Amphiphilic copolymer marine antifouling material and preparation method and application thereof

Abstract

The application belongs to the technical field of marine antifouling materials, and discloses an amphiphilic copolymer marine antifouling material and a preparation method and application thereof. The antifouling material is prepared from mixed monomers containing hydrophilic vinyl monomers, hydrophobic vinyl monomers, acrylic ester monomers and methacrylic ester monomers through free radical copolymerization under the action of an initiator, and is a vinyl copolymer with hydrophilic segments and hydrophobic segments. According to the application, hydrophilic and hydrophobic side chains are bonded on a single copolymer main chain through molecular design, and the microphase separation and dynamic rearrangement of the hydrophilic and hydrophobic segments in a water environment are utilized to form an amphiphilic polymer brush structure with the dual functions of fouling resistance and fouling detachment. The material solves the performance defects of traditional physical blending or single hydrophilic / hydrophobic coating, and exhibits excellent comprehensive antifouling performance under static and dynamic conditions. Moreover, the preparation process is simple, and the material is suitable for industrial production and high-performance environment-friendly marine antifouling coatings.

Description

Technical Field

[0001] This invention belongs to the field of marine antifouling materials technology, specifically relating to an amphiphilic copolymer marine antifouling material with both fouling resistance and fouling desorption functions, its preparation method, and its application in antifouling coatings. Background Technology

[0002] Marine biofouling—the phenomenon where microorganisms, algae, and invertebrates (such as barnacles and shellfish) attach to, colonize, and damage the surfaces of ships, underwater sensors, aquaculture cages, and other facilities—seriously impacts the economic efficiency and safety of shipping, marine engineering facilities, and aquaculture. Globally, the direct and indirect economic losses caused by this phenomenon reach tens of billions of US dollars annually, manifesting as increased ship drag, significantly increased fuel consumption (up to 40% or more), distortion of monitoring instrument signals, and accelerated corrosion of metal structures. Applying antifouling coatings is currently the most effective and economical protective measure. However, existing mainstream antifouling technologies all have their own insurmountable drawbacks, which are analyzed in detail below: Firstly, hydrophilic antifouling coatings based on polyethylene glycol (PEG) work by forming a dense hydrated layer to physically prevent the initial adhesion of proteins and microorganisms. However, PEG coatings swell excessively in aquatic environments, leading to a sharp decrease in their mechanical strength. The dry contact angle is typically less than 30°, making the coating highly susceptible to cracking and peeling. More importantly, the pure hydrophilic surface experiences chain segment collapse in a dry state and lacks an effective fouling desorption mechanism. Once initial adhesion occurs, subsequent fouling organisms proliferate rapidly. Studies have shown that after immersion in seawater for 30 days, the tensile strength of pure PEG coatings decreases by more than 60%, and the desorption rate for diatoms is typically less than 50%.

[0003] Secondly, hydrophobic low surface energy coatings based on polydimethylsiloxane (PDMS) work by utilizing low surface energy to make it difficult for fouling organisms to adhere firmly, thus facilitating their desorption under water flow shear. However, under static or low-speed (flow rate <1 knot) conditions, these coatings lack active antifouling components, making it easy for biofouling precursors (such as proteins and bacteria) to colonize, resulting in attachment rates of large fouling organisms such as barnacles exceeding 80%, and severely insufficient static antifouling effect.

[0004] Thirdly, traditional release-type antifouling coatings (such as self-polishing coatings based on cuprous oxide) rely on the continuous release of antifouling agents for their antifouling effect. However, this system suffers from a significant contradiction between "burst release" and "depletion": the initial release concentration is often >50 ppb, posing a threat to non-target marine organisms; and the effective antifouling period is only 12–18 months, making it difficult to meet long-term requirements. Unlike this approach that relies on the release of toxic substances, this invention achieves physical antifouling through the intrinsic amphiphilic molecular structure of the material, eliminating the need for heavy metal antifouling agents such as cuprous oxide, thus fundamentally avoiding the environmental risks of release-type coatings.

[0005] Notably, marine fouling larvae exhibit active surface recognition behavior during attachment. Studies have shown that barnacle larvae repeatedly explore substrate surfaces with their antennae before final attachment, and the adhesion of their temporary attachment proteins differs significantly across different wettable surfaces—the adhesion on hydrophobic surfaces (21 ± 2 nN) is much higher than on hydrophilic surfaces (7.2 ± 1 nN). Based on this, the design concept of amphiphilic surfaces has emerged: since larvae have different affinities for hydrophobic or hydrophilic surfaces, they first need to identify and confirm surface suitability before attachment. Amphiphilic surfaces, which simultaneously possess hydrophilic and hydrophobic microregions, can cause "confusion" for larvae during exploration, requiring more time for surface inspection, thus reducing their attachment probability. This behavioral mechanism provides an important theoretical basis for the design of amphiphilic antifouling materials.

[0006] In summary, existing coating technologies generally suffer from the inherent defect of "static surface chemical structure," meaning that once the coating surface is covered by a biofilm, it lacks effective self-renewal or dynamic reconstruction capabilities, leading to irreversible degradation of antifouling performance over time. How to achieve a synergistic effect of "inhibiting initial adhesion" and "promoting fouling desorption" in a single coating, while simultaneously considering environmental protection and long-term effectiveness, is a pressing technical challenge in this field. Based on the above background, this invention synthesizes an amphiphilic copolymer through molecular design. Its surface hydrophilic / hydrophobic segments can dynamically rearrange in an aqueous environment to form a continuously stable amphiphilic polymer brush structure, aiming to resolve the aforementioned contradictions from the intrinsic structure of the material. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies, such as poor mechanical properties of hydrophilic coatings, static antifouling failure of hydrophobic coatings, and the contradiction between explosive release and degradation of traditional release coatings. This invention provides an amphiphilic copolymer marine antifouling material with a simple synthesis route and dual functions of fouling resistance and fouling desorption, as well as its preparation method.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides an amphiphilic copolymer marine antifouling material, wherein the antifouling material is a vinyl copolymer having hydrophilic and hydrophobic segments. The antifouling material is mainly prepared by free radical copolymerization of the following components in parts by weight: 100 parts vinyl monomer, 0.5-3 parts initiator, and 100-400 parts organic solvent; wherein the vinyl monomer includes 10-30 parts hydrophilic monomer, 10-30 parts hydrophobic monomer, 30-60 parts acrylate monomer, and 10-30 parts methacrylate monomer.

[0009] In the copolymer structure of this invention, hydrophilic side chains (such as polyethylene glycol segments, hydroxyl groups, or zwitterionic groups) extend under hydration to form a hydrated layer, inhibiting the initial adhesion of proteins and microorganisms; hydrophobic side chains (such as polydimethylsiloxane or fluorinated alkyl segments) impart low surface energy to the surface, reducing the ability of fouling organisms to adhere firmly. Acrylic monomers provide flexibility and adhesion to the main chain, while methacrylate monomers contribute to the rigidity of the main chain and the regulation of the glass transition temperature. The four types of monomers achieve a uniform distribution of hydrophilic / hydrophobic microregions through random copolymerization, synergistically exerting impedance and desorption functions.

[0010] Further, the hydrophilic monomer is vinyl-terminated polyethylene glycol with a number-average molecular weight of 500 g / mol to 5000 g / mol, preferably 1000 g / mol to 3000 g / mol. The hydrophilic monomer can also be hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate, or other hydroxyl-containing acrylate hydrophilic monomers. The hydrophilic monomer can also be a betaine-type zwitterionic precursor having the structure shown in formula (I): (I) Wherein, R1 represents H or CH3, and R2 represents an alkyl group with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms.

[0011] Further, the hydrophobic monomer is a vinyl-terminated polydimethylsiloxane with a number-average molecular weight of 500 g / mol to 5000 g / mol, preferably 1000 g / mol to 3000 g / mol. The hydrophobic monomer can also be a fluoroalkyl olefin monomer, such as trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecylfluoroheptyl methacrylate, dodecylfluoroheptyl acrylate, perfluorohexylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, perfluorodecylethyl methacrylate, perfluorodecylethyl methacrylate, etc.

[0012] Further, the acrylate monomers are one or more of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate. Methyl acrylate and ethyl acrylate are preferred as the acrylate monomers.

[0013] Further, the methacrylate monomers are one or more of methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate. Methyl methacrylate and ethyl methacrylate are preferred.

[0014] Further, the initiator is one or more of azobisisobutyronitrile (AIBN), azobisisovalerate, and benzoyl peroxide, preferably azobisisobutyronitrile. The organic solvent is one or more of alcohol solvents (such as isopropanol, n-butanol, isobutanol, propylene glycol methyl ether), ketone solvents (such as methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone, cyclohexanone), ester solvents (such as ethyl acetate, butyl acetate), and aromatic solvents (such as toluene, xylene), preferably a mixed solvent of xylene and n-butanol.

[0015] Secondly, the present invention provides a method for preparing the above-mentioned amphiphilic copolymer marine antifouling material, characterized by comprising the following steps: in an inert gas atmosphere, the vinyl monomer and the initiator are dissolved in the organic solvent, and after deoxygenation treatment, a free radical copolymerization reaction is carried out at 60-100°C (preferably 70-80°C) for 12-48 hours (preferably 24 hours). After the reaction is completed, the mixture is cooled to room temperature, and a polymer solution with a solid content of 20%-50% is obtained by direct discharge without precipitation or purification treatment, thereby obtaining the amphiphilic copolymer marine antifouling material.

[0016] Furthermore, the deoxygenation treatment includes: subjecting the mixed system to a freezing-vacuuming-thawing cycle 3 to 6 times, preferably 5 times. The inert gas is nitrogen or argon, preferably nitrogen.

[0017] Furthermore, the organic solvent is a mixture of xylene and n-butanol, wherein the mass ratio of xylene to n-butanol is (1-4):1, preferably 2:1.

[0018] Thirdly, embodiments of the present invention also provide an amphiphilic copolymer marine antifouling material prepared by the aforementioned preparation method; and embodiments of the present invention also provide the application of the aforementioned amphiphilic copolymer marine antifouling material in the preparation of marine antifouling coatings or in the field of antifouling in marine environments. The coating may further include conventional additives such as iron oxide red, talc, dispersants, defoamers, and antisettling agents, as well as organic mixed solvents, which are ground and dispersed to a fineness of less than 20 μm before application.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) Intrinsic amphiphilic synergy, breaking through performance bottlenecks: This invention introduces both hydrophilic segments (such as polyethylene glycol segments, hydroxyl side groups, etc.) and hydrophobic segments (such as polydimethylsiloxane segments, fluorinated alkyl side groups, etc.) into the molecular chain through free radical copolymerization, forming a vinyl copolymer with an amphiphilic structure. The hydrophilic segments form a dense hydration layer underwater, giving the coating excellent fouling resistance (protein adsorption rate reduced by more than 80%), while the hydrophobic segments give the coating low surface energy to facilitate fouling desorption (algae desorption rate reaches more than 95%). The synergy of the two makes the coating exhibit excellent comprehensive antifouling performance under both static and dynamic conditions, overcoming the shortcomings of traditional single hydrophilic or hydrophobic coatings that are ineffective in addressing one aspect while neglecting the other.

[0020] (2) Meets stringent static antifouling requirements: Tests showed that the coating of this invention can adsorb bovine serum albumin at a relative level as low as 15%–20%, and desorb Navicula as high as 92%–98%, effectively solving the problem that traditional low surface energy coatings are easily colonized by organisms at low speeds (<5 knots). In a static seawater immersion test lasting up to 180 days, no large fouling organisms such as barnacles and oysters were found firmly attached to the coating surface, and only a small amount of diatoms could be removed by a low-pressure water gun, indicating that it has excellent long-term static antifouling capabilities. Compared with the comparative example, the coating of this invention had zero area of ​​large fouling organisms attached after 6 months of static immersion, while the purely hydrophobic coating had an attachment area of ​​over 60%, highlighting the key role of hydrophilic components under static conditions.

[0021] (3) Environmentally friendly and long-lasting stability: The material of this invention does not contain traditional toxic materials such as organotin and cuprous oxide, and complies with environmental regulations. At the same time, since the amphiphilic segments can dynamically migrate and reconstruct in the aquatic environment, even if the coating surface is slightly contaminated, it can restore its antifouling activity upon re-immersion in water, avoiding the "release-depletion" failure mode of traditional release coatings. The coating can maintain stable antifouling activity even after long-term immersion in seawater, and has the potential for long-term service.

[0022] (4) Simple process and controllable cost: One-pot free radical polymerization is adopted, the synthesis route is short, the monomer conversion rate can reach more than 92%, the production cost is significantly reduced compared with block copolymers, and it is suitable for industrial scale-up production. Detailed Implementation

[0023] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0024] Example 1 1. Dissolve 20 g of vinyl-terminated polyethylene glycol (PEG-MA, Mn=2000 g / mol), 20 g of vinyl-terminated polydimethylsiloxane (PDMS-MA, Mn=2000 g / mol), 40 g of ethyl acrylate (EA), 20 g of ethyl methacrylate (EMA), and 1.5 g of azobisisobutyronitrile (AIBN) in a mixed solvent of 100 g of xylene and 50 g of n-butanol. The mixture is subjected to a freeze-vacuum-thaw cycle five times to remove oxygen, followed by nitrogen protection and reaction in an oil bath at 75°C for 24 hours. After the reaction, the mixture is cooled and discharged to obtain a polymer solution with a solid content of approximately 40%, which is the amphiphilic copolymer marine antifouling material, denoted as P-1.

[0025] 2. Preparation and performance testing of antifouling coatings Coating formulation: P-1 resin solution (35 parts based on solid resin), iron oxide red (5 parts), talc (10 parts), dispersant BYK-110 (0.5 parts), defoamer BYK-077 (0.3 parts), polyamide wax (2 parts), mixed organic solvent (xylene: propylene glycol methyl ether acetate = 7:3, 20 parts).

[0026] Preparation and Testing: The above components were dispersed uniformly at high speed and ground to a fineness of <20μm. The resulting coating was applied to an epoxy-primed tinplate and cured at 60℃ for 24 hours, with the dry film thickness controlled at 150±10μm. Contact angle, protein adsorption capacity, algae desorption rate, and adhesion were tested according to relevant standards.

[0027] Example 2 1. Dissolve 30 g PEG-MA (Mn=2000 g / mol), 10 g PDMS-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-2.

[0028] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0029] Example 3 1. Dissolve 10 g PEG-MA (Mn=2000 g / mol), 30 g PDMS-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-3.

[0030] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0031] Example 4 1. Dissolve 20 g PEG-MA (Mn=2000 g / mol), 20 g PDMS-MA (Mn=2000 g / mol), 30 g EA, 30 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-4.

[0032] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0033] Example 5 1. Dissolve 20 g PEG-MA (Mn=2000 g / mol), 20 g PDMS-MA (Mn=2000 g / mol), 50 g EA, 10 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-5.

[0034] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0035] Example 6 1. Dissolve 20 g PEG-MA (Mn=2000 g / mol), 20 g PDMS-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 0.8 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-6.

[0036] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0037] Example 7 1. Dissolve 20 g PEG-MA (Mn=2000 g / mol), 20 g PDMS-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 3.0 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain the amphiphilic copolymer marine antifouling material P-7.

[0038] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0039] The specific material feeding quality data for each embodiment are shown in Table 1 below: Table 1. Mass of each component fed into Examples 1-7 (unit: grams) Examples 1 through 7 were all prepared using the same steps, with only the monomer ratio and initiator dosage varying according to Table 1. The resulting seven antifouling materials were named P-1 through P-7, respectively.

[0040] <Supplementary Notes> Examples 1-7 above use vinyl-terminated polyethylene glycol (PEG-MA) and vinyl-terminated polydimethylsiloxane (PDMS-MA) as illustrative examples of hydrophilic / hydrophobic macromonomers. Those skilled in the art will understand that in other embodiments, the hydrophilic monomer can also be a hydroxyl-containing hydrophilic monomer such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or polyethylene glycol methacrylate; the hydrophobic monomer can also be a fluoroalkyl-containing olefinic hydrophobic monomer such as trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecylfluoroheptyl methacrylate, dodecylfluoroheptyl acrylate, perfluorohexylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, or perfluorodecylethyl methacrylate. These alternative solutions can also achieve the amphiphilic synergistic antifouling effect of the present invention and all fall within the protection scope of the present invention.

[0041] Performance testing The above polymer solution was coated onto tinplate treated with epoxy primer and cured at 60°C for 24 hours, with the dry film thickness controlled at 150±10μm. The following performance tests were performed on each coating: (1) Static water contact angle: The static contact angle of deionized water on the coating surface was tested using a contact angle measuring instrument and the seat drop method.

[0042] (2) Protein adsorption amount: The coated sample was immersed in a fluorescently labeled bovine serum albumin (BSA-FITC, concentration 1 mg / mL) solution and incubated at 37°C for 2 hours. After washing, the adsorption amount was measured by a fluorescence spectrophotometer. The relative adsorption rate was calculated with the adsorption amount of the uncoated bare steel plate as 100%.

[0043] (3) Algae desorption rate: The coated sample was placed in artificial seawater, inoculated with Navicula incerta, and statically soaked for 14 days. Then, it was rinsed in a water flow of 0.5 m / s for 10 minutes. The number of attached algae cells before and after rinsing was counted, and the desorption rate was calculated.

[0044] (4) Coating adhesion: The cross-cut adhesion test was conducted according to GB / T 9286-1998 standard, and the rating was 0 to 5.

[0045] The test results for each embodiment are summarized in Table 2.

[0046] Table 2. Performance test results of the antifouling coatings prepared in Examples 1-7 Comparative Example To highlight the synergistic effect of the four components—hydrophilic monomer, hydrophobic monomer, acrylate monomer, and methacrylate monomer—in this invention, the following comparative examples are provided: Comparative Example 1 (containing only hydrophilic and hydrophobic macromonomers, excluding small molecule acrylates and methacrylates): 1. Dissolve 50 g of PEG-MA (Mn=2000 g / mol), 50 g of PDMS-MA (Mn=2000 g / mol), and 1.5 g of AIBN in a mixed solvent of 100 g of xylene and 50 g of n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain a copolymer material denoted as D-1.

[0047] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0048] Comparative Example 2 (containing hydrophilic components, without hydrophobic components): 1. Dissolve 40 g PEG-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain a copolymer material denoted as D-2.

[0049] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0050] Comparative Example 3 (containing hydrophobic components, without hydrophilic components): 1. Dissolve 40 g PDMS-MA (Mn=2000 g / mol), 40 g EA, 20 g EMA, and 1.5 g AIBN in a mixed solvent of 100 g xylene and 50 g n-butanol. Perform the same polymerization and post-treatment steps as in Example 1 to obtain a copolymer material denoted as D-3.

[0051] 2. Preparation and performance testing of antifouling coating: The same coating formulation and testing methods as in Example 1 were used.

[0052] The comparative materials were prepared into coatings using the same method as in Examples 1-7, and their performance was tested. The results are shown in Table 3.

[0053] Table 3. Performance test results of the antifouling coatings prepared in Comparative Examples 1–3 Table 4 Comparison of antifouling performance of Example 1 and Comparative Examples 1-3 after 6 months of static immersion in shallow sea Results Analysis As shown in Table 2, the water contact angles of embodiments P-1 to P-7 of the present invention range from 58° to 72°, falling within a suitable hydrophilic-hydrophobic balance range. This ensures both the hydration of the hydrophilic segments underwater (with a minimum BSA adsorption rate of only 15%) and the low surface energy characteristics of the hydrophobic segments (with a maximum algae desorption rate of 98%), while maintaining adhesion strength of 1 to 2, demonstrating excellent overall performance. Among these, P-1 exhibits the most balanced overall performance and is the optimal embodiment of the present invention. Furthermore, the dry films of the coatings in all embodiments did not show blistering, peeling, or significant discoloration after immersion in seawater for 6 months, indicating excellent resistance to seawater corrosion.

[0054] Analysis of the comparative results in Table 3 shows that: Comparative Example 1, due to the lack of acrylate monomers, resulted in excessive stiffness of the polymer backbone, leading to brittle coatings. Furthermore, the lack of ester groups to regulate the hydrophilic-hydrophobic balance resulted in a significant decrease in desorption rate. Comparative Example 2 (pure hydrophilic system) was excessively hydrophilic, resulting in severe swelling in wet conditions, poor adhesion, and an extremely low desorption rate (only 45%), while protein adsorption was as high as 45%. Comparative Example 3 (pure hydrophobic system), although achieving a desorption rate of 82%, had a protein adsorption rate as high as 78%, indicating severely insufficient static antifouling ability and easy colonization by organisms under static conditions.

[0055] The above comparisons fully demonstrate that the hydrophilic monomers, hydrophobic monomers, acrylate monomers, and methacrylate monomers in this invention produce a significant synergistic effect under specific ratios. The absence of any one of these components or an imbalance in their ratios prevents the achievement of excellent overall antifouling performance. In particular, Comparative Example 3 showed a large biofouling area of ​​up to 60% after 6 months of static immersion, while Example 1 of this invention showed zero. This directly reflects the irreplaceable role of the hydrophilic segments in inhibiting initial adhesion.

[0056] Furthermore, the coating of Example 1 of the present invention and the coatings of Comparative Examples 1-3 were subjected to a 6-month shallow sea static immersion experiment, and the results are shown in Table 4. These results further confirm the significant advancement and practical value of the technical solution of the present invention.

[0057] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An amphiphilic copolymer marine antifouling material, characterized in that, The antifouling material is a vinyl copolymer with hydrophilic and hydrophobic segments; The antifouling material is mainly prepared by free radical copolymerization of the following components in parts by weight: 100 parts vinyl monomer, 0.5-3 parts initiator, and 100-400 parts organic solvent; The vinyl monomers include 10-30 parts of hydrophilic monomers, 10-30 parts of hydrophobic monomers, 30-60 parts of acrylate monomers, and 10-30 parts of methacrylate monomers.

2. The amphiphilic copolymer marine antifouling material according to claim 1, characterized in that, The hydrophilic monomer is one or more of vinyl-terminated polyethylene glycol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and polyethylene glycol methacrylate, wherein the number average molecular weight of the vinyl-terminated polyethylene glycol is 500 g / mol to 5000 g / mol, preferably 1000 g / mol to 2000 g / mol; or the hydrophilic monomer is a betaine-type zwitterionic precursor having the structure shown in formula (I): （I） Wherein, R1 represents H or CH3, and R2 represents an alkyl group with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms.

3. The amphiphilic copolymer marine antifouling material according to claim 1, characterized in that, The hydrophobic monomer is one or more of the following: vinyl-terminated polydimethylsiloxane, trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, perfluorohexylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, and perfluorodecylethyl methacrylate. The number average molecular weight of the vinyl-terminated polydimethylsiloxane is 500 g / mol to 5000 g / mol, preferably 1000 g / mol to 3000 g / mol.

4. The amphiphilic copolymer marine antifouling material according to claim 1, characterized in that: The acrylate monomers are one or more selected from methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate, preferably ethyl acrylate; the methacrylate monomers are one or more selected from methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate, preferably ethyl methacrylate.

5. The amphiphilic copolymer marine antifouling material according to claim 1, characterized in that, The initiator is one or more of azobisisobutyronitrile, azobisisovalerate, and benzoyl peroxide, preferably azobisisobutyronitrile; the organic solvent is one or more of alcohol solvents, ketone solvents, ester solvents, and aromatic solvents, preferably a mixture of xylene and n-butanol.

6. A method for preparing an amphiphilic copolymer marine antifouling material as described in any one of claims 1-5, characterized in that, Includes the following steps: In an inert gas atmosphere, the vinyl monomer and initiator are dissolved in the organic solvent. After deoxygenation treatment, a free radical copolymerization reaction is carried out at 60-100°C for 12-48 hours. After the reaction is completed, the mixture is cooled and discharged to obtain a solution of the amphiphilic copolymer, thus preparing the amphiphilic copolymer marine antifouling material.

7. The preparation method according to claim 6, characterized in that, The deoxygenation treatment includes: subjecting the mixed system to a freezing-vacuuming-thawing cycle 3 to 6 times, preferably 5 times; the inert gas is nitrogen or argon, preferably nitrogen; the reaction temperature is preferably 70 to 80°C, and the reaction time is preferably 24 hours.

8. The preparation method according to claim 6, characterized in that, The organic solvent is a mixture of xylene and n-butanol, wherein the mass ratio of xylene to n-butanol is (1-4):1, preferably 2:

1.

9. A marine antifouling coating, characterized in that, The coating comprises an amphiphilic copolymer marine antifouling material as described in any one of claims 1-5 as a film-forming substance, as well as pigments, fillers, additives and organic solvents; the mass fraction of the amphiphilic copolymer solid resin in the coating is 20% to 50%.

10. The use of the amphiphilic copolymer marine antifouling material according to any one of claims 1-5 or the marine antifouling coating according to claim 9 for preventing marine biofouling on ships, offshore platforms or aquaculture facilities.

Images