Modified organic silicon marine antifouling paint based on boric acid ester dynamic crosslinking and coating

Abstract

The invention discloses a modified organic silicon marine antifouling paint and coating based on dynamic crosslinking of boric acid ester, and the modified organic silicon marine antifouling paint based on dynamic crosslinking of boric acid ester comprises the following components in parts by weight: 20-40 parts of a component A; 4-10 parts of a component B; 1-3 parts of a component C; wherein the component A comprises hydroxyl-terminated polydimethylsiloxane, borate modified polysiloxane, an auxiliary agent, a pigment filler and a first solvent, the component B comprises a curing agent and a second solvent, and the component C comprises a catalyst and a third solvent. Hydrolysis of boric acid ester bonds increases the hydrogen-bond interaction between the coating and a base material, and meanwhile, ether groups are introduced to strengthen the hydrogen-bond interaction effect, so that the coating can be firmly adhered to the intermediate paint in a seawater soaking environment.

Description

Technical Field

[0001] The present invention belongs to the technical fields of marine antifouling coatings and underwater coating protection, and relates to a modified silicone marine antifouling coating and coating based on borate dynamic crosslinking. Background Art

[0002] With the continuous deepening of human marine development activities, various marine facilities such as ships, offshore platforms, and underwater pipelines face serious biofouling problems in the long-term immersion environment. Marine fouling not only affects the service life and operating efficiency of facilities, but also causes increased energy consumption, increased maintenance frequency, and significantly increased operating costs.

[0003] The current mainstream marine antifouling coatings are mainly divided into three categories: toxic antifouling coatings based on the release of metal oxides, non-toxic fouling release antifouling coatings based on low surface energy materials, and bionic anti-fouling systems that have developed rapidly in recent years. Among them, the low surface energy antifouling coatings based on silicone materials have been widely used in the field of environmental protection antifouling due to their good flexibility, low toxicity, and excellent hydrophobicity and non-adhesion properties.

[0004] Silicone antifouling coatings usually use polydimethylsiloxane as the matrix, and its surface free energy can be as low as 20–25 mJ / m 2 , which can effectively reduce the initial attachment of marine organisms, especially mollusks. However, traditional silicone coatings have two significant bottlenecks: one is that due to the dominance of highly non-polar –Si(CH3)2– groups in the main chain structure, there is a lack of effective interfacial bonding force with the substrate (especially polar substrates such as metals or epoxy intermediate paints), resulting in easy coating peeling; the other is that during long-term service, the penetration of water molecules in seawater and the interfacial hydration effect will further damage the interfacial bonding between the coating and the substrate, thus exacerbating the adhesion attenuation phenomenon. These problems significantly limit the application stability and durability of silicone antifouling coatings in complex and harsh marine environments. Summary of the Invention

[0005] Object of the Invention: The object of the present invention is to solve the problem of weak adhesion of the coating to various polar substrates or intermediate paints, and to provide a modified silicone marine antifouling coating and coating based on borate dynamic crosslinking.

[0006] Technical Solution: The modified silicone marine antifouling coating based on borate dynamic crosslinking of the present invention, by weight, (1) 20–40 parts of component A; (2) 4–10 parts of component B; (3) 1–3 parts of component C;

[0007] Among them,

[0008] Component A, by weight, includes:

[0009]

[0010]

[0011] Component B includes, by weight:

[0012] Curing agent 5-15 parts

[0013] 20-50 parts of the second solvent

[0014] Component C, calculated by weight, includes:

[0015] Catalyst 5-10 parts

[0016] 15 to 40 parts of the third solvent;

[0017] The present invention synthesizes a borate-modified polysiloxane polymer, which is a long-chain segment structure. The final cured coating is a three-dimensional network elastomer coating generated by hydroxyl-terminated polydimethylsiloxane and a curing agent under the action of a catalyst, and the borate-modified polysiloxane polymer does not react during the curing of the coating into a coating, and exists in the gaps of the three-dimensional network structure in a free state. At the same time, the borate-modified polysiloxane polymer acts as a high molecular weight substance, and can be stabilized in the three-dimensional network structure elastomer in the form of curling, winding, etc., and can also move appropriately. Based on this mode, the borate-modified polysiloxane polymer exists in the cured coating in a free state, and the hydration layer in the immersion process is destroyed through the borate bond and ether bond on its side chain, so that the three-dimensional network structure has a strong adhesiveness.

[0018] Preferably, the hydroxyl-terminated polydimethylsiloxane is selected from α,ω-dihydroxy polydimethylsiloxane having a viscosity of 2800 to 10000 mPa·s at 25°C.

[0019] Preferably, the borate-modified polysiloxane is synthesized by free radical copolymerization and borate cross-linking reaction at the same time, and the specific steps are as follows:

[0020] (1) In a nitrogen-protected reactor, boric acid, a monomer with a hydroxypropyl group and an unsaturated group, an acrylate monomer with an ether group, a methyl vinyl MQ type silicone resin, an initiator azobisisobutyronitrile, and a mixed solvent are added in sequence, then stirred evenly and heated to 65-75° C. to react for 12-18 hours;

[0021] (2) pouring the reaction product into methanol at 0-8°C and filtering it multiple times, and dissolving the filtered product in ethyl acetate;

[0022] (3) Pour the product / ethyl acetate mixture into excess n-hexane at 0-8°C for precipitation, filter and dry, and the obtained precipitated product is the borate-modified polysiloxane.

[0023] Preferably, the boric acid is selected from commercially available boric acid with a molecular formula of H3BO3, without any specific brand or manufacturer requirement.

[0024] Preferably, the monomer having a hydroxypropyl group and an unsaturated group is selected from one of 2-hydroxy-1-methylethyl methacrylate, 1-hydroxypropyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 2-hydroxy-1-methylethyl acrylate, N-(3-hydroxypropyl)acrylamide, and 2,3-dihydroxypropyl acrylate.

[0025] Preferably, the acrylic ester monomer having an ether group is selected from 2-methoxyethyl acrylate, 1-allyloxy-2,3-propylene oxide, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0026] Preferably, the M:Q value of the methyl vinyl MQ type silicone resin is ≥1.3:1, or the methyl vinyl MQ type silicone resin is liquid at 25°C.

[0027] Preferably, the mixed solvent is a mixed solvent that can dissolve relevant reactants, without special requirements.

[0028] Specifically, the present invention provides a mixed solvent prepared by mixing acetone, methanol, and ethyl acetate in a weight ratio of 3:3:4.

[0029] Preferably, the weight ratio of the boric acid, the monomer with hydroxypropyl and unsaturated groups, the acrylate monomer with ether groups, the methyl vinyl MQ type silicone resin, the initiator azobisisobutyronitrile, and the mixed solvent is 5: (10-20): (2-5): (20-40): (0.2-0.8): (50-100).

[0030] Preferably, the auxiliary agent is selected from at least one of a wetting and dispersing agent, a defoaming agent and a leveling agent.

[0031] Specifically, the wetting and dispersing agent is selected from BYK116, BYK169 of BYK Company, 901, 903 of Deqian Company. The defoaming agent is selected from BYK065, BYK066N of BYK Company, EFKA2020 of Efka of the Netherlands. The leveling agent is selected from BYK308, BYK310, BYK373 of BYK of Germany.

[0032] Preferably, the pigment extender is common in the art and there are no special requirements. As a preferred solution, it is selected from, but not limited to, one of calcium carbonate, iron(III) oxide, titanium dioxide, barium sulfate, kaolin, zinc oxide.

[0033] Preferably, the first solvent is selected from one of toluene, xylene, acetone.

[0034] Preferably, the curing agent is selected from one of tetraethyl orthosilicate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(isobutenyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane.

[0035] Preferably, the second solvent is selected from one of acetone, methyl ethyl ketone, acetylacetone.

[0036] Preferably, the catalyst is selected from one of dibutyltin dilaurate, stannous octoate, organobismuth.

[0037] Preferably, the third solvent is selected from one of acetylacetone, cyclohexanone, toluene.

[0038] Preferably, the modified silicone marine antifouling coating based on borate dynamic crosslinking of the present invention can be prepared according to the conventional coating preparation method. First, components A, B, and C are prepared separately and stored in sealed containers.

[0039] Specifically, the present invention provides a specific preparation method, which is not limited to this preparation method in actual application. The specific steps are as follows:

[0040] (1) In a dispersion stirring device, hydroxy-terminated polydimethylsiloxane, borate-modified polysiloxane, additives, and 50% of the first solvent are added in sequence. Then, it is dispersed at 100 rpm for 20 min. After that, the pigment extender and 50% of the first solvent are added to the dispersion stirring device, and it is continuously dispersed at the same rotation speed for 20 min to prepare component A, which is then stored in sealed containers;

[0041] (2) Using a dispersion stirring device, the curing agent and the second solvent are dispersed at 50 rpm for 10 min to prepare component B, which is then stored in sealed containers;

[0042] (3) Using a dispersion stirring device, the catalyst and the third solvent are dispersed at 50 rpm for 10 min to prepare component C, which is then stored in sealed containers;

[0043] Preferably, the present invention also provides a coating prepared from the modified silicone marine antifouling coating based on borate dynamic crosslinking. Components A, B, and C are mixed evenly using conventional dispersion processes and equipment, and are applied by spraying, rolling, brushing, etc. After curing for at least 48 h, a coating with a film thickness of 150 - 250 μm is prepared.

[0044] Beneficial effects: Compared with the prior art, the present invention has the following remarkable advantages:

[0045] 1. Through the free radical copolymerization reaction and the borate cross-linking reaction simultaneously, the borate group is introduced into the side chain of the modified polysiloxane molecular chain, providing support for the subsequent dynamic reversible change (hydrolysis) of the borate bond to release hydrogen bond action.

[0046] 2. The borate-modified polysiloxane is stored in the gaps of the cured three-dimensional network structure in a free state, and the overall cured coating is still constructed by flexible three-dimensional polydimethylsiloxane, ensuring that the coating still has excellent low surface energy characteristics.

[0047] 3. The free borate-modified polysiloxane molecular chain has a hydrophilic segment. At the same time, in order to encapsulate the free borate-modified polysiloxane polymer, the internal molecular gaps in the cured three-dimensional silicone coating increase. Combining the hydrophilic groups and the enlarged molecular gaps, water molecules are more likely to diffuse during the immersion in seawater, thereby inducing the hydrolysis of the borate bond to release a large amount of hydrogen bond action.

[0048] 4. The ether group introduced in the side chain can also promote the generation of hydrogen bond action. The ether group itself can form hydrogen bond action with other polar groups. After a large amount of hydrogen bond action is released due to the reversible change of the borate, the ether group further strengthens the hydrogen bond effect, thereby ensuring that the coating maintains a lasting, stable and excellent bonding effect during seawater immersion. Specific embodiments

[0049] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those of ordinary skill in the art can make several deformations and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0050] The coating of the present invention realizes the generation of hydrogen bond action when immersed in seawater by introducing a borate dynamic reversible structure, thereby ensuring that the coating has excellent bonding effect. At the same time, the borate-modified polysiloxane polymer exists in a free state inside the three-dimensional flexible polysiloxane coating, ensuring that the cured coating still has excellent hydrophobic effect and low surface free energy, and maintains good antifouling properties.

[0051] The raw materials used in the examples are shown in Table 1. Specifically, when implementing, it is not limited to the raw materials in Table 1, and corresponding products can be selected according to the foregoing. Other raw materials used in the examples are all commercially available chemical reagents.

[0052] Table 1:

[0053]

[0054]

[0055] Preparation of Borate-Modified Polysiloxane 1

[0056] Boric acid, monomer 2-1 with hydroxypropyl and unsaturated groups, acrylate monomer 3-1 with ether groups, methyl vinyl MQ silicone resin 4-1, initiator azobisisobutyronitrile, and mixed solvent were proportioned at a weight ratio of 5:15:2:35:0.8:60. The specific preparation process is as follows:

[0057] (1) In a reaction kettle under nitrogen protection, boric acid, monomer 2-1 with hydroxypropyl and unsaturated groups, acrylate monomer 3-1 with ether groups, methyl vinyl MQ silicone resin 4-1, initiator azobisisobutyronitrile, and mixed solvent were added in sequence. Then, it was stirred evenly and heated to 65 °C for reaction for 18 h;

[0058] (2) The reaction product was poured into methanol at 5 °C and filtered multiple times. The filtered product was dissolved in ethyl acetate;

[0059] (3) The product / ethyl acetate mixture was poured into excessive n-hexane at 0 °C for precipitation, filtered and dried. The obtained precipitate product is borate-modified polysiloxane 1.

[0060] Preparation of Borate-Modified Polysiloxane 2

[0061] Boric acid, monomer 2-2 with hydroxypropyl and unsaturated groups, acrylate monomer 3-3 with ether groups, methyl vinyl MQ silicone resin 4-2, initiator azobisisobutyronitrile, and mixed solvent were proportioned at a weight ratio of 5:10:5:40:0.7:100. The specific preparation process is as follows:

[0062] (1) In a reaction kettle under nitrogen protection, boric acid, monomer 2-2 with hydroxypropyl and unsaturated groups, acrylate monomer 3-3 with ether groups, methyl vinyl MQ silicone resin 4-2, initiator azobisisobutyronitrile, and mixed solvent were added in sequence. Then, it was stirred evenly and heated to 70 °C for reaction for 15 h;

[0063] (2) The reaction product was poured into methanol at 8 °C and filtered multiple times. The filtered product was dissolved in ethyl acetate;

[0064] (3) The product / ethyl acetate mixture was poured into excessive n-hexane at 8 °C for precipitation, filtered and dried. The obtained precipitate product is borate-modified polysiloxane 2.

[0065] Preparation of Borate-Modified Polysiloxane 3

[0066] Boric acid, monomer 2-3 with hydroxypropyl and unsaturated groups, acrylate monomer 3-2 with ether groups, methyl vinyl MQ silicone resin 4-2, initiator azobisisobutyronitrile, and a mixed solvent are formulated in a weight ratio of 5:20:4:20:0.2:50. The specific preparation process is as follows:

[0067] (1) In a reaction kettle under nitrogen protection, boric acid, the monomer with hydroxypropyl and unsaturated groups, the acrylate monomer with ether groups, methyl vinyl MQ silicone resin, initiator azobisisobutyronitrile, and the mixed solvent are added in sequence. Then, it is stirred evenly and heated to 75 °C for reaction for 12 h;

[0068] (2) The reaction product is poured into methanol at 0 °C and filtered multiple times. The filtered product is dissolved in ethyl acetate;

[0069] (3) The product / ethyl acetate mixture is poured into excessive n-hexane at 4 °C for precipitation, filtered and dried. The obtained precipitated product is the boric acid ester-modified polysiloxane 3.

[0070] Examples 1-5

[0071] The component ratios of Groups A, B, and C in Examples 1-5 are shown in Table 2, and the component ratios of each component in Examples 1-5 are shown in Table 3.

[0072] Table 2

[0073] Component Example 1 Example 2 Example 3 Example 4 Example 5 A 20 25 35 40 40 B 4 4 5 8 10 C 1 1.5 3 3 2

[0074] Table 3

[0075]

[0076]

[0077] The preparation steps of the modified silicone marine antifouling coating based on boric acid ester dynamic crosslinking in Examples 1-5 are as follows. In actual application, it is prepared according to the conventional method of marine antifouling coatings, and is not limited to this preparation method.

[0078] (1) In a dispersion and stirring device, hydroxyl-terminated polydimethylsiloxane, boric acid ester-modified polysiloxane, additives, and 50% of the first solvent are added in sequence. Then, it is dispersed at 100 rpm for 20 min. After that, the pigment and filler and 50% of the first solvent are added to the dispersion and stirring device, and it is continuously dispersed at the same rotation speed for 20 min to prepare Component A, which is then sealed and stored;

[0079] (2) Using a dispersion and stirring device, the curing agent and the second solvent are dispersed at 50 rpm for 10 min to prepare Component B, which is then sealed and stored;

[0080] (3) using a dispersing and stirring device to disperse the catalyst and the third solvent at 50 rpm for 10 min, i.e., preparing component C, and then sealing and storing;

[0081] (4) Component A, component B, and component C are mixed uniformly using conventional dispersion processes and equipment, and applied by spraying, rolling, brushing, etc. After curing for at least 48 hours, a coating with a film thickness of 150 to 250 μm is prepared.

[0082] Comparative Example 1 (Modified organosilicon marine antifouling coating without borate)

[0083] Compared with Example 1, no boric acid was added in the process of preparing the modified polymer in Comparative Example 1, and the remaining components and weight parts were the same, and the preparation process was also the same as that of Example 1.

[0084] Comparative Example 2 (Ordinary silicone low surface energy marine antifouling coating)

[0085] The common organosilicon low surface energy marine antifouling paint comprises the following raw materials in parts by weight: 90.0 parts of polysiloxane resin, 30.0 parts of pigment and filler, 4.0 parts of cross-linking curing agent, 1.5 parts of catalyst, 0.5 parts of auxiliary agent and 10.0 parts of solvent.

[0086] The polysiloxane resin is α, ω-dihydroxy polydimethylsiloxane with a viscosity of 10000 mPa·s; the pigment is zinc oxide; the cross-linking curing agent is tetraethyl orthosilicate; the catalyst is dibutyltin disilicate; the auxiliary agent is 0.5 parts of BYK161 dispersant from BYK; and the solvent is xylene.

[0087] (1) 90.0 parts of α,ω-dihydroxy polydimethylsiloxane with a viscosity of 10000 mPa·s and 30.0 parts of micron-sized zinc oxide were added to a disperser and dispersed at 300 rpm for 30 min. Subsequently, 0.5 parts of BYK161 dispersant from BYK was added to the disperser at 200 rpm and dispersed for 30 min. The mixture was then ground with a sand mill to a fineness of less than 40 μm to prepare a pre-dispersed slurry and canned for standby use.

[0088] (2) 4.0 parts of tetraethyl orthosilicate and 10.0 parts of xylene were mixed evenly to prepare a crosslinking curing agent component, which was then canned for standby use; 1.5 parts of dibutyltin dioxysilicate and 20.0 parts of xylene were mixed evenly to prepare a catalyst component, which was then canned for standby use;

[0089] (3) Before use, the pre-dispersed slurry, the cross-linking curing agent component, and the catalyst component are stirred uniformly according to the ratio. After the obtained coating is applied and cured, a common organic silicon low surface energy marine antifouling coating with a thickness of 150 to 200 μm is obtained.

[0090] <Specific test experiments and conditions>

[0091] Test 1: Surface free energy

[0092] The contact angles of deionized water and diiodomethane on the surface of the cured coating were measured using an XG-CAMC3 full-automatic contact angle measuring instrument produced by Shanghai Xuanzhun Instrument Co., Ltd. Before measurement, the coating surface needs to be cleaned with anhydrous ethanol and dried, and then the surface free energy of the coating is calculated according to the Owens two-liquid method.

[0093] Test 2: Adhesion measurement by pull-off method (epoxy intermediate paint)

[0094] The adhesion of the coating applied on the epoxy intermediate paint was measured using a BGD500 digital display semi-automatic adhesion tester produced by Guangzhou Biogda Precision Instrument Co., Ltd. The steel plate needs to be polished with 800-mesh sandpaper before use, and the epoxy intermediate paint used is the epoxy micaceous iron oxide intermediate paint produced by Shanghai Jinsi Emperor. Before testing the adhesion, all coatings were immersed in sterilized seawater for 7 days.

[0095] Test 3: Antifouling performance

[0096] At least 108 units of Streptococcus salivarius were dispersed in 20 mL of tryptic soy broth and cultured at 38 °C and 5% CO2 for 2 hours. Subsequently, the suspension was further diluted and inoculated into agar supplemented with 5% sheep blood, and cultured at 38 °C and 5% CO2 for 48 hours. Then, the suspension containing six colony-forming units was dispersed in 10 mL of tryptic soy broth. Subsequently, 20 mL of the above bacterial suspension was covered on the coating in the range of 10×5 cm and cultured at 38 °C and 5% CO2 for 24 hours. After the culture, each sample needs to be rotated and rinsed in 45 mL of distilled water for 30 seconds, and then rinsed with 50 mL of distilled water to remove non-sticky substances. The bacteria adhered to the surface were observed using a Simga300 scanning electron microscope produced by Carl Zeiss AG, Germany.

[0097] The specific test results of Examples 1-5 and Comparative Examples 1-2 are shown in Table 4.

[0098] Table 4

[0099]

[0100] Through the above tests, it can be confirmed that the coatings prepared in Examples 1-5 also have a lower surface free energy compared with the coatings of the comparative examples, and thus exhibit excellent antifouling performance. The advantage of the present invention is that the examples have excellent adhesion on various polar substrates, far stronger than the comparative examples, showing excellent bonding effects.

Claims

1. A modified silicone marine antifouling coating based on borate dynamic crosslinking, characterized in that, By weight parts, it includes: 20 - 40 parts of component A; 4 - 10 parts of component B; 1 - 3 parts of component C; Among them, Component A, by weight parts, includes: Component B, by weight parts, includes: 5 - 15 parts of curing agent 20 - 50 parts of second solvent Component C, by weight parts, includes: 5 - 10 parts of catalyst 15 - 40 parts of third solvent.

2. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 1, wherein The borate - modified polysiloxane is prepared by the following steps: (1) In a reaction kettle under nitrogen protection, boric acid, a monomer with a hydroxypropyl and an unsaturated group, an acrylate monomer with an ether group, methyl vinyl MQ - type silicone resin, initiator azobisisobutyronitrile, and a mixed solvent are added in sequence. Then, it is stirred evenly and heated to 65 - 75 °C for reaction for 12 - 18 h; (2) The reaction product is poured into methanol at 0 - 8 °C and filtered multiple times, and the filtered product is dissolved in ethyl acetate; (3) The product / ethyl acetate mixture is poured into excessive n - hexane at 0 - 8 °C for precipitation, filtered and dried, and the obtained precipitate product is the borate - modified polysiloxane.

3. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 2, characterized in that, The monomer with a hydroxypropyl and an unsaturated group is selected from one of 2 - hydroxy - 1 - methylethyl methacrylate, 1 - hydroxypropyl - 3 - vinylimidazolium bis(trifluoromethanesulfonyl)imide, 2 - hydroxy - 1 - methylethyl acrylate, N - (3 - hydroxypropyl)acrylamide, 2,3 - dihydroxypropyl acrylate.

4. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 2, characterized in that, The acrylate monomer with an ether group is selected from one of 2 - methoxyethyl acrylate, 1 - allyloxy - 2,3 - epoxypropane, 2-(2 - ethoxyethoxy)ethyl acrylate.

5. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 2, wherein The M:Q value of the methyl vinyl MQ - type silicone resin ≥ 1.3:1, or the methyl vinyl MQ - type silicone resin is a liquid at 25 °C.

6. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 2, wherein The weight ratio of boric acid, the monomer with a hydroxypropyl and an unsaturated group, the acrylate monomer with an ether group, methyl vinyl MQ - type silicone resin, initiator azobisisobutyronitrile, and the mixed solvent is 5:(10 - 20):(2 - 5):(20 - 40):(0.2 - 0.8):(50 - 100).

7. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 1, characterized in that, The hydroxyl - terminated polydimethylsiloxane is selected from α,ω - dihydroxypolydimethylsiloxane with a viscosity of 2800 - 10000 mPa·s at 25 °C.

8. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 1, characterized in that, The curing agent is selected from one of tetraethyl orthosilicate, 3 - (methacryloyloxy)propyltrimethoxysilane, 3 - (isobutenyloxy)propyltrimethoxysilane, γ - methacryloyloxypropyltriisopropoxysilane.

9. The modified silicone marine antifouling coating based on borate dynamic crosslinking according to claim 1, wherein, The catalyst is selected from one of dibutyltin dilaurate, stannous octoate, organic bismuth.

10. A coating, characterized in that, It is obtained by coating with the state - crosslinked modified fouling - release marine antifouling coating according to any one of claims 1 - 9.

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