Antifouling coating composition, method for its production and use

Abstract

The application provides an antifouling coating composition, a preparation method and application thereof. The antifouling coating composition comprises a hydroxyl-terminated polysiloxane shown in formula I, a compound shown in formula II and / or formula III, a crosslinking agent shown in formula IV and a catalyst; wherein E comprises an amine group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group or a mercapto group, M comprises Cu, Zn or Ag, A comprises an unsubstituted or substituted C1-C6 alkyl group, B comprises a hydrolysable group, D comprises an amine group, an epoxy group, a glycidyl ether group, a hydroxyl group or a mercapto group, 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6. By using the antifouling coating composition, an antifouling coating layer with strong intrinsic dynamic and static antifouling ability, excellent mechanical properties, erosion resistance, corrosion resistance, long service life and the like can be formed on the surface of marine facilities, and good protection is formed on the marine facilities.

Description

TECHNICAL FIELD

[0001] The present application relates to an antifouling coating composition, a preparation method and application thereof. BACKGROUND

[0002] Facilities such as ships, oil platforms and buoys are often immersed in seawater for a long time, and marine microorganisms, animals and plants are often attached, grown and reproduced on the surface of the facilities, thereby causing damage to the facilities. Especially for ships and other facilities, the biofouling formed by marine organisms on the surface of the facilities is also easy to cause the increase of the weight of the facilities and the increase of the frictional resistance of the facilities when sailing, thereby causing the decrease of the sailing speed of the facilities and the increase of the energy consumption of the facilities.

[0003] At present, the method for preventing marine organisms from attaching and growing on the surface of marine facilities mainly adds an antifouling coating on the surface of the marine facilities. The traditional antifouling coating mainly drives away or kills marine organisms by adding biological toxic substances such as inorganic or organic bactericides, thereby preventing biofouling. However, these biological toxic substances are easy to be released into seawater, which not only causes the rapid failure of the antifouling coating, but also causes the pollution of the marine environment. In recent years, researchers have proposed a kind of antifouling coating based on organosilicon, which can better prevent the attachment of marine organisms due to its low surface energy characteristics. Although this kind of organosilicon antifouling coating has the advantages of environmental friendliness, etc., its static antifouling ability is poor. SUMMARY

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

[0005] In order to achieve the above-mentioned purpose of the application, the technical scheme adopted by the present application comprises:

[0006] The first aspect of the present application provides an antifouling coating composition, which comprises a hydroxyl-terminated polysiloxane represented by formula I, a compound represented by formula II and / or formula III, a crosslinking agent represented by formula IV and a catalyst, and the mass ratio of a:b:c:d is 60≤a≤85, 0

[0007] ;

[0008] ;

[0009] ;

[0010]

[0011] wherein E comprises an amine group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group, or a mercapto group, M comprises Cu, Zn, or Ag, A is selected from unsubstituted or substituted C1-C6 alkyl, B comprises a hydrolysable group, D comprises an amine group, an epoxy group, a glycidyl ether group, a hydroxyl group, or a mercapto group, p, q, m, n, x, y are integers, and 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6.

[0012] A second aspect of the present application provides a method for preparing the antifouling coating composition, comprising:

[0013] In a protective atmosphere, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and subjected to an addition reaction to obtain a hydroxyl-terminated polysiloxane represented by Formula I;

[0014] At least the hydroxyl-terminated polysiloxane is uniformly mixed with a compound represented by Formula II and / or Formula III, a crosslinking agent represented by Formula IV, and a catalyst to obtain the antifouling coating composition.

[0015] A third aspect of the present application provides an antifouling coating layer formed by the antifouling coating composition.

[0016] A fourth aspect of the present application provides a protective structure comprising a protective coating layer covering a surface of a substrate, wherein the protective coating layer comprises the antifouling coating layer.

[0017] A fifth aspect of the present application provides an object, at least a part of a surface of which is covered with the antifouling coating layer.

[0018] A sixth aspect of the present application provides a use of the antifouling coating composition or the antifouling coating layer for preventing fouling on a surface of an object, in particular a surface of a marine facility.

[0019] A seventh aspect of the present application provides a method for preventing fouling on a surface of an object, comprising: applying the antifouling coating composition on at least a part of a surface of the object to form an antifouling coating layer.

[0020] Compared with the prior art, the antifouling coating composition provided by the application can utilize the hydroxyl groups provided by the hydroxyl-terminated polysiloxane to react with the carboxyl groups, amine groups or oxime groups provided by the compound represented by formula II and / or formula III and the amine groups, epoxy groups, glycidyl ether groups, hydroxyl groups or mercapto groups provided by the crosslinking agent represented by formula IV, so that the antifouling coating has excellent mechanical properties and intrinsic dynamic antifouling ability, and the hydrophilic structure and / or antibacterial functional E groups provided by the hydroxyl-terminated polysiloxane represented by formula I are utilized, so that the antifouling coating has good, long-acting and stable anti-biofilm adhesion performance and toxic killing of surface-attached fouling organisms, and realizes intrinsic static antifouling. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments described in the application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0022] Figure 1 is a real sea hanging piece photo of the antifouling coating sample in example 1, example 4, example 6, example 8 and comparative example 1-5 of the application;

[0023] Figure 2 is a biofilm adhesion resistance performance result graph of the antifouling coating sample in example 2, example 8, example 11, example 13-16 and comparative example 1 of the application. DETAILED DESCRIPTION

[0024] In order to fully understand the purpose, technical content and characteristics of the application, the application scheme and implementation process will be described in detail below in combination with specific embodiments and drawings.

[0025] Some embodiments of the application provide an antifouling coating composition comprising hydroxyl-terminated polysiloxane represented by formula I, a compound represented by formula II and / or formula III, a crosslinking agent represented by formula IV and a catalyst with a mass ratio of a:b:c:d, 60≤a≤85, 0

[0026] ;

[0027] ;

[0028] ;

[0029] ;

[0030] wherein E comprises an amine group, an epoxy group, a phenyl group, a furan ring, a hydroxyl group, or a mercapto group, M comprises Cu, Zn, or Ag, A is selected from unsubstituted or substituted C1-C6 alkyl, B comprises a hydrolysable group, D comprises an amine group, an epoxy group, a glycidyl ether group, a hydroxyl group, or a mercapto group, p, q, m, n, x, y are each an integer, and 3≤p:q≤∞, 0≤m≤2, 0≤n≤2, 0≤x≤2, 1≤y≤6.

[0031] In one embodiment, the hydroxyl-terminated polysiloxane comprises an addition reaction product of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane and / or a click reaction product of the addition reaction product and a compound having a mercapto group, wherein the tetramethyltetavinylsilane is present in the addition reaction system in an amount of 0 to 30% by mole of octamethylcyclotetrasiloxane.

[0032] In one embodiment, the hydroxyl-terminated polysiloxane has a weight average molecular weight of 30,000 to 100,000, preferably 30,000 to 50,000.

[0033] Further, the starting material (i.e., the aforementioned compound having a mercapto group) for the click reaction of the hydroxyl-terminated polysiloxane comprises one of 2-mercaptoethylamine, 2-phenylethyl mercaptan, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptifuran, 3-mercapto-1-propanol, and the like, and is preferably 2-mercaptoethylamine, 2-methyl-3-mercaptifuran, and the like, but is not limited thereto.

[0034] In one embodiment, the hydrolysable group of the crosslinking agent of Formula IV comprises an alkoxy group. In some cases, it can also be an oxime group, and the like. Exemplary, the crosslinking agent of Formula IV can comprise, but is not limited to, one or more of a combination of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, tetraethyl orthosilicate condensate, and the like.

[0035] In a more preferred embodiment, 65≤a≤75, 5

[0036] 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, organo hafnium compounds, titanates, or zirconates, etc. Typical catalysts include dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin di-neodecanoate, dibutyltin dimethoxide, dibutyltin dibenzoate, dibutyltin acetylacetonate, dibutyltin acetylacetonate, dibutyltin alkylacetylacetonate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin di-neodecanoate, dioctyltin dimethoxide, dioctyltin dibenzoate, dioctyltin acetylacetonate, dioctyltin acetylacetonate, dioctyltin alkylacetylacetonate, dimethyltin dibutyrate, dimethyltin bineodecanoate, dimethyltin bineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin octoate, tin stearate, iron stearate, iron 2-ethylhexanoate, lead octoate, lead 2- ethyloctanoate, cobalt 2-ethylhexanoate, cobalt naphthenate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc stearate, metal triflate, triethyltin tartrate, stannous octoate, methyltriphenyltin triceroate, isobutyltin triceroate, bismuth 2-ethylhexanoate, bismuth octoate, bismuth neodecanoate, titanium naphthenate, zirconium naphthenate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, triethanolamine titanate, tetra(isopropenoxy)- titanate, tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl zirconate, tetra(2-ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropenoxy)-zirconate, tetrabutyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and chelated titanates such as diisopropyl bis(acetylacetonato) titanate, diisopropyl bis(ethylacetylacetonato) titanate, and diisopropyl bis(ethylacetoacetate) titanate, etc. The catalyst in the present application is preferably dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, or dioctyltin dilaurate, etc., but is not limited thereto.

[0037] In one embodiment, the anti-fouling coating composition can further include a combination of one or more of a solvent, a filler, and an additive, which can include a combination of one or more of a reinforcing agent, a thixotropic agent, a thickening agent, an anti-settling agent, a dehydrating agent, a dispersing agent, a wetting agent, a surfactant, a binder, a plasticizer, and a pigment, etc., but is not limited thereto.

[0038] The amount of solvent added can be determined according to the actual construction requirements, for example, it can be controlled to be 0-35% of the total mass of the antifouling coating composition, preferably 1-30%. In some cases, no solvent can be added, which is beneficial to cost saving and environmental protection. The solvent suitable for the present application can be selected from one or more of aromatic hydrocarbons, ketones, esters, ethers, alcohols, aliphatic hydrocarbon organic solvents, for example, it can be selected from xylene, 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-butanol, isobutyl alcohol, benzyl alcohol, butoxy ethanol or 1-methoxy-2-propanol, etc.

[0039] The amount of filler added also depends on the actual application requirements, which can be controlled to be 0-20% of the total mass of the antifouling coating composition, preferably 0.1-10%, more preferably 0.1-5%. The filler suitable for the present application can be selected from inorganic fillers such as zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, silicon dioxide or silicate, etc. It can also be selected from solid silicone resin powder. More preferably, the filler in the present application can be selected from silica aerogel powder, etc., which is beneficial to improve the anti-erosion performance of the antifouling coating.

[0040] The amount of any one of the thixotropic agent, thickening agent, anti-settling agent and dehydrating agent can be 0-10% of the total mass of the antifouling coating composition, preferably 0.1-5%, more preferably 0.1-2%. The thixotropic agent, thickening agent and anti-settling agent, etc. 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 sieve and zeolite. The dehydrating agent can be selected from 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.

[0041] In addition, an appropriate amount of inorganic or organic pigments, such as iron oxide black, iron oxide red, iron oxide yellow, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, aluminum flake, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminate, carbazole dioxazine, isoindoline orange, bis-acetoacetyl- toluidine, benzimidazolone, quinophthalone yellow, isoindoline yellow, tetra-chloroisoindoline, quinoline yellow, and the like, can be added to the antifouling coating composition. Further, the pigments can be added in an amount of 0 to 20% by total mass of the antifouling coating composition, preferably 0.5 to 15%.

[0042] In the present application, the synergistic effect of the main components, i.e. the hydroxyl-terminated polysiloxane represented by Formula I, the compounds represented by Formula II and / or Formula III, and the crosslinking agent represented by Formula IV, endows the antifouling coating formed by the antifouling coating composition with excellent dynamic and static antifouling properties. Among them, the backbone of the hydroxyl-terminated polysiloxane represented by Formula I is a flexible main chain of Si-O-Si, which endows the coating with excellent dynamic deformation ability. Under the action of seawater scouring or mechanical stress, the free rotation of the Si-O segment and the low surface energy characteristics can effectively reduce the adhesion strength of the fouling organisms, achieving dynamic antifouling. Meanwhile, the E groups (such as amine groups, epoxy groups, furan rings, hydroxyl groups or mercapto groups, etc.) introduced by the side chains can also effectively enhance the static antifouling performance of the coating. For example, the hydrophilic groups such as hydroxyl groups can combine with water molecules through hydrogen bonding to form a hydration layer, thereby inhibiting the initial adhesion of proteins and microorganisms. For example, the antibacterial functional groups such as amine groups and furan rings can destroy the cell membranes of microorganisms through charge interaction or redox reaction, thereby inhibiting the formation of biofilms. The compounds represented by Formula II and Formula III both contain furan rings and -N-OH groups. The hydrophobic-π non-covalent interaction of the furan ring can interfere with the structure of the adhesion proteins secreted by the fouling organisms, thereby reducing the 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 groups (such as amine groups) in the crosslinking agent represented by Formula IV, thereby endowing the coating with self-repairing ability and maintaining the durability of the antifouling performance. In particular, for the compound represented by Formula III, on the one hand, the metal ions M contained therein can be slowly released through hydrolysis, thereby producing a long-acting inhibitory effect on bacteria, algae and the like, further enhancing the static antifouling performance of the coating. On the other hand, the metal ions can form coordination bonds with -N-OH, thereby enhancing the crosslinking density of the coating and improving the dynamic antifouling performance such as the scouring resistance of the coating. The groups B (such as alkoxy groups) contained in the crosslinking agent represented by Formula IV can be hydrolyzed to generate silanol groups (Si-OH) during the curing process of the coating, which can condense with the hydroxyl groups in the compound represented by Formula I or the active groups in the compounds represented by Formula II / III, thereby forming a stable Si-O-Si three-dimensional network to ensure the mechanical strength of the coating. The groups D (such as amine groups and epoxy groups) can react with the E groups of Formula I, for example, the ring-opening reaction of amine groups and epoxy groups, thereby forming covalent crosslinking points to enhance the cohesion of the coating, and / or dynamically bonding with the -N-OH groups of Formula II / III to form a hydrogen bond or ionic bond dynamic network, thereby making the coating have elastic deformation ability at the microscale and adapt to the dynamic stress of the marine environment.

[0043] In summary, the antifouling coating composition of the present application can achieve the following technical effects through the mutual cooperation 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.

[0044] Some embodiments of the present application provide a method for preparing the antifouling coating composition, which comprises:

[0045] In a protective atmosphere, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out to obtain the hydroxyl-terminated polysiloxane shown in formula I;

[0046] At least the hydroxyl-terminated polysiloxane shown in formula I is uniformly mixed with the compound shown in formula II and / or formula III, the crosslinking agent shown in formula IV and the catalyst to obtain the antifouling coating composition.

[0047] In a preferred embodiment, the method for preparing the antifouling coating composition specifically comprises: in a protective atmosphere and under the temperature condition of 80-100°C, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out for 3-8h to obtain the hydroxyl-terminated polysiloxane.

[0048] Some other embodiments of the present application provide a method for preparing the antifouling coating composition, which comprises:

[0049] In a protective atmosphere, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out to obtain the hydroxyl-terminated polysiloxane shown in formula I;

[0050] The hydroxyl-terminated polysiloxane obtained is subjected to click reaction with the compound having thiol group to obtain the hydroxyl-terminated polysiloxane shown in formula I, so as to obtain the hydroxyl-terminated polysiloxane shown in formula I;

[0051] At least the hydroxyl-terminated polysiloxane shown in formula I is uniformly mixed with the compound shown in formula II and / or formula III, the crosslinking agent shown in formula IV and the catalyst to obtain the antifouling coating composition.

[0052] In a preferred embodiment, the compound having thiol group can include one of 2-mercaptoethylamine, 2-phenyl ethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptifuran, 3-mercapto-1-propanol and the like, and preferably 2-mercaptoethylamine, 2-methyl-3-mercaptifuran and the like, but is not limited thereto.

[0053] In a preferred embodiment, the method for preparing the antifouling coating composition specifically comprises: mixing and performing addition reaction of tetramethyltetavinylsilane and octamethylcyclotetrasiloxane in a protective atmosphere and at a temperature of 80-100°C for 3-8h to obtain an addition reaction product;

[0054] Mixing and performing click reaction of the addition reaction product and a compound having a thiol group in a molar ratio of 1:0.9-1:1.1 under ultraviolet light irradiation and at a temperature of 25-35°C for 3-8h to obtain a hydroxyl-terminated polysiloxane represented by Formula I.

[0055] In a preferred embodiment, the compound having a thiol group can include one of 2-mercaptoethylamine, 2-phenyl ethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptifuran, 3-mercapto-1-propanol, and the like, and preferably 2-mercaptoethylamine, 2-methyl-3-mercaptifuran, and the like, but is not limited thereto.

[0056] In some cases, in the addition reaction system, the tetramethyltetavinylsilane accounts for 0-30% of the molar amount of octamethylcyclotetrasiloxane.

[0057] In some cases, one or more of the aforementioned solvents, fillers, and adjuvants can also be added to the antifouling coating composition.

[0058] The operation of uniformly mixing the hydroxyl-terminated polysiloxane represented by Formula I with the compound represented by Formula II and / or Formula III, the crosslinking agent represented by Formula IV, and a catalyst, and the like can be performed at room temperature.

[0059] Some embodiments of the present application provide an antifouling coating layer formed of the antifouling coating composition.

[0060] The antifouling coating composition or antifouling coating layer of the present application can be applied to the field of marine antifouling, and in particular, can be applied to the surface antifouling of marine facilities.

[0061] Some embodiments of the present application provide a protective structure including a protective coating layer covering the surface of a base, the protective coating layer including the antifouling coating layer.

[0062] Some embodiments of the present application provide an object having at least a part of the surface thereof covered with the antifouling coating layer.

[0063] Some embodiments of the present application provide a method for surface antifouling of an object, which includes applying the antifouling coating composition to at least a part of the surface of the object to form an antifouling coating layer.

[0064] The method for applying the antifouling coating composition to the surface of the object can be selected from spin coating, blade coating, spray coating, and the like, so that the antifouling coating uniformly covers the surface of the object.

[0065] The object can be a marine facility such as a ship, an oil extraction platform, a buoy, and the like, or a marine structure such as a lighthouse, a protective dike, a cross-sea bridge, and the like.

[0066] The hydroxyl-terminated polysiloxane provided in the application can enhance the intrinsic static antifouling ability of the silicone resin by introducing the E group having the electrically neutral hydrophilic structure and the antibacterial function on the silicone polymer chain segment. The antifouling coating composition provided in the application can form an antifouling coating on the surface of the marine facility, which has the advantages of strong intrinsic dynamic and static antifouling ability, excellent mechanical property, erosion resistance, corrosion resistance, long service life, and the like, and can provide good protection for the marine facility.

[0067] The technical solutions of the application will be further described below in combination with several embodiments. However, the implementation of the application is not limited to these specific details, but can also be implemented in other ways different from those described herein. Therefore, the specific embodiments presented in the application are only examples and are not limiting.

[0068] The antifouling agents of Formula II and Formula III used in the following examples are self-made, and the specific preparation method is described in detail in ZL202011142150.8.

[0069] The preparation method of the hydroxyl-terminated polysiloxane represented by Formula I used in the following examples is as follows.

[0070] The preparation method of the hydroxyl-terminated polysiloxane (Q1) represented by Formula I includes: under the protection of nitrogen and at a temperature of 80-100°C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the amount of tetramethyltetavinylsilane in the reaction is 0% of the molar amount of octamethylcyclotetrasiloxane, the reaction time is 3-4h, and the weight average molecular weight is about 30000.

[0071] The preparation method of the hydroxyl-terminated polysiloxane (Q2) represented by Formula I includes: under the protection of nitrogen and at a temperature of 80-100°C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the amount of tetramethyltetavinylsilane in the reaction is 0% of the molar amount of octamethylcyclotetrasiloxane, the reaction time is 4-6h, and the weight average molecular weight is about 50000.

[0072] The preparation method of the hydroxyl-terminated polysiloxane (Q3) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 0% of the mole amount of octamethylcyclotetrasiloxane, the reaction time is 6-8 h, and the weight average molecular weight is about 80000.

[0073] The preparation method of the hydroxyl-terminated polysiloxane (Q4) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 10% of the mole amount of octamethylcyclotetrasiloxane, the reaction time is 3-8 h; the above addition reaction product is mixed with 2-mercaptoethylamine in a mole ratio of 1:1, dissolved in tetrahydrofuran solvent, and subjected to click reaction under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q4) shown in formula I with a weight average molecular weight of about 50000.

[0074] The preparation method of the hydroxyl-terminated polysiloxane (Q5) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 20% of the mole amount of octamethylcyclotetrasiloxane, the reaction time is 3-8 h; the above addition reaction product is mixed with 2-mercaptoethylamine in a mole ratio of 1:1, dissolved in tetrahydrofuran solvent, and subjected to click reaction under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q5) shown in formula I with a weight average molecular weight of about 50000.

[0075] The preparation method of the hydroxyl-terminated polysiloxane (Q6) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 10% of the mole amount of octamethylcyclotetrasiloxane, the reaction time is 3-8 h; the above addition reaction product is mixed with 2-mercaptoethylamine in a mole ratio of 1:1, dissolved in tetrahydrofuran solvent, and subjected to click reaction under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q6) shown in formula I with a weight average molecular weight of about 55000.

[0076] The preparation method of the hydroxyl-terminated polysiloxane (Q7) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 30% of the mole fraction of octamethylcyclotetrasiloxane, and the reaction time is 3-8 h; the above addition reaction product and 1-propanethiol are mixed in a molar ratio of 1:1 and dissolved in tetrahydrofuran solvent, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q7) shown in formula I with a weight average molecular weight of about 80000.

[0077] The preparation method of the hydroxyl-terminated polysiloxane (Q8) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 15% of the mole fraction of octamethylcyclotetrasiloxane, and the reaction time is 3-8 h; the above addition reaction product and 3-mercaptopropionic acid are mixed in a molar ratio of 1:1 and dissolved in tetrahydrofuran solvent, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q8) shown in formula I with a weight average molecular weight of about 70000.

[0078] The preparation method of the hydroxyl-terminated polysiloxane (Q9) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100 DEG C, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane, wherein the mole fraction of tetramethyltetavinylsilane in the reaction is 10% of the mole fraction of octamethylcyclotetrasiloxane, and the reaction time is 3-8 h; the above addition reaction product and 3-mercapto-1-propanol are mixed in a molar ratio of 1:1 and dissolved in tetrahydrofuran solvent, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35 DEG C for 3-8 h, thereby preparing the hydroxyl-terminated polysiloxane (Q9) shown in formula I with a weight average molecular weight of about 50000.

[0079] The preparation method of the hydroxyl-terminated polysiloxane (Q10) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100℃, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the amount of tetramethyltetravinylsilane in the reaction is 10% of the molar amount of octamethylcyclotetrasiloxane, and the reaction time is 3-8h; the above addition reaction product and 2-methyl-3-mercaptfuran are mixed and dissolved in tetrahydrofuran solvent according to a molar ratio of 1:1.1, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35℃ for 3-8h, to prepare the hydroxyl-terminated polysiloxane (Q10) shown in formula I with a weight average molecular weight of about 80000.

[0080] The preparation method of the hydroxyl-terminated polysiloxane (Q11) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100℃, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the amount of tetramethyltetravinylsilane in the reaction is 15% of the molar amount of octamethylcyclotetrasiloxane, and the reaction time is 3-8h; the above addition reaction product and 2-methyl-3-mercaptfuran are mixed and dissolved in tetrahydrofuran solvent according to a molar ratio of 1:1, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35℃ for 3-8h, to prepare the hydroxyl-terminated polysiloxane (Q11) shown in formula I with a weight average molecular weight of about 50000.

[0081] The preparation method of the hydroxyl-terminated polysiloxane (Q12) shown in formula I comprises: under the protection of nitrogen and at a temperature of 80-100℃, the hydroxyl-terminated polysiloxane is prepared by addition reaction of octamethylcyclotetrasiloxane and tetramethyltetravinylsilane, wherein the amount of tetramethyltetravinylsilane in the reaction is 30% of the molar amount of octamethylcyclotetrasiloxane, and the reaction time is 3-8h; the above addition reaction product and 2-methyl-3-mercaptfuran are mixed and dissolved in tetrahydrofuran solvent according to a molar ratio of 1:0.9, and a click reaction is carried out under the condition of ultraviolet light irradiation and at a temperature of 25-35℃ for 3-8h, to prepare the hydroxyl-terminated polysiloxane (Q12) shown in formula I with a weight average molecular weight of about 50000.

[0082] The preparation steps of the antifouling coating composition in the following examples 1-21 comprise: uniformly mixing the hydroxyl-terminated polysiloxane, the compound shown in formula II and / or formula III, the crosslinking agent shown in formula IV and the catalyst to prepare the antifouling coating composition, and the formulations of each example are shown in table 1.

[0083] Table 1 Formulations of antifouling coating compositions in examples 1-21 and comparative examples 1-5

[0084] ;

[0085]

[0086] The antifouling performance of the antifouling coating formed by each coating composition provided by Examples 1-21 and Comparative Examples 1-5 was tested, and the results are shown in Tables 2-3, respectively. The real sea hanging piece photos of the antifouling coating samples in Examples 1, 4, 6, 8, and Comparative Example 1-5 are shown in Figure 1 The biofilm adhesion resistance performance of the antifouling coating samples in Examples 2, 8, 11, 13-16, and Comparative Example 1 is shown in Figure 2 , wherein Examples 11 and 12 are slightly worse in antifouling performance due to the addition of the rigid phenyl group, which restricts the free movement of the flexible chain segment; the volume of the propyl group in Example 13 is larger than that of the methyl group, which increases the chain spacing and reduces the crosslinking density, and the segment movement is slightly reduced due to steric hindrance.

[0087] Table 2 Performance test results of the antifouling coating in Examples 1-21

[0088]

[0089] Table 3 Performance test results of the antifouling coating in Comparative Examples 1-5

[0090] ;

[0091] Notes:

[0092] 1. The hanging piece for real sea antifouling performance in Tables 2-3 is in a certain sea area, and the hanging piece performance rating standard for the sample with the antifouling coating is shown in Table 4.

[0093] 2. The test method for the antifouling performance of each coating in Tables 2-3 is as follows: according to GB / T 5370-2007 “Antifouling paint sample shallow sea immersion test method”, real sea hanging plate test is carried out in a certain sea area during 2023.01-2024.10, and the surface coating is not treated in any way.

[0094] 3. The data shown in Tables 2-3 are typical values after testing multiple samples.

[0095] Table 4 Hanging piece performance rating standard

[0096]

[0097] Obviously, the hydroxyl-terminated polysiloxane provided by the present application can realize the intrinsic antifouling of silicone resin by introducing groups with electrically neutral hydrophilic structure and antibacterial function on the silicone polymer chain segment, and has the advantages of strong dynamic and static antifouling ability, and can form good protection for marine facilities.

[0098] The above examples are only intended to illustrate the technical concept and the effect of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and implement it accordingly. However, these examples do not constitute a limitation on the scope of protection of the present application. Any equivalent transformation or modification made on the basis of the spirit and technical concept of the present application should be covered by the claims of the present application.

Claims

1. An antifouling coating composition characterised in that: The antifouling coating composition comprises a hydroxyl-terminated polysiloxane represented by Formula I, a compound represented by Formula II and / or Formula III, a crosslinking agent represented by Formula IV, and a catalyst, with a mass ratio of a:b:c:d, 60≤a≤85, 0 ； ； ； ; Wherein, E comprises amine group, epoxy group, phenyl group, furan ring, hydroxyl group or mercapto group, M comprises Cu, Zn or Ag, A comprises unsubstituted or substituted C1-C6 alkyl, B comprises hydrolysable group, D comprises amine group, epoxy group, glycidyl ether group, hydroxyl group or mercapto 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, characterized in that: The hydroxyl-terminated polysiloxane comprises an addition reaction product of octamethylcyclotetrasiloxane and tetramethyltetavinylsilane and / or a click reaction product of the addition reaction product and a compound with mercapto group; wherein, in the addition reaction system, the tetramethyltetavinylsilane accounts for 0-30% of the molar amount of octamethylcyclotetrasiloxane.

3. The antifouling coating composition according to claim 2, characterized in that: The compound with mercapto group comprises one of 2-mercaptoethylamine, 2-phenyl ethanethiol, 1-propanethiol, 3-mercaptopropionic acid, 2-methyl-3-mercaptifuran and 3-mercapto-1-propanol.

4. The antifouling coating composition according to claim 1, characterized in that: The weight average molecular weight of the hydroxyl-terminated polysiloxane is 30000-100000.

5. The antifouling coating composition according to claim 1, characterized in that: The hydrolysable group of the crosslinking agent represented by Formula IV comprises alkoxy group.

6. The antifouling coating composition according to claim 1, characterized in that: The crosslinking agent represented by Formula IV comprises one or more of a combination of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyl ether propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and tetraethyl orthosilicate condensate.

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

8. The antifouling coating composition according to claim 1, characterized in that: The antifouling coating composition further comprises one or more of a combination of solvent, filler and auxiliary agent.

9. The antifouling coating composition according to claim 8, characterized in that: The auxiliary agent comprises one or more of a combination of reinforcing agent, thixotropic agent, thickening agent, anti-settling agent, dehydrating agent, dispersing agent, wetting agent, surfactant, adhesive, plasticizer and pigment.

10. A process for the preparation of the antifouling coating composition according to any one of claims 1 to 9, characterized in that, Comprise: In a protective atmosphere, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out to obtain the hydroxyl-terminated polysiloxane represented by Formula I; The antifouling coating composition is prepared by uniformly mixing at least the hydroxyl-terminated polysiloxane, the compound represented by Formula II and / or Formula III, the crosslinking agent represented by Formula IV and the catalyst.

11. The method of claim 10, wherein, Comprise: In a protective atmosphere and under the temperature condition of 80-100℃, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out for 3-8h to obtain the hydroxyl-terminated polysiloxane; wherein, in the addition reaction system, the tetramethyltetavinylsilane accounts for 0-30% of the molar amount of octamethylcyclotetrasiloxane.

12. The method of claim 10, wherein, Specifically comprise: In a protective atmosphere and under the temperature condition of 80-100℃, tetramethyltetavinylsilane is mixed with octamethylcyclotetrasiloxane and addition reaction is carried out for 3-8h to obtain the addition reaction product; 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 under ultraviolet light irradiation and at a temperature of 25°C to 35°C and subjected to a click reaction for 3 to 8 hours, thereby obtaining the hydroxyl-terminated polysiloxane.

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

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 by: At least a portion of the surface of the object is covered with the antifouling coating of claim 13.

16. A method for preventing fouling of a surface of an object, characterized by, Comprising: An antifouling coating is formed by applying the antifouling coating composition of any one of claims 1-9 to at least a portion of the surface of the object.

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