting agent, a surfactant, an adhesive, a plasticizer, and a pigment, but is not limited thereto.

[0025] Wherein, the addition of solvent can be determined according to actual construction demand, for example, can be controlled to 0~35% of the antifouling coating composition gross mass, preferably 1~30%.In some cases, solvent can be not added at all, and this is conducive to cost saving and environmental protection.The solvent applicable to the application can be selected from one or more of aromatic hydrocarbons, ketones, esters, ethers, alcohols, aliphatic hydrocarbon organic solvents, for example, can be selected from dimethylbenzene, toluene, mesitylene, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, tetrahydrofuran, n-butyl alcohol, isobutyl alcohol, benzyl alcohol, butoxyethanol or 1-methoxy-2-propanol etc.

[0026] The amount of filler added depends on the actual application requirements and can be controlled to 0-20% of the total mass of the antifouling coating composition, preferably 0.1-10%, and more preferably 0.1-5%. Suitable fillers for this application can be selected from inorganic fillers such as zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, silica, or silicates, or solid silicone resin powders. Preferably, the filler used in this application can be silica aerogel powder, which helps improve the erosion resistance of the antifouling coating.

[0027] The amount of any one of the thixotropic agent, thickener, anti-settling agent, and dehydrating agent added can be 0-10% of the total mass of the antifouling coating composition, preferably 0.1-5%, and more preferably 0.1-2%. The thixotropic agent, thickener, and anti-settling agent can be selected from one or more combinations of fumed silica, organically modified clay, amide wax, polyamide wax, amide derivative, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, etc. The dehydrating agent can be selected from calcium sulfate hemihydrate, anhydrous calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, and zeolites. The dehydrating agent may be trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, triethyl orthopropionate, trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tri-tert-butyl borate, trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, ethyl polysilicate, etc.

[0028] In addition, the antifouling coating composition may further include an appropriate amount of inorganic or organic pigments, such as black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, aluminum flakes, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminate, carbazole diazines, isoindoline orange, bis-acetoacetyl-tolidine, benzimidazolone, quinophthalone yellow, isoindoline yellow, tetrachloroisoindoline, quinoline yellow, etc. Furthermore, the amount of the pigment added may be 0-20% of the total mass of the antifouling coating composition, preferably 0.5-15%.

[0029] In this application, the antifouling coating formed from the antifouling coating composition exhibits excellent dynamic and static antifouling properties through the synergistic combination of the main components, namely, a hydroxyl-terminated polysiloxane represented by Formula I, compounds represented by Formula II and / or Formula III, and a crosslinker represented by Formula IV. The hydroxyl-terminated polysiloxane represented by Formula I has a flexible Si-O-Si backbone, which imparts excellent dynamic deformation capabilities to the coating. Under seawater erosion or mechanical stress, the free rotation and low surface energy of the Si-O segments effectively reduce the adhesion strength of fouling organisms, achieving dynamic antifouling. Furthermore, the E groups introduced into its side chains (such as amines, epoxy groups, furan rings, hydroxyl groups, or thiol groups) can effectively enhance the static antifouling properties of the coating. For example, electrically neutral hydrophilic groups such as hydroxyl groups can bind to water molecules through hydrogen bonding, forming a hydration layer that inhibits the initial adhesion of proteins and microorganisms. Furthermore, antimicrobial functional groups such as amines and furan rings can disrupt microbial cell membranes through charge interactions or redox reactions, inhibiting biofilm formation. The compounds represented by Formula II and Formula III both contain a furan ring and an -N-OH group. The hydrophobic -π non-covalent interaction of the furan ring can interfere with the structure of adhesion proteins secreted by fouling organisms, reducing their adhesion stability. The -N-OH group can form a reversible hydrogen bond network with the hydroxyl groups in the hydroxyl-terminated polysiloxane represented by Formula I and / or the D group (e.g., amine group) in the crosslinker represented by Formula IV, imparting self-healing capabilities to the coating and maintaining the durability of its antifouling properties. In particular, for the compound represented by Formula III, the metal ion M contained therein can be slowly released through hydrolysis, exerting a long-lasting inhibitory effect on bacteria, algae, and the like, further enhancing the static antifouling properties of the coating. Furthermore, the metal ion can form coordination bonds with the -N-OH group, increasing the coating's crosslinking density and improving its dynamic antifouling properties, such as scour resistance. The group B (such as an alkoxy group) contained in the cross-linking agent represented by Formula IV can be hydrolyzed to form a silanol group (Si-OH) during the curing process of the coating, and condensed with the hydroxyl group in the compound represented by Formula I or the active group in the compound represented by Formula II / III to form a stable Si-O-Si three-dimensional network, thereby ensuring the mechanical strength of the coating; the group D (such as an amino group or an epoxy group) contained therein can react with the E group of Formula I, for example, the amino group and the epoxy group undergo a ring-opening reaction to form a covalent cross-linking point, thereby enhancing the cohesion of the coating, and / or dynamically bond with the -N-OH of Formula II / III to form a hydrogen bond or ionic bond dynamic network, thereby enabling the coating to have elastic deformation ability at the microscale and adapt to the dynamic stress of the marine environment.

[0030] In summary, in the antifouling coating composition of the present application, at least the following technical effects can be achieved through the mutual synergy of the above-mentioned main components: first, dynamic antifouling of the coating: the flexibility of Si-O chain, reversible hydrogen bond network and low surface energy characteristics, together achieve excellent "easy shedding" effect of fouling. Second, static antifouling of the coating: the synergistic effect of hydrophilic hydration layer, antibacterial group and metal ions effectively inhibits bioadhesion and colonization. Third, long-acting of the coating: the controllable balance of three-dimensional covalent network and dynamic bond ensures the structural integrity and functional activity of the coating in long-term immersion.

[0031] Some embodiments of the present application provide a method for preparing the antifouling coating composition, comprising: mixing tetramethyltetavinylsilane and octamethylcyclotetrasiloxane in a protective atmosphere and carrying out addition reaction to obtain the hydroxyl-terminated polysiloxane shown in formula I; uniformly mixing at least the hydroxyl-terminated polysiloxane shown in formula I, the compound shown in formula II and / or formula III, the crosslinking agent shown in formula IV and the catalyst, thereby preparing the antifouling coating composition.

[0032] In a preferred embodiment, the method for preparing the antifouling coating composition specifically comprises: mixing tetramethyltetavinylsilane and octamethylcyclotetrasiloxane in a protective atmosphere and at a temperature of 80-100°C and carrying out addition reaction for 3-8h to obtain the hydroxyl-terminated polysiloxane.

[0033] Some other embodiments of the present application provide a method for preparing the antifouling coating composition, comprising: mixing tetramethyltetavinylsilane and octamethylcyclotetrasiloxane in a protective atmosphere and carrying out addition reaction to obtain the hydroxyl-terminated polysiloxane shown in formula I; obtaining the hydroxyl-terminated polysiloxane shown in formula I by carrying out click reaction between the obtained hydroxyl-terminated polysiloxane and the compound with thiol group to obtain the hydroxyl-terminated polysiloxane shown in formula I; uniformly mixing at least the hydroxyl-terminated polysiloxane shown in formula I, the compound shown in formula II and / or formula III, the crosslinking agent shown in formula IV and the catalyst, thereby preparing the antifouling coating composition.

[0034] In a preferred embodiment, the compound with thiol group can include one of 2-mercaptoethylamine, 2-phenyl ethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptifuran, 3-mercapto-1-propanol, etc., and preferably 2-mercaptoethylamine, 2-methyl-3-mercaptifuran, etc., but not limited thereto.

[0035] In a preferred embodiment, the preparation method of the antifouling coating composition specifically comprises: mixing tetramethyltetravinylsilane and octamethylcyclotetrasiloxane in a protective atmosphere at a temperature of 80° C. to 100° C. and performing an addition reaction for 3 to 8 hours to obtain an addition reaction product; Under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C, the addition reaction product is mixed with a compound having a thiol group in a molar ratio of 1:0.9 to 1:1.1 and a click reaction is carried out for 3 to 8 hours to obtain a hydroxyl-terminated polysiloxane represented by formula I.

[0036] In a preferred embodiment, the compound having a thiol group may include one of 2-mercaptoethylamine, 2-phenylethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptofuran, 3-mercapto-1-propanol, etc., preferably 2-mercaptoethylamine, 2-methyl-3-mercaptofuran, etc., but not limited to this.

[0037] In some cases, in the addition reaction system, the tetramethyltetravinylsilane accounts for 0 to 30% of the molar amount of octamethylcyclotetrasiloxane.

[0038] In some cases, one or more of the aforementioned solvents, fillers and additives may be added to the antifouling coating composition.

[0039] The operation of uniformly mixing the hydroxyl-terminated polysiloxane of formula I with the compound of formula II and / or formula III, the crosslinking agent of formula IV, and the catalyst can be performed at room temperature.

[0040] Some embodiments of the present application provide an antifouling coating formed from the antifouling coating composition.

[0041] The antifouling coating composition or antifouling coating of the present application can be applied to the field of marine antifouling, especially to the surface antifouling of marine facilities.

[0042] Some embodiments of the present application provide a protective structure, comprising a protective coating covering a surface of a substrate, wherein the protective coating comprises the anti-fouling coating.

[0043] Some embodiments of the present application provide an object, at least a portion of the surface of the object being covered with the anti-fouling coating.

[0044] Some embodiments of the present application provide a method for antifouling the surface of an object, comprising: applying the antifouling coating composition on at least a portion of the surface of the object to form an antifouling coating layer.

[0045] The antifouling coating composition can be applied to the surface of an object by various methods such as spin coating, scraping coating, and spraying, so that the antifouling coating layer evenly covers the surface of the object.

[0046] The objects may be marine facilities such as ships, oil platforms, buoys, etc., or marine buildings such as lighthouses, dikes, and cross-sea bridges.

[0047] The hydroxyl-terminated polysiloxane provided herein enhances the intrinsic static antifouling ability of silicone resins by introducing E groups with electrically neutral hydrophilic structures and antibacterial properties into the silicone polymer chain segments. The antifouling coating composition described herein can be used to form an antifouling coating on the surface of marine facilities, exhibiting strong intrinsic dynamic and static antifouling capabilities, excellent mechanical properties, erosion resistance, corrosion resistance, and a long service life, thereby providing excellent protection for marine facilities.

[0048] The technical solution of the present application will be further described below in conjunction with several embodiments. However, the implementation of the present application is not limited to these specific details and can also be implemented in other ways different from those described herein. Therefore, the specific embodiments presented in the present application are only for illustration and not for limitation.

[0049] The antifouling agents of formula II and formula III used in the following examples are homemade. For detailed preparation methods, please refer to ZL202011142150.8.

[0050] The preparation method of the hydroxyl-terminated polysiloxane of formula I used in the following examples is as follows.

[0051] The preparation method of the hydroxyl-terminated polysiloxane (Q1) represented by formula I comprises: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 0% of the molar amount of octamethylcyclotetrasiloxane in the reaction, the reaction time is 3 to 4 hours, and the weight-average molecular weight is about 30,000.

[0052] The preparation method of the hydroxyl-terminated polysiloxane (Q2) represented by formula I comprises: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 0% of the molar amount of octamethylcyclotetrasiloxane in the reaction, the reaction time is 4 to 6 hours, and the weight-average molecular weight is about 50,000.

[0053] The preparation method of the hydroxyl-terminated polysiloxane (Q3) represented by formula I comprises: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 0% of the molar amount of octamethylcyclotetrasiloxane in the reaction, the reaction time is 6 to 8 hours, and the weight-average molecular weight is about 80,000.

[0054] The preparation method of the hydroxyl-terminated polysiloxane (Q4) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 10% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 2-mercaptoethylamine in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q4) represented by formula I with a weight-average molecular weight of approximately 50,000.

[0055] The preparation method of the hydroxyl-terminated polysiloxane (Q5) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 20% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 2-mercaptoethylamine in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q5) represented by formula I with a weight-average molecular weight of approximately 50,000.

[0056] The preparation method of the hydroxyl-terminated polysiloxane (Q6) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 10% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 2-phenylethanethiol in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q6) represented by formula I with a weight-average molecular weight of approximately 55,000.

[0057] The preparation method of a hydroxyl-terminated polysiloxane (Q7) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 30% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 1-propanethiol in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare a hydroxyl-terminated polysiloxane (Q7) represented by formula I with a weight-average molecular weight of approximately 80,000.

[0058] The preparation method of the hydroxyl-terminated polysiloxane (Q8) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 15% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 3-mercaptopropionic acid in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q8) represented by formula I with a weight-average molecular weight of approximately 70,000.

[0059] The preparation method of a hydroxyl-terminated polysiloxane (Q9) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 10% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above-mentioned addition reaction product is mixed with 3-mercapto-1-propanol in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare a hydroxyl-terminated polysiloxane (Q9) represented by formula I with a weight-average molecular weight of approximately 50,000.

[0060] The preparation method of a hydroxyl-terminated polysiloxane (Q10) represented by formula I comprises: under nitrogen protection and a temperature of 80°C to 100°C, preparing the hydroxyl-terminated polysiloxane by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 10% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; taking the above addition reaction product and 2-methyl-3-mercaptofuran at a molar ratio of 1:1.1, mixing and dissolving the mixture in a tetrahydrofuran solvent, and carrying out a click reaction under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q10) represented by formula I with a weight-average molecular weight of approximately 80,000.

[0061] The preparation method of a hydroxyl-terminated polysiloxane (Q11) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 15% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above addition reaction product is mixed with 2-methyl-3-mercaptofuran in a molar ratio of 1:1 and dissolved in a tetrahydrofuran solvent, and a click reaction is carried out under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare a hydroxyl-terminated polysiloxane (Q11) represented by formula I with a weight-average molecular weight of approximately 50,000.

[0062] The preparation method of the hydroxyl-terminated polysiloxane (Q12) represented by formula I includes: under nitrogen protection and a temperature of 80°C to 100°C, the hydroxyl-terminated polysiloxane is prepared by an addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the tetramethyltetravinylsilane accounts for 30% of the molar amount of the octamethylcyclotetrasiloxane in the reaction, and the reaction time is 3 to 8 hours; the above addition reaction product is mixed with 2-methyl-3-mercaptofuran in a molar ratio of 1:0.9, dissolved in a tetrahydrofuran solvent, and subjected to a click reaction under ultraviolet light irradiation conditions and a temperature of 25°C to 35°C for 3 to 8 hours to prepare the hydroxyl-terminated polysiloxane (Q12) represented by formula I with a weight-average molecular weight of approximately 50,000.

[0063] The preparation steps of the antifouling coating compositions in the following Examples 1-21 include: uniformly mixing a hydroxyl-terminated polysiloxane with a compound represented by Formula II and / or Formula III, a crosslinking agent represented by Formula IV, and a catalyst to prepare the antifouling coating composition. The formulations of the various Examples are shown in Table 1.

[0064] Table 1 Formulas of antifouling coating compositions in Examples 1-21 and Comparative Examples 1-5 ;

[0065] The antifouling properties of the antifouling coatings formed from the coating compositions provided in Examples 1-21 and Comparative Examples 1-5 were tested, and the results are shown in Tables 2 and 3, respectively. Figure 1 As shown, the anti-biofilm adhesion performance of the antifouling coating samples in Example 2, Example 8, Example 11, Examples 13-16 and Comparative Example 1 is as follows Figure 2 As shown, in Examples 11 and 12, the addition of the rigid group phenyl restricts the free movement of the flexible chain segments, resulting in slightly poor antifouling performance; in Example 13, the volume of the propyl group is larger than that of the methyl group, which increases the chain spacing and reduces the cross-linking density. The segment movement results in a slight decrease in dynamic antifouling performance due to steric hindrance.

[0066] Table 2 Performance test results of the antifouling coating in Examples 1-21

[0067] Table 3 Performance test results of the antifouling coating in Comparative Examples 1-5 ; Remark: 1. The coupons for the actual antifouling performance of the coatings in Tables 2 and 3 are for a certain sea area. For the coupon performance rating standards for samples with antifouling coatings, please refer to Table 4.

[0068] 2. The antifouling performance of the coatings listed in Tables 2 and 3 was tested using the following methods: Based on GB / T 5370-2007, Shallow Sea Immersion Test Method for Antifouling Paint Panels, actual sea trials were conducted in a specific sea area between January 2023 and October 2024, without any surface treatment.

[0069] 3. The data shown in Tables 2 and 3 are typical values ​​after testing multiple samples.

[0070] Table 4 Coupon performance rating standards

[0071] Obviously, the hydroxyl-terminated polysiloxane provided in the present application can realize the intrinsic antifouling of silicone resin by introducing groups with electrically neutral hydrophilic structure and antibacterial function into the silicone polymer chain segment, and has the advantages of strong dynamic and static antifouling capabilities, which can provide good protection for marine facilities.

[0072] The above embodiments are intended only to illustrate the technical concepts and effects of this application, with the goal of enabling those familiar with this technical field to understand the content of this application and implement it accordingly. However, these embodiments do not constitute a limitation on the scope of protection of this application. Any equivalent transformations or modifications made based on the spirit and technical ideas of this application should be covered by the claims of this application.

Claims

1. An antifouling coating composition, characterized in that: The antifouling coating composition comprises a hydroxyl-terminated polysiloxane of formula I, a compound of formula II and / or formula III, a crosslinking agent of formula IV, and a catalyst in a mass ratio of a:b:c:d, 60≤a≤85, 0<b≤20, 0<c≤10, 0.01≤d≤5; ； ； ； ; Wherein, E comprises an amino group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group or a thiol group, M comprises Cu, Zn or Ag, A comprises an unsubstituted or substituted C1-C6 alkyl group, B comprises a hydrolyzable group, D comprises an amino group, an epoxy group, a glycidyl ether group, a hydroxyl group or a thiol group, p, q, m, n, x, y are all integers, and 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6.

2. The antifouling coating composition according to claim 1, wherein: The hydroxyl-terminated polysiloxane includes an addition reaction product of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane and / or a click reaction product of the addition reaction product and a compound having a thiol group; wherein, in the addition reaction system, the tetramethyltetravinylsilane accounts for 0 to 30% of the molar weight of octamethylcyclotetrasiloxane.

3. The antifouling coating composition according to claim 2, characterized in that: The compound having a thiol group includes one of 2-mercaptoethylamine, 2-phenylethylmercaptan, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptofuran, and 3-mercapto-1-propanol.

4. The antifouling coating composition according to claim 1, wherein: The weight average molecular weight of the hydroxyl-terminated polysiloxane is 30,000-100,000.

5. The antifouling coating composition according to claim 1, characterized in that: The hydrolyzable groups of the cross-linking agent represented by Formula IV include alkoxy groups.

6. The antifouling coating composition according to claim 1, characterized in that: The crosslinking agent represented by formula IV includes one or more combinations of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and ethyl orthosilicate condensate.

7. The antifouling coating composition according to claim 1, wherein: 65≤a≤75,5<b≤15,2<c≤5,0.05≤d≤4.

8. The antifouling coating composition according to claim 1, wherein: The antifouling coating composition further comprises a combination of one or more of a solvent, a filler and an adjuvant.

9. The antifouling coating composition according to claim 8, characterized in that: The auxiliary agent includes one or more combinations of reinforcing agents, thixotropic agents, thickeners, anti-settling agents, dehydrating agents, dispersants, wetting agents, surfactants, adhesives, plasticizers and pigments.

10. A method for preparing the antifouling coating composition according to any one of claims 1 to 9, characterized in that: include: In a protective atmosphere, tetramethyltetravinylsilane and octamethylcyclotetrasiloxane are mixed and subjected to an addition reaction to obtain a hydroxyl-terminated polysiloxane represented by formula I; At least the hydroxyl-terminated polysiloxane is uniformly mixed with the compound represented by formula II and / or formula III, the crosslinking agent represented by formula IV and a catalyst to prepare the antifouling coating composition.

11. The method according to claim 10, characterized in that include: In a protective atmosphere at a temperature of 80° C. to 100° C., tetramethyltetravinylsilane and octamethylcyclotetrasiloxane are mixed and subjected to an addition reaction for 3 to 8 hours to obtain the hydroxyl-terminated polysiloxane; wherein, in the addition reaction system, the tetramethyltetravinylsilane accounts for 0 to 30% of the molar weight of the octamethylcyclotetrasiloxane.

12. The method according to claim 10, characterized in that Specifically include: In a protective atmosphere at a temperature of 80° C. to 100° C., tetramethyltetravinylsilane and octamethylcyclotetrasiloxane are mixed and subjected to an addition reaction for 3 to 8 hours to obtain an addition reaction product; Under ultraviolet light irradiation conditions and a temperature of 25° C. to 35° C., the addition reaction product and a compound having a thiol group are mixed in a molar ratio of 1:0.9 to 1:1.1 and subjected to a click reaction for 3 to 8 hours to obtain the hydroxyl-terminated polysiloxane.

13. An antifouling coating, characterized in that: The coating layer is formed from the antifouling coating composition according to any one of claims 1 to 9.

14. A protective structure comprising a protective coating covering a surface of a substrate, characterized in that: The protective coating comprises the antifouling coating of claim 13.

15. An object, characterized in that: At least a portion of the surface of the object is covered with the antifouling coating according to claim 13.

16. A method for antifouling the surface of an object, characterized in that: include: Apply the antifouling coating composition according to any one of claims 1 to 9 to at least a portion of the surface of an object to form an antifouling coating.

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