A high adhesion strength biomimetic antifouling paint composition and a method for preparing the same

Abstract

The present application relates to the technical field of paint, and particularly discloses a high-adhesion-strength bionic antifouling paint composition and a preparation method thereof, which comprises an adhesion agent and an antifouling agent, and the adhesion agent and the antifouling agent are sprayed in sequence; wherein the adhesion agent comprises a hyperbranched polymer, the hyperbranched polymer takes pentaerythritol tetraacrylate as a main body, and is sequentially grafted with polyethylene glycol diacrylate and amino-terminated polyethylene glycol; the antifouling agent component contains epoxy resin, polyetherimide, silicone-modified polyimide, sea urchin-shaped amino-terminated silicone filler, polyaniline and a curing agent. The present application can make the antifouling layer formed by the antifouling agent better adhere to the surface of the ship body through the mechanism of the adhesion agent that is accelerated to coagulate when encountering water; the antifouling layer reduces the adhesion of marine organisms with extremely low surface energy and bionic mechanism, and at the same time, protects the adhesion base material layer formed by the adhesion agent with good toughness and excellent stability, so as to give the ship body excellent antifouling effect and maintain long-acting antifouling performance.

Description

Technical Field

[0001] This invention relates to the technical field of coatings, and more specifically, to a biomimetic anti-fouling coating composition with high adhesion strength and a method for preparing the same. Background Technology

[0002] Marine biofouling is a major concern for marine industrial facilities, including accelerated hull corrosion and increased fuel consumption during ship operation. The use of antifouling coatings is currently the most effective way to reduce marine biofouling. Traditional marine antifouling coatings typically contain one or more inorganic copper-based antifouling additives that reduce biofouling on the hull surface by releasing toxic substances. However, these toxic substances have long degradation times in water and can easily spread into the marine environment, adversely affecting non-target organisms. Currently, the main research direction in antifouling and drag-reducing coating technology in the industry is low surface energy antifouling and drag reduction, including silicone-based and organofluorine-based low surface energy coatings.

[0003] In related technologies, Zhao et al. constructed an amphiphilic membrane surface derived from a block copolymer containing hydrophilic polyethylene oxide (PEO) and low surface energy polydimethylsiloxane (PDMS) segments. This membrane surface can achieve drag reduction and exhibit good antifouling performance against biofouling such as algae. However, after testing, it was found that the ether or ester bonds of PEG copolymers are easily degraded under light and humid conditions, resulting in a short protection time.

[0004] Chen et al. reported that amphiphilic films derived from amphiphilic fluorinated copolymers exhibit excellent resistance to and release of various types of dirt. Compared to low surface energy antifouling coatings made from silicones, research progress on low surface energy coatings made from fluoropolymers has not been smooth, mainly due to the high curing temperature, high price, and insufficient adhesion of fluoropolymers.

[0005] Based on the above situation, the industry urgently needs to develop a marine antifouling coating that can not only have high antifouling performance, but also adhere to the ship surface for a long time to maintain its antifouling effect. Summary of the Invention

[0006] To address the problem that traditional marine antifouling coatings struggle to achieve both excellent antifouling performance and long-lasting antifouling capabilities, this application provides a biomimetic antifouling coating composition with high adhesion strength and its preparation method.

[0007] In a first aspect, this application provides a biomimetic anti-fouling coating composition with high adhesion strength, employing the following technical solution:

[0008] A biomimetic anti-fouling coating composition with high adhesion strength includes a tackifier and an anti-fouling agent, wherein the tackifier and the anti-fouling agent are sprayed sequentially;

[0009] The tackifier includes a hyperbranched polymer, which is mainly composed of pentaerythritol tetraacrylate and sequentially grafted with polyethylene glycol diacrylate and amino-terminated polyethylene glycol.

[0010] The antifouling agent comprises the following components by weight percentage:

[0011] 50-70% epoxy resin, 10-20% polyetherimide, 6-8% silicone-modified polyimide, 5-15% urchin-like amino-terminated silicone filler, 5-8% polyaniline, and 4-6% curing agent.

[0012] By adopting the above technical solution, this application uses a two-component coating for sequential spraying. The tackifier promotes gelation when it comes into contact with water, so that the anti-fouling agent has high bonding strength when immersed in water. The anti-fouling agent achieves the anti-fouling effect by using biomimetic principles. At the same time, the anti-fouling agent acts as a protective layer to reduce the impact of microorganisms on the tackifier, thereby reducing the possibility of ester bond degradation of the tackifier.

[0013] Pentaerythritol tetraacrylate is an acrylate monomer with olefin-terminated ends. Polyethylene glycol diacrylate (PEG) has polyethylene glycol as its main chain, with acrylate grafted at both ends to form olefin-terminated polyester segments. Pentaerythritol tetraacrylate and PEG acrylate undergo a Michael addition reaction, resulting in a hyperbranched polymer structure with easily movable polymer segments. The double bonds at the ends of the polymer intermediates open, reacting with amino groups via Michael addition to form a hyperbranched polymer with hydrophilic amino groups at the ends. Upon contact with water, the hydrophobic framework of the hyperbranched polymer shrinks, and the hyperbranched polymer aggregates under the influence of water, rapidly expelling moisture from the substrate surface. The hydrophilic amino groups are exposed, allowing for full contact with the substrate and achieving rapid adhesion through hydrogen bonding and electrostatic interactions. The tackifying substrate layer becomes more viscous upon contact with water, allowing the antifouling coating to adhere even more firmly to the ship's surface.

[0014] The antifouling agent primarily consists of epoxy resin, polyether amide, and silicone-modified polyimide. The epoxy resin rapidly forms a film under the action of an amine curing agent and the amino groups in the tackifying substrate layer, creating the antifouling layer. Due to the good compatibility between polyether amide and epoxy resin and polyaniline, it acts as a bridge, promoting the compatibility of polyaniline, silicone-modified polyimide, and epoxy resin. The antifouling layer exhibits high adhesion strength to the tackifying substrate layer, enabling it to adhere effectively to the hull surface. Simultaneously, the hyperbranched structure of the tackifying substrate layer and the flexible silicone segments of the antifouling layer impart good overall toughness, effectively resisting the impact of seawater.

[0015] Meanwhile, polyaniline, silicone-modified polyimide, and urchin-shaped amino-terminated silicone filler impart a low surface energy to the antifouling layer formed by the antifouling agent, reducing the adhesion of marine organisms and their secretions. The sharp protrusions of the urchin-shaped amino-terminated silicone filler can trap air, helping to improve the surface hydrophobicity of the antifouling layer and reduce the contact area of ​​organisms on the ship, thereby effectively reducing the possibility of marine organisms adsorbing onto the hull surface. The addition of polyaniline can also impart a certain degree of conductivity to the antifouling layer. Applying a pulsed current to the ship surface can generate an electric field, which can be used to knock down the tiny organisms adsorbed on the hull surface, further enhancing the defouling effect.

[0016] In addition, polyaniline has a stable conjugated structure and a high cross-linking density of the antifouling layer, which can play a good protective role, weaken the influence of environmental factors such as radiation and humidity on the ester groups of the tackifying substrate layer, and make the tackifying substrate layer stably adhere to the hull surface.

[0017] Based on this, the combined effect of the tackifying substrate layer and the antifouling layer endows the hull with excellent antifouling effect and maintains long-term antifouling performance.

[0018] Furthermore, the epoxy resin is composed of aliphatic glycidyl ether epoxy resin and glycidyl ester type epoxy resin in a weight ratio of 1:(0.5~1.5).

[0019] By adopting the above technical solutions, epoxy resins include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, and glycidyl ester epoxy resin. This application uses aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin to give the antifouling layer good toughness. The antifouling layer can have excellent impact resistance and adhere to the hull surface for a long time. Furthermore, due to the low viscosity of the two resins, the antifouling agent has excellent flowability and can flow well on the hull surface, fully covering the tackifying substrate layer and assisting the tackifying substrate layer in achieving excellent protective effects.

[0020] Furthermore, the preparation method of the urchin-shaped amino-terminated organosilicon filler is as follows:

[0021] The surfactant and catalyst are dissolved in water, and tetraethyl orthosilicate is added. The mixture is heated to 75-85°C and refluxed for 6-12 hours. After cooling, washing, and drying, the mixture is heated to 500-600°C at a rate of 2-4°C / min and held for 4-6 hours to obtain sea urchin-shaped silica powder.

[0022] Sea urchin-shaped silica powder was ultrasonically dispersed in anhydrous ethanol, then aminosilane coupling agent and ammonia were added, the temperature was raised to 75-85℃ and refluxed for 6-12 hours, and then cooled, washed and dried to obtain sea urchin-shaped amino-terminated organosilicon filler.

[0023] The weight ratio of tetraethyl orthosilicate, surfactant, catalyst and water is 100:(9~11):(6.5~7):(600~800); the weight-volume ratio of urchin-shaped silica powder, aminosilane coupling agent and ammonia is 100g:(200~400)mL:(100~200)mL.

[0024] By adopting the above technical solution, sea urchin-shaped silicon powder is first prepared, and then modified by an aminosilane coupling agent, so that the sea urchin-shaped silicon powder has excellent compatibility with the epoxy resin of the antifouling agent, and the sea urchin-shaped amino-terminated organosilicon filler can be firmly embedded in the antifouling layer.

[0025] Furthermore, the weight ratio of the urchin-shaped amino-terminated silicone filler to the epoxy resin is 1:5.5.

[0026] Furthermore, the particle size of the urchin-shaped amino-terminated organosilicon filler is controlled at 10±2μm.

[0027] By adopting the above technical solution and adjusting the weight ratio of sea urchin-shaped amino-terminated silicone filler and epoxy resin, the sea urchin-shaped amino-terminated silicone filler can be effectively dispersed in the antifouling layer. Furthermore, by controlling the particle size range of the sea urchin-shaped amino-terminated silicone filler, the filler can be more clearly protruded from the surface of the antifouling layer, while reducing the agglomeration of the filler and the possibility of it falling off.

[0028] Furthermore, the organosilicon-modified polyimide is obtained by reacting an amino-terminated silane prepolymer with pyromellitic dianhydride at a molar ratio of (0.6–0.8):1;

[0029] The amino-terminated silane prepolymer is obtained by reacting γ-aminopropyltriethoxysilane with hydroxyl-terminated silicone oil.

[0030] By adopting the above technical solution, the ratio of silane segments to imide segments in silicone-modified polyimide is optimized to a suitable range, so that silicone-modified polyimide can have both good flexibility and good compatibility with epoxy resin and polyetherimide.

[0031] Furthermore, the weight ratio of polyaniline to epoxy resin is 1:6.875.

[0032] By adopting the above technical solution and adjusting the weight ratio of polyaniline and epoxy resin, the antifouling layer can have both good electrical conductivity and reduce the possibility of cracking caused by excessive rigidity.

[0033] Furthermore, the curing agent is an aliphatic polyamine curing agent.

[0034] By adopting the above technical solution, the curing agent for epoxy resin includes, but is not limited to, amine curing agents and acid anhydride curing agents. In this application, an aliphatic polyamine curing agent is selected. Aliphatic polyamines have high activity, which allows epoxy resin to be cured at room temperature.

[0035] Furthermore, the pentaerythritol tetraacrylate, polyethylene glycol diacrylate, and amino-terminated polyethylene glycol are reacted in a molar ratio of 1:2:3.

[0036] By adopting the above technical solution and controlling the proportions of each raw material, the amino content on the surface of the hyperbranched polymer is moderate, the curing speed of the anti-fouling agent on the surface of the tackifying substrate layer is controlled, and the curing rate of the anti-fouling agent is avoided from being too high, so that the anti-fouling agent can fully cover the surface of the tackifying substrate layer.

[0037] Secondly, this application provides a method for preparing a biomimetic anti-fouling coating composition with high adhesion strength, using the following technical solution:

[0038] A method for preparing a biomimetic anti-fouling coating composition with high adhesion strength includes the following steps:

[0039] Prepare hyperbranched polymers according to weight percentages to form a tackifier;

[0040] Prepare epoxy resin, polyetherimide, silicone-modified polyimide, urchin-like amino-terminated silicone filler, polyaniline, and curing agent according to weight percentages, and mix them to form an antifouling agent;

[0041] By packaging the tackifier and antifouling agent separately, a biomimetic antifouling coating composition with high adhesion strength is obtained.

[0042] By adopting the above technical solution and using the step-by-step application of anti-fouling coating, both the tackifier and the anti-fouling agent can be cured at room temperature and form a film quickly. Attached Figure Description

[0043] Figure 1 This is a SEM image of an urchin-shaped amino-terminated organosilicon filler. Detailed Implementation

[0044] Unless otherwise specified, the sources of raw materials involved in the following preparation examples, embodiments, and comparative examples are as follows:

[0045] Polyethylene glycol diacrylate: CAS No. 26570-48-9, Mn=700, sourced from Merck Chemicals;

[0046] Amino-terminated polyethylene glycol: CAS No. 24991-53-5, Mn=2000, sourced from Merck Chemicals;

[0047] Aminosilane coupling agent: Brand KH-570;

[0048] Hydroxyl-terminated silicone oil: Grade MY1203, hydroxyl content ≥8.5%, viscosity ≤30 mm 2 / S;

[0049] Aliphatic glycidyl ether epoxy resin: grade DER 325, sourced from Guangzhou Qian'an Chemical Co., Ltd.;

[0050] Glycidyl ester type epoxy resin: grade TDE-90, sourced from Guangzhou Qian'an Chemical Co., Ltd.;

[0051] Polyetherimide: Model ULTEM 1000, sourced from SABIC Innovative Materials.

[0052] Polyaniline: CAS No. 5612-44-2, sourced from Hubei Yunmei Technology Co., Ltd.;

[0053] Fatty amine curing agent: Hexamethylenediamine, analytical grade;

[0054] Preparation examples of hyperbranched polymers

[0055] Preparation Example 1

[0056] Hyperbranched polymers are prepared according to the following steps:

[0057] Under nitrogen protection, pentaerythritol tetraacrylate was added to the reaction vessel. Under stirring, polyethylene glycol diacrylate was added dropwise to pentaerythritol tetraacrylate. The molar ratio of pentaerythritol tetraacrylate to polyethylene glycol diacrylate was 1:2. The temperature was raised to 45°C and the reaction was maintained for 2 hours to obtain a polymer intermediate.

[0058] Triethanolamine was then added to the reaction system to dissolve the polymer intermediate, followed by amino-terminated polyethylene glycol. The mixture was heated to 80°C and kept at that temperature for 1 hour to obtain the hyperbranched polymer.

[0059] Preparation example of organosilicon-modified polyimide

[0060] Preparation Example I

[0061] Organosilicon-modified polyimide is prepared according to the following steps:

[0062] Under nitrogen protection, γ-aminopropyltriethoxysilane was added to the reaction vessel. Under stirring, hydroxyl-terminated silicone oil was added dropwise to the reaction vessel at a molar ratio of γ-aminopropyltriethoxysilane to hydroxyl-terminated silicone oil of 1:1. During the dropwise addition, a water pump was used to remove the ethanol generated in the reaction vessel. After the dropwise addition was completed, the reaction system was maintained at 50°C and the reaction was continued at this temperature for 3 hours before being stopped. Excess monomers were removed by vacuum distillation to obtain an amino-terminated silane prepolymer.

[0063] Under nitrogen protection, N,N-dimethylacetamide was added to the reaction vessel, and amino-terminated silane prepolymer was added under stirring. The volume molar ratio of N,N-dimethylacetamide to amino-terminated silane prepolymer was 50 mL: 1 mol.

[0064] Pyromellitic dianhydride was added in batches, with a molar ratio of amino-terminated silane prepolymer to pyromellitic dianhydride of 0.7:1. The pyromellitic dianhydride was added in three batches, and the reaction was continued at 25°C for 48 h. Triethylamine and acetic anhydride were then added, with a molar ratio of triethylamine, acetic anhydride, and pyromellitic dianhydride of 0.01:0.01:1. The reaction was continued for another 48 h. The solvent and impurities were evaporated under reduced pressure, and the product was washed with anhydrous ethanol and then vacuum dried for 3 h to obtain organosilicon-modified polyimide.

[0065] Preparation Examples II-III

[0066] The difference between the organosilicon-modified polyimide and that in Preparation Example I lies in the different molar ratio of the amino-terminated silane prepolymer to pyromellitic dianhydride, as detailed below:

[0067] In Preparation Example II, the molar ratio of amino-terminated silane prepolymer to pyromellitic dianhydride was 0.6:1;

[0068] In Preparation Example III, the molar ratio of amino-terminated silane prepolymer to pyromellitic dianhydride was 0.8:1.

[0069] Example of preparation of urchin-shaped amino-terminated organosilicon filler

[0070] Preparation example a

[0071] The sea urchin-shaped amino-terminated silicone filler was prepared according to the following steps:

[0072] By weight, 0.1 kg of surfactant cetyltrimethylammonium bromide and 0.05 kg of catalyst sodium salicylate were added to 7 kg of water, heated to 80 °C, and stirred to dissolve. Then, 0.02 kg of catalyst triethylamine was added to the mixture. After the triethylamine dissolved, 1 kg of tetraethyl orthosilicate was added. The mixture was refluxed at 80 °C for 6 h, cooled to 20 °C, washed by centrifugation with anhydrous ethanol and water, vacuum dried, and ground. The mixture was then heated to 550 °C at a rate of 3 °C / min and held for 5 h to obtain sea urchin-shaped silica powder.

[0073] Take 1 kg of the above-mentioned sea urchin-shaped silica powder, add it to anhydrous ethanol, and disperse it by ultrasonication; then add 3 L of aminosilane coupling agent and 1.5 L of ammonia water (ammonia water concentration of 22.5 wt%), heat to 80 °C and keep it under reflux for 8 h. After the reaction is completed, stop heating, cool to 20 °C, wash with anhydrous ethanol and water by centrifugation, and vacuum dry to obtain sea urchin-shaped amino-terminated organosilicon filler.

[0074] See Figure 1Under this preparation method, the size of the amino-terminated organosilicon filler reaches 10 μm, and it can be sieved according to the required size.

[0075] Preparation Example b

[0076] The sea urchin-shaped amino-terminated silicone filler was prepared according to the following steps:

[0077] By weight, 0.09 kg of surfactant cetyltrimethylammonium bromide and 0.05 kg of catalyst sodium salicylate were added to 6 kg of water, heated to 80 °C, and stirred to dissolve. Then, 0.015 kg of catalyst triethylamine was added to the mixture. After the triethylamine dissolved, 1 kg of tetraethyl orthosilicate was added. The mixture was refluxed at 80 °C for 6 h, cooled to 20 °C, washed by centrifugation with anhydrous ethanol and water, vacuum dried, and ground. The mixture was then heated to 500 °C at a rate of 3 °C / min and held for 6 h to obtain sea urchin-shaped silica powder.

[0078] Take 1 kg of the above-mentioned sea urchin-shaped silica powder and put it into anhydrous ethanol for ultrasonic dispersion; then add 2 L of aminosilane coupling agent and 1 L of ammonia water (ammonia water concentration of 22.5 wt%), heat to 75 °C and keep under reflux for 12 h. After the reaction is completed, stop heating, cool to 20 °C, wash with anhydrous ethanol and water by centrifugation, and vacuum dry to obtain sea urchin-shaped amino-terminated organosilicon filler.

[0079] Preparation example c

[0080] The sea urchin-shaped amino-terminated silicone filler was prepared according to the following steps:

[0081] By weight, 0.11 kg of surfactant cetyltrimethylammonium bromide and 0.05 kg of catalyst sodium salicylate were added to 8 kg of water, heated to 80 °C, and stirred to dissolve. Then, 0.02 kg of catalyst triethylamine was added to the mixture. After the triethylamine dissolved, 1 kg of tetraethyl orthosilicate was added. The mixture was heated to 85 °C and refluxed for 6 h. After cooling to 20 °C, the mixture was washed by centrifugation with anhydrous ethanol and water, vacuum dried, and ground. Then, the mixture was heated to 600 °C at a rate of 4 °C / min and held for 4 h to obtain sea urchin-shaped silica powder.

[0082] Take 1 kg of the above-mentioned sea urchin-shaped silica powder and put it into anhydrous ethanol for ultrasonic dispersion; then add 4 L of aminosilane coupling agent and 2 L of ammonia water (ammonia water concentration of 22.5 wt%), heat under reflux for 6 h, stop heating after the reaction is completed, cool to 20 °C, wash by centrifugation with anhydrous ethanol and water, and vacuum dry to obtain sea urchin-shaped amino-terminated organosilicon filler. Example

[0083] Example 1

[0084] A biomimetic antifouling coating composition with high adhesion strength, comprising a tackifier and an antifouling agent;

[0085] The thickener is composed of a hyperbranched polymer derived from Preparation Example 1;

[0086] The antifouling agent, by weight percentage, consists of the following components: 27.5% epoxy resin DER 325, 27.5% epoxy resin TDE-90, 13% polyetherimide ULTEM 1000, 8% silicone-modified polyimide, 10% urchin-like amino-terminated silicone filler, 8% polyaniline, and 6% hexamethylenediamine.

[0087] Among them, the sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0088] Prepare according to the following steps:

[0089] Hyperbranched polymers are packaged individually;

[0090] Weigh each component of the antifouling agent according to the weight percentage, stir the above components at 100 rpm / min, mix evenly, and then package.

[0091] According to 68g / m 2 The coating amount is first applied by spraying an adhesion promoter onto the ship's surface, which cures to form an adhesion-enhancing substrate layer; then, according to a 100g / m² application rate... 2 The anti-fouling agent is sprayed onto the surface of the tackifying substrate layer in a certain amount, and the anti-fouling agent forms an anti-fouling layer after curing.

[0092] Example 2

[0093] A biomimetic antifouling coating composition with high adhesion strength differs from Example 1 in that the composition of the antifouling agent is different, as detailed below:

[0094] The antifouling agent, by weight percentage, consists of the following components: 35% epoxy resin DER 325, 35% epoxy resin TDE-90, 10% polyetherimide ULTEM 1000, 6% silicone-modified polyimide, 5% urchin-like amino-terminated silicone filler, 5% polyaniline and 4% hexamethylenediamine.

[0095] The sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0096] Example 3

[0097] A biomimetic antifouling coating composition with high adhesion strength differs from Example 1 in that the composition of the antifouling agent is different, as detailed below:

[0098] The antifouling agent, by weight percentage, consists of the following components: 25% epoxy resin DER 325, 25% epoxy resin TDE-90, 18% polyetherimide ULTEM 1000, 7% silicone-modified polyimide, 15% urchin-like amino-terminated silicone filler, 5% polyaniline, and 5% hexamethylenediamine.

[0099] The sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0100] Examples 4-5

[0101] A biomimetic antifouling coating composition with high adhesion strength differs from Example 1 in that the urchin-like amino-terminated silicone filler used in the antifouling agent has a different source, as detailed below:

[0102] In Example 4, the sea urchin-shaped amino-terminated organosilicon filler was derived from Preparation Example b. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 20±5μm.

[0103] In Example 5, the sea urchin-shaped amino-terminated organosilicon filler was derived from Preparation Example c. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 2 ± 1 μm.

[0104] Examples 6-7

[0105] A biomimetic anti-fouling coating composition with high adhesion strength differs from Example 1 in that the source of the organosilicon-modified polyimide is different, as detailed below:

[0106] In Example 6, the organosilicon-modified polyimide was derived from Preparation Example II;

[0107] In Example 7, the organosilicon-modified polyimide was derived from Preparation Example III.

[0108] Examples 8-10

[0109] A biomimetic anti-fouling coating composition with high adhesion strength differs from Example 1 in that the composition of the epoxy resin is different, as detailed below:

[0110] In Example 8, the antifouling agent, by weight percentage, consists of the following components: 36.7% epoxy resin DER 325, 18.3% epoxy resin TDE-90, 13% polyetherimide ULTEM 1000, 8% silicone-modified polyimide, 10% urchin-like amino-terminated silicone filler, 8% polyaniline, and 6% hexamethylenediamine;

[0111] Among them, the sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0112] In Example 9, the antifouling agent, by weight percentage, consists of the following components: 22% epoxy resin DER 325, 33% epoxy resin TDE-90, 13% polyetherimide ULTEM 1000, 8% silicone-modified polyimide, 10% sea urchin-like amino-terminated silicone filler, 8% polyaniline, and 6% hexamethylenediamine.

[0113] Among them, the sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0114] In Example 10, the antifouling agent, by weight percentage, consists of the following components: 55% bisphenol A type epoxy resin E-51, 13% polyetherimide ULTEM 1000, 8% silicone-modified polyimide, 10% urchin-like amino-terminated silicone filler, 8% polyaniline, and 6% hexamethylenediamine.

[0115] The sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm. Comparative Example

[0116] Comparative Example 1

[0117] An anti-fouling coating is prepared by the following method:

[0118] The antifouling coating is cured by an antifouling agent, which, by weight percentage, consists of the following components: 27.5% epoxy resin DER 325, 27.5% epoxy resin TDE-90, 13% polyetherimide ULTEM 1000, 8% silicone-modified polyimide, 10% urchin-like amino-terminated silicone filler, 8% polyaniline, and 6% hexamethylenediamine.

[0119] Among them, the sea urchin-shaped amino-terminated organosilicon filler was derived from preparation example a. After two sieving processes, the particle size of the sea urchin-shaped amino-terminated organosilicon filler was controlled to be 10±2μm.

[0120] According to 100g / m 2 The antifouling agent is sprayed onto the surface of the ship in a certain amount of spraying volume, and after the antifouling agent cures, it forms an antifouling coating.

[0121] Comparative Example 2

[0122] An anti-fouling coating is applied using a commercially available epoxy polysiloxane coating with the brand name SeaLion Resilient, at a spraying rate of 100 g / m².2 .

[0123] Comparative Example 3

[0124] An anti-fouling coating is applied using a commercially available modified perfluoropolyether coating with the brand name OPTOOLDAC-HP, with a coating amount of 100 g / m². 2 .

[0125] Performance testing

[0126] Prepare a clean iron plate, and spray paint the surface of the iron plate to obtain the substrate.

[0127] Samples were prepared according to the methods described in Examples 1-10 and Comparative Examples 1-3, and the following tests were performed:

[0128] 1. Anti-fouling testing:

[0129] The sample was placed in seawater and soaked for 12 months. An electric current of 0.5A was applied to the sample each month for 24 hours. After 12 months, the epiphyte density on the sample was calculated as: number of epiphytes on the sample surface / sample area, unit: organisms / m². 2 The higher the density of epiphytes, the worse the antifouling effect.

[0130] 2. Long-lasting stain resistance:

[0131] 2.1 Durable antifouling effect under water flow impact:

[0132] The test sample was placed in the test chamber to simulate water flow impact, with the water flow impact force per unit area set at 1 kN / m². 2 The simulated water flow impact was conducted for 240 hours. After the impact, the antifouling test was repeated, and the epiphyte density was recorded 12 months later.

[0133] 2.2 Stain-resistant and long-lasting effect under light exposure:

[0134] The test sample was placed in the test chamber and subjected to strong light irradiation at an intensity of 1120 W / m². 2 After 240 hours of irradiation, the antifouling test was repeated, and the epiphytic density was recorded 12 months later.

[0135] Table 1. Antifouling performance test data of Examples 1-10 and Comparative Examples 1-3

[0136]

[0137] in conclusion

[0138] The test data shows that:

[0139] First, Example 1 and Comparative Example 1 form a single comparison. In Comparative Example 1, only an antifouling agent was sprayed, and the antifouling effect was superior after immersion in still water for 12 months. Although the antifouling effect of the antifouling agent was slightly inferior to that of the fluorinated antifouling agent, it was significantly better than that of the silicone antifouling agent. However, Comparative Example 1 lacked the adhesion-enhancing substrate layer. Under the impact of strong water flow, the adhesion density increased significantly, with an increase of 146.88%, which was much higher than the increase in Comparative Example 1. This indicates that the adhesion-enhancing substrate layer and the antifouling layer have a synergistic effect on antifouling ability, giving the hull long-term antifouling capability.

[0140] Second, Example 1 and Comparative Example 2 form a single comparison. Comparative Example 2 is a commercially available silicone antifouling coating. According to the experimental data, although the commercially available silicone antifouling coating has a certain antifouling ability in the early stage, its adhesion is poor. Under the same spraying amount, after 12 months of strong water flow impact, the silicone antifouling coating layer is damaged and the epiphytic density increases significantly, with an increase of 130.37%.

[0141] Third, Example 1 and Comparative Example 3 form a single comparison. Comparative Example 3 is a commercially available fluorinated antifouling coating. According to the experimental data, although the commercially available fluorinated antifouling coating has better antifouling ability than Example 1 in the initial stage, its adhesion is extremely poor. Under the same spraying amount, after 12 months of strong water flow impact, the damaged area of ​​the fluorinated antifouling coating layer is high and the epiphytic density increases significantly, with an increase of 203.84%.

[0142] Fourth, by comparing Examples 1-3, it can be seen that when the proportion of urchin-shaped amino-terminated organosilicon filler is controlled within a moderate range and the amount of polyaniline added is high, it can effectively reduce the epiphytic density of marine organisms through current and biomimetic means, thus achieving a good antifouling effect.

[0143] Fifth, by comparing Examples 1 and 4-5, it can be seen that changing the preparation parameters of the sea urchin-shaped amino-terminated organosilicon filler will affect the particle size of the filler, and the size of the filler will affect its morphology on the surface of the antifouling layer, which will have a certain impact on the epiphytic density of marine organisms.

[0144] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0145] Furthermore, the above-described embodiments merely illustrate several implementation methods of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A biomimetic anti-fouling coating composition with high adhesion strength, characterized in that: Includes a tackifier and an anti-fouling agent, which are sprayed sequentially; The tackifier includes a hyperbranched polymer, which is mainly composed of pentaerythritol tetraacrylate and sequentially grafted with polyethylene glycol diacrylate and amino-terminated polyethylene glycol. The antifouling agent comprises the following components by weight percentage: 50-70% epoxy resin, 10-20% polyetherimide, 6-8% silicone-modified polyimide, 5-15% urchin-like amino-terminated silicone filler, 5-8% polyaniline, and 4-6% curing agent.

2. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 1, characterized in that: The epoxy resin is composed of aliphatic glycidyl ether epoxy resin and glycidyl ester type epoxy resin in a weight ratio of 1:(0.5-1.5).

3. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 1, characterized in that: The preparation method of the urchin-shaped amino-terminated organosilicon filler is as follows: The surfactant and catalyst are dissolved in water, and tetraethyl orthosilicate is added. The mixture is heated to 75-85°C and refluxed for 6-12 hours. After cooling, washing, and drying, the mixture is heated to 500-600°C at a rate of 2-4°C / min and held for 4-6 hours to obtain sea urchin-shaped silica powder. Sea urchin-shaped silica powder was ultrasonically dispersed in anhydrous ethanol, then aminosilane coupling agent and ammonia were added, the temperature was raised to 75-85℃ and refluxed for 6-12 hours, and then cooled, washed and dried to obtain sea urchin-shaped amino-terminated organosilicon filler. The weight ratio of tetraethyl orthosilicate, surfactant, catalyst and water is 100:(9~11):(6.5~7):(600~800); the weight-volume ratio of urchin-shaped silica powder, aminosilane coupling agent and ammonia is 100g:(200~400)mL:(100~200)mL.

4. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 3, characterized in that: The weight ratio of the urchin-shaped amino-terminated silicone filler to the epoxy resin is 1:5.

5.

5. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 4, characterized in that: The particle size of the urchin-shaped amino-terminated organosilicon filler is controlled at 10±2μm.

6. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 5, characterized in that: The organosilicon-modified polyimide is obtained by reacting an amino-terminated silane prepolymer with pyromellitic dianhydride at a molar ratio of (0.6–0.8):

1. The amino-terminated silane prepolymer is obtained by reacting γ-aminopropyltriethoxysilane with hydroxyl-terminated silicone oil.

7. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 1, characterized in that: The weight ratio of polyaniline to epoxy resin is 1:6.

875.

8. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 1, characterized in that: The curing agent is an aliphatic polyamine curing agent.

9. The biomimetic anti-fouling coating composition with high adhesion strength as described in claim 1, characterized in that: The pentaerythritol tetraacrylate, polyethylene glycol diacrylate, and amino-terminated polyethylene glycol are reacted in a molar ratio of 1:2:

3.

10. A method for preparing a high-adhesion-strength biomimetic anti-fouling coating composition according to any one of claims 1-9, comprising the following steps: Prepare hyperbranched polymers according to weight percentages to form a tackifier; Prepare epoxy resin, polyetherimide, silicone-modified polyimide, urchin-like amino-terminated silicone filler, polyaniline, and curing agent according to weight percentages, and mix them to form an antifouling agent; By packaging the tackifier and antifouling agent separately, a biomimetic antifouling coating composition with high adhesion strength is obtained.

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