Preparation method of modified cuprous oxide antifouling material, product and application thereof

Abstract

The application relates to a preparation method of modified cuprous oxide antifouling material and products and applications thereof, and is beneficial to polyol reduction preparation of alcohol hydroxyl on the surface of cuprous oxide nanoparticles, quaternary ammonium salt cation modification of the cuprous oxide nanoparticles, improvement of the antifouling performance of the cuprous oxide nanoparticles, further construction of a silicone polymer layer on the surface of the quaternary ammonium salt modified cuprous oxide nanoparticles, hindering of adhesion of marine microorganisms by the low-surface-energy silicone polymer layer, and facilitation of release control of the cuprous oxide and stability of copper ion release. The modified cuprous oxide antifouling material has efficient and stable antifouling effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, and relates to a preparation method of modified cuprous oxide antifouling material, a product and application thereof, in particular to a marine antifouling material and a preparation method thereof. BACKGROUND

[0002] During ocean voyage, up to 4000 kinds of microorganisms, marine plants and marine animals in the ocean are easy to adhere to the ship bottom, which will increase the ship resistance, reduce the ship speed, increase the fuel consumption and mechanical wear; the adhesion of marine organisms will also damage the paint film and accelerate the corrosion of steel plate, and increase the frequency and time of ship maintenance. With the continuous exploration of human beings on marine resources and the vigorous development of shipbuilding industry, the problem of marine biofouling is becoming more and more obvious. Coating antifouling paint is the most economical and effective measure to reduce marine fouling of ships and has the widest range of application. Antifouling paint is generally coated on the ship bottom above the rust paint, and is in the outermost layer; the main function is to release toxic materials through the diffusion, hydrolysis or other ways of the paint film, so as to prevent marine organisms from adhering to the ship bottom. Antifouling agent is the main component of the antifouling coating. The widely used antifouling agent is cuprous oxide. The current problem of antifouling paint is that the effective component is released at a relatively fast speed in the early stage, showing good effect, but because the antifouling agent is consumed too fast, there is almost no antifouling agent released in the later stage, so that the material surface is attached and fouled by marine organisms. Therefore, a large proportion of cuprous oxide is often added in the antifouling paint, usually more than 50wt%, in order to provide a relatively ideal long-term antifouling effect. However, if a high amount of cuprous oxide is continuously used, excessive copper ions will be released into the marine environment and continuously enriched in the marine ecological system, which poses a great threat to the safety of the marine ecological system and human health.

[0003] In the long term, to protect the marine environment, copper-containing antifouling agents should be slow-released, minimizing the amount of cuprous oxide added while maintaining antifouling performance. Patent CN113402977A discloses a composite antifouling coating with controlled release of cuprous oxide and its preparation method. Cuprous oxide is encapsulated onto a composite nanocarrier, and the compactness of the composite nanocarrier is controlled by pH, enabling uniform and quantitative release of the encapsulated cuprous oxide. Patent CN116676011A utilizes in-situ reduction of metallic copper on cellulose to produce a cellulose-loaded metallic copper antifouling powder. This antifouling powder can exchange copper and sodium ions in the presence of seawater, achieving slow release of copper ions. Patent CN116285465A uses catechol monomers to impregnate and deposit on the surface of cuprous oxide core material, encapsulating a reducing organic layer rich in phenolic hydroxyl groups, providing physical isolation and a chemical reduction microenvironment, thereby preventing oxygen, water, light, etc. from corroding the core material, inhibiting the oxidative corrosion of the core material, significantly improving the stability of cuprous oxide, and exhibiting a steady copper ion release rate.

[0004] As can be seen, existing technical solutions for reducing the amount of cuprous oxide added mostly rely on coating the material to achieve controlled release of copper ions, thereby reducing the amount of cuprous oxide added while still ensuring antifouling performance. As a single inorganic material, cuprous oxide has limited antibacterial and antimicrobial properties. Improving its antifouling properties is also an effective way to reduce its dosage. Summary of the Invention

[0005] The present invention provides a method for preparing a modified cuprous oxide antifouling material. The alcoholic hydroxyl groups on the surface of cuprous oxide nanoparticles, which are prepared by polyol reduction, are then modified with quaternary ammonium salt cations to improve the antifouling properties of the cuprous oxide nanoparticles. An organosilicon polymer layer is further constructed on the surface of the quaternary ammonium salt-modified cuprous oxide nanoparticles. The low surface energy organosilicon polymer layer can hinder the adhesion of marine microorganisms and help control the release of cuprous oxide. Therefore, only a small amount of the modified cuprous oxide antifouling material of the present invention is required to achieve the same antifouling effect as conventional cuprous oxide antifouling materials.

[0006] Another object of the present invention is to provide a modified cuprous oxide antifouling material product prepared by the above method.

[0007] Another object of the present invention is to provide an application of the above product.

[0008] The object of the present invention is achieved by the following scheme: A method for preparing a modified cuprous oxide antifouling material, characterized in that it comprises the following steps:

[0009] Step 1): mix the divalent copper salt solution and the dihydric alcohol mixture uniformly at room temperature, and then transfer into a hydrothermal reactor and seal. Heat to 160-180℃, and react for 30-60 min. The obtained product is centrifuged and filtered, and then washed with anhydrous ethanol and deionized water for 3 times to obtain cuprous oxide nanoparticles.

[0010] Step 2): disperse the cuprous oxide nanoparticles prepared in step 1) in deionized water, and then ultrasonically disperse them uniformly. Adjust the pH value of the dispersion to 11.0 by using a sodium hydroxide solution. Heat to 60-80℃, and then drop in a certain amount of an epoxy-terminated allyl polyether aqueous solution at intervals, and react for 4-6 h. After the reaction is completed, cool to room temperature, and then filter to obtain a precipitate, which is soaked in acetone, and then filtered and dried to obtain an epoxy-terminated allyl polyether-modified cuprous oxide nanoparticle.

[0011] Step 3): ultrasonically disperse the epoxy-terminated allyl polyether-modified cuprous oxide nanoparticles prepared in step 2) and an initiator potassium persulfate in distilled water, and then add a certain amount of dimethyldiallylammonium chloride into a three-necked flask, heat to 60-80℃, and react for 15-30 min. Then add the initiator potassium persulfate, an epoxy-terminated vinyl silicone and distilled water, and react for 15-30 min. Finally, heat to react for 4-6 h, and then cool to room temperature naturally, and then wash with ethanol and deionized water for 3 times to obtain the modified cuprous oxide antifouling material.

[0012] The divalent copper salt in step 1) is one of copper nitrate, copper acetate and copper chloride.

[0013] The concentration of the divalent copper salt solution in step 1) is 0.5 mol / L.

[0014] The dihydric alcohol in step 1) is one of butanediol, pentanediol and hexanediol.

[0015] The molar ratio of the dihydric alcohol to the divalent copper salt in step 1) is 0.5-1:1.

[0016] The structural formula of the epoxy-terminated allyl polyether in step 2) is as follows:

[0017]

[0018] wherein m is 4-8, and n is 4-8.

[0019] The mass ratio of the epoxy-terminated allyl polyether added in step 2) to the cuprous oxide nanoparticles is 2-4:1.

[0020] The mass ratio of the dimethyldiallylammonium chloride, the epoxy-terminated vinyl silicone and the epoxy-terminated allyl polyether-modified cuprous oxide nanoparticles added in step 3) is (2-4):(2-4):1.

[0021] The application provides a modified cuprous oxide antifouling material prepared according to any of the above methods, wherein the modified cuprous oxide antifouling material has a particle size D50 of less than 150 nm and a particle size D90 of less than 250 nm.

[0022] The application provides an application of the modified cuprous oxide antifouling material in a marine antifouling coating.

[0023] Compared with the prior art, the modified cuprous oxide antifouling material has the following advantages:

[0024] The divalent copper ions are reduced by using a dihydric alcohol with appropriate reducing capacity to obtain cuprous oxide nanoparticles with alcohol hydroxyl groups adsorbed on the surface. The cuprous oxide nanoparticles with alcohol hydroxyl groups adsorbed on the surface are further combined with an epoxy-terminated allyl polyether through an etherification reaction to obtain end-alkenyl modified cuprous oxide nanoparticles. The end-alkenyl groups on the surface of the end-alkenyl modified cuprous oxide nanoparticles are used for polymerization with dimethyldiallylammonium chloride to obtain quaternary ammonium salt modified cuprous oxide nanoparticles. Finally, a layer of hydrophobic organosilicon polymer is constructed on the surface of the quaternary ammonium salt modified cuprous oxide nanoparticles through polymerization with an end-vinyl silicone, and a hydrophobic coated quaternary ammonium salt modified cuprous oxide nanoparticle antifouling material is obtained.

[0025] The inner layer of the hydrophobic coated quaternary ammonium salt modified cuprous oxide nanoparticle antifouling material is composed of cuprous oxide inorganic nanoparticles, which has broad-spectrum antibacterial properties, and organic quaternary ammonium salt antibacterial stability and high efficiency. As an antifouling agent applied to an antifouling coating, the amount of cuprous oxide added can be significantly reduced. The low-surface-energy organosilicon polymer outer layer can hinder the adhesion of marine microorganisms, protect the cuprous oxide particles in the inner layer, and inhibit the rapid oxidation of monovalent copper ions, thereby achieving a slow and stable release effect. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 Test results of copper ion leaching rates of antifouling coatings prepared from the antifouling materials obtained in Example 1 and Comparative Examples 1-4;

[0027] Figure 2 Particle size curve of the modified cuprous oxide antifouling material of Example 1. DETAILED DESCRIPTION

[0028] The technical solutions of the application will be further described below according to specific examples. The protection scope of the application is not limited to the following examples, and these examples are listed only for illustrative purposes and do not limit the application in any way.

[0029] Example 1

[0030] A preparation method of a modified cuprous oxide antifouling material, characterized by comprising the following steps:

[0031] (1): 200 ml of 0.5 mol / L copper nitrate trihydrate aqueous solution and 4.51 g (0.05 mol) of 1,2-butanediol mixture were mixed uniformly at room temperature, transferred into a hydrothermal reactor, sealed, heated to 160°C, and reacted for 60 min; the obtained product was centrifuged, filtered, washed with anhydrous ethanol and deionized water for 3 times, and copper(I) oxide nanoparticles were obtained;

[0032] (2): 5 g of copper(I) oxide nanoparticles prepared in step (1) were dispersed in 100 mL of deionized water, ultrasonically dispersed, the pH value of the dispersion was adjusted to 11.0 by using 2 mol / L sodium hydroxide solution, heated to 60°C, and 11 mL of 0.5 mol / L epoxy-terminated allyl polyether (m=4, n=4, molecular weight 522) aqueous solution was added dropwise in four times with 1 h interval, and reacted for 4 h; a total of 11.48 g of epoxy-terminated allyl polyether (m=4, n=4) was added; after the reaction was completed, the mixture was cooled to room temperature, and the precipitate was obtained by suction filtration, soaked in acetone, suction filtered and dried to obtain epoxy-terminated allyl polyether modified copper(I) oxide nanoparticles;

[0033] (3): 5 g of epoxy-terminated allyl polyether modified copper(I) oxide nanoparticles prepared in step (2), 0.1 g of initiator potassium persulfate were ultrasonically dispersed in 34.8 g of distilled water, 15 g of dimethyldiallylammonium chloride was added into a three-necked flask, heated to 80°C and reacted for 15 min, then 0.1 g of initiator potassium persulfate, 15 g of vinyl-terminated silane and 30 g of distilled water were added, reacted for 15 min, and finally reacted for 4 h with temperature maintained, and then naturally cooled to room temperature, and washed with ethanol and deionized water for 3 times to obtain the modified copper(I) oxide antifouling material.

[0034] In step 1) of the example, the molar ratio of diol to divalent copper salt was 0.5:1; the mass ratio of epoxy-terminated allyl polyether (m=4, n=4) to copper(I) oxide nanoparticles was 2.3:1; in step 3), the mass ratio of dimethyldiallylammonium chloride, vinyl-terminated silane and epoxy-terminated allyl polyether modified copper(I) oxide nanoparticles was 3:3:1.

[0035] The structural formula of the epoxy-terminated allyl polyether in step 2) is as follows:

[0036]

[0037] In the formula, m=4, n=4.

[0038] The particle size D50 of the obtained modified copper(I) oxide antifouling material was 116 nm, and the particle size D90 was 211 nm. The particle size curve is shown in Figure 2 .

[0039] Example 2

[0040] A preparation method of a modified copper(I) oxide antifouling material, characterized in that the method comprises the following steps:

[0041] Step 1): At room temperature, mix 200 ml of a 0.5 mol / L copper acetate monohydrate aqueous solution with 7.81 g (0.075 mol) of 1,2-pentanediol. The mixture is then placed in a sealed hydrothermal reactor. The temperature is raised to 180°C and the reaction is continued for 30 minutes. The resulting product is centrifuged and filtered, then washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles.

[0042] Step 2): Disperse 5g of cuprous oxide nanoparticles prepared in step 1) in 100mL of deionized water, and ultrasonicate to uniformly disperse the cuprous oxide nanoparticles. Adjust the pH value of the dispersion to 11.0 with a 2mol / L sodium hydroxide solution; raise the temperature to 80°C, and dropwise add 10mL of a 0.5mol / L aqueous solution of epoxy-terminated allyl polyether (m=4, n=8, molecular weight 754) four times every 1h, and react for 4h; a total of 15.08g of epoxy-terminated allyl polyether (m=4, n=8) is added; after the reaction is completed, cool to room temperature, filter the precipitate, soak it in acetone, filter it again, and dry it to obtain terminal olefin-modified cuprous oxide nanoparticles;

[0043] Step 3): 5 g of terminal olefin-modified cuprous oxide nanoparticles and 0.1 g of initiator potassium persulfate prepared in step 2) were ultrasonically dispersed in 44.8 g of distilled water, 10 g of dimethyldiallylammonium chloride was added to a three-necked flask, the temperature was raised to 60° C. and the reaction was continued for 30 min, and then 0.1 g of initiator potassium persulfate, 10 g of terminal vinyl silicon and 30 g of distilled water were added and the reaction was continued for 30 min; finally, the reaction was kept warm for 5 h, the mixture was naturally cooled to room temperature, and the mixture was washed three times with ethanol and deionized water to obtain a modified cuprous oxide antifouling material;

[0044] In step 1) of this embodiment, the molar ratio of the diol to the divalent copper salt is 0.75:1; in step 2), the mass ratio of the epoxy-terminated allyl polyether (m=4, n=8) to the cuprous oxide nanoparticles is 3.0:1; and in step 3), the mass ratio of dimethyldiallylammonium chloride, vinyl-terminated silicon, and alkenyl-terminated cuprous oxide nanoparticles is 2:2:1.

[0045] The particle size D50 of the obtained modified cuprous oxide antifouling material is 121 nm, and D90 is 234 nm.

[0046] Example 3

[0047] A method for preparing a modified cuprous oxide antifouling material, characterized by comprising the following steps:

[0048] Step 1): At room temperature, mix 200 ml of a 0.5 mol / L aqueous solution of cupric chloride dihydrate with 11.82 g (0.1 mol) of 1,2-hexanediol. The mixture is then placed in a sealed hydrothermal reactor. The temperature is raised to 170°C and the reaction is continued for 45 minutes. The resulting product is centrifuged and filtered, then washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles.

[0049] Step 2): Disperse 5g of cuprous oxide nanoparticles prepared in step 1) in 100mL of deionized water and sonicate to evenly disperse the cuprous oxide nanoparticles. Adjust the pH of the dispersion to 11.0 with a 2mol / L sodium hydroxide solution. Raise the temperature to 80°C and dropwise add 10mL of a 0.5mol / L aqueous solution of epoxy-terminated allyl polyether (m=8, n=8, molecular weight 930) four times every 1h. React for 4h; a total of 18.60g of epoxy-terminated allyl polyether (m=8, n=8) is added. After the reaction is complete, cool to room temperature, filter the precipitate, soak it in acetone, and then filter and dry it to obtain terminal olefin-modified cuprous oxide nanoparticles.

[0050] Step 3): Ultrasonic dispersion of 5g of the terminal olefin-modified cuprous oxide nanoparticles prepared in step 2) and 0.1g of potassium persulfate (initiator) in 34.8g of distilled water was performed. 20g of dimethyldiallylammonium chloride was added to a three-necked flask. The temperature was raised to 60°C and the reaction was continued for 30 minutes. Then, 0.1g of potassium persulfate (initiator), 20g of vinyl-terminated silicon, and 20g of distilled water were added and the reaction was continued for 30 minutes. Finally, the reaction was kept at this temperature for 6 hours, cooled naturally to room temperature, and washed three times with ethanol and deionized water to obtain the modified cuprous oxide antifouling material.

[0051] In this example, the molar ratio of diol to divalent copper salt in step 1) was 1:1; in step 2), the mass ratio of epoxy-terminated allyl polyether (m=8, n=8) to cuprous oxide nanoparticles was 3.7:1; and in step 3), the mass ratio of dimethyldiallylammonium chloride, vinyl-terminated silicon, and alkenyl-terminated cuprous oxide nanoparticles was 4:4:1. The resulting modified cuprous oxide antifouling material had a particle size D50 of 124 nm and a D90 of 228 nm.

[0052] Comparative Example 1

[0053] Comparative Example 1: Cuprous oxide nanoparticles were prepared using the same raw materials and process as in step 1) of Example 1, without the modification treatments in steps 2) and 3), and used as an antifouling material.

[0054] A mixture of 200 ml of 0.5 mol / L copper nitrate trihydrate aqueous solution and 4.51 g (0.05 mol) of 1,2-butanediol was mixed uniformly at room temperature, transferred into a hydrothermal reactor, sealed, heated to 160°C, and reacted for 60 min. The obtained product was centrifuged, filtered, washed with anhydrous ethanol and deionized water for 3 times, and copper(I) oxide nanoparticles were obtained.

[0055] Comparative Example 2

[0056] Comparative Example 2 was prepared by using the same raw materials and process as in Step 1) and Step 2 of Example 1 to obtain end-alkenyl copper(I) oxide nanoparticles.

[0057] (1): A mixture of 200 ml of 0.5 mol / L copper nitrate trihydrate aqueous solution and 4.51 g (0.05 mol) of 1,2-butanediol was mixed uniformly at room temperature, transferred into a hydrothermal reactor, sealed, heated to 160°C, and reacted for 60 min. The obtained product was centrifuged, filtered, washed with anhydrous ethanol and deionized water for 3 times, and copper(I) oxide nanoparticles were obtained;

[0058] (2): 5 g of copper(I) oxide nanoparticles prepared in Step (1) were dispersed in 100 mL of deionized water, ultrasonically dispersed, and the pH value of the dispersion was adjusted to 11.0 with 2 mol / L sodium hydroxide solution. The temperature was raised to 60°C, and 11 mL of 0.5 mol / L end-epoxy allyl polyether (m=4, n=4, molecular weight 522) aqueous solution was added dropwise in four times at an interval of 1 h. The reaction was carried out for 4 h. A total of 11.48 g of end-epoxy allyl polyether (m=4, n=4) was added. After the reaction was completed, the temperature was cooled to room temperature, and the precipitate was obtained by suction filtration, soaked in acetone, and then suction filtered and dried to obtain end-alkenyl modified copper(I) oxide nanoparticles.

[0059] Step 3): 5 g of end-alkenyl modified copper(I) oxide nanoparticles prepared in Step 2), 0.1 g of initiator potassium persulfate were ultrasonically dispersed in 79.9 g of distilled water, 15 g of dimethyldiallylammonium chloride was added to a three-necked flask, the temperature was raised to 80°C, and the reaction was carried out for 15 min, and then the temperature was maintained for 4 h. The temperature was naturally cooled to room temperature, and the product was washed with ethanol and deionized water for 3 times to obtain quaternary ammonium salt modified copper(I) oxide nanoparticles as an antifouling material.

[0060] Comparative Example 3

[0061] The modified copper(I) oxide antifouling material in this comparative example was prepared according to the following steps:

[0062] Step 1): 200ml of 0.5mol / L copper nitrate trihydrate aqueous solution and 3.60g (0.04mol) of 1,2-butanediol mixture were mixed uniformly at room temperature, and then were transferred into a hydrothermal reactor and sealed. The temperature was increased to 160℃, and the reaction was carried out for 60min. The obtained product was centrifuged and filtered, and was washed with anhydrous ethanol and deionized water for 3 times to obtain cuprous oxide nanoparticles.

[0063] Steps 2) and 3) of Comparative Example 3 were the same as those of Example 1.

[0064] In the present comparative example, the molar ratio of dihydric alcohol to divalent copper salt was 0.4:1.

[0065] Comparative Example 4

[0066] The modified cuprous oxide antifouling material in the present comparative example was prepared according to the following steps:

[0067] Step 1): 200ml of 0.5mol / L copper nitrate trihydrate aqueous solution and 10.81g (0.12mol) of 1,2-butanediol mixture were mixed uniformly at room temperature, and then were transferred into a hydrothermal reactor and sealed. The temperature was increased to 160℃, and the reaction was carried out for 60min. The obtained product was centrifuged and filtered, and was washed with anhydrous ethanol and deionized water for 3 times to obtain cuprous oxide nanoparticles.

[0068] Steps 2) and 3) of Comparative Example 4 were the same as those of Example 1.

[0069] In the present comparative example, the molar ratio of dihydric alcohol to divalent copper salt was 1.2:1.

[0070] The antifouling materials obtained in each example and comparative example were prepared into antifouling coatings according to the following basic formula:

[0071] .

[0072] The present application reduces the amount of cuprous oxide added while ensuring antifouling performance, so that the amount of cuprous oxide added in the above antifouling coating basic formula is 15wt%, while the amount of cuprous oxide added in general antifouling coatings is 40~60wt%.

[0073] Antimicrobial performance testing was performed on antifouling coatings prepared from the modified cuprous oxide antifouling materials obtained in the Examples and Comparative Examples (Comparative Example 1 utilizes cuprous oxide nanoparticles not modified with quaternary ammonium salts or organosilicon-modified). The results shown in Table 2 demonstrate that the antifouling coating prepared from the modified cuprous oxide antifouling material in the Examples achieved an antimicrobial efficiency of 99.99%. This is due to the inherently strong antimicrobial properties of the cuprous oxide nanoparticles, and the quaternary ammonium salt bound to the surface of the cuprous oxide nanoparticles, an organic antimicrobial agent with stable and effective antimicrobial properties. The combination of the inorganic antimicrobial nanoparticles and the organic antimicrobial molecules of the quaternary ammonium salts results in a highly effective antifouling coating, even when prepared using the antifouling material described herein at a 15 wt% addition level.

[0074] Comparative Example 1 uses cuprous oxide nanoparticles that are not modified with quaternary ammonium salts and silicone as antifouling materials. Although the cuprous oxide nanoparticles have good antibacterial properties, the antibacterial properties of the coating film are average due to the small amount of cuprous oxide added in the coating formula.

[0075] The cuprous oxide nanoparticles of Comparative Example 2 were modified with quaternary ammonium but not with organosilicon, and showed the same antibacterial properties as in the examples.

[0076] In step 1) of Comparative Example 3, the molar ratio of 1,2-butanediol to divalent copper salt was 0.4:1. Under the hydrothermal reaction conditions, 1,2-butanediol acted as a reducing agent, reducing divalent copper ions to monovalent copper ions while being oxidized to 1,2-butanediol. The low molar ratio of 1,2-butanediol to divalent copper salt resulted in the majority of the 1,2-butanediol being consumed, leaving insufficient 1,2-butanediol molecules adsorbed on the surface of the cuprous oxide nanoparticles to participate in the etherification reaction with the epoxy-terminated allyl polyether in step 2). Consequently, the number of epoxy-terminated allyl polyether molecules bound to the surface of the modified cuprous oxide was relatively small, leaving insufficient molecules to participate in the polymerization reaction with dimethyldiallylammonium chloride in step 3). Consequently, fewer quaternary ammonium salt groups were bound to the surface of the modified cuprous oxide nanoparticles. Consequently, the antibacterial activity was slightly improved compared to Comparative Example 1, but not as high as that of the Examples.

[0077] In Comparative Example 4, the molar ratio of 1,2-butanediol to divalent copper salt is 1.2:1. The molar ratio of 1,2-butanediol to divalent copper salt is relatively high. Under the hydrothermal reaction conditions, part of the monovalent copper ions are further reduced to elemental copper. Since elemental copper has better antibacterial properties than cuprous oxide, the antibacterial results of Comparative Example 4 are better than those of Comparative Examples 1 and 2. Elemental copper has a poorer affinity for diols than cuprous oxide, and the number of epoxy-terminated allyl polyether molecules bound in step 2) is also relatively small, so the antibacterial properties are not as good as those of Example 4.

[0078] .

[0079] The copper ion permeation rate of the antifouling coatings prepared from the antifouling materials obtained in Example 1 and Comparative Examples 1-4 was measured according to the national standard GB / T 6824-2008 "Determination of copper ion permeation rate of ship bottom antifouling paint". The results are shown in Table 1. Figure 1 .

[0080] Figure 1 The test results show that the antifouling coating prepared by the modified cuprous oxide antifouling material in Example 1 has a relatively stable copper ion release rate. After 90 days of testing, the copper ion leakage rate is 23 μg·cm -2 ·d -1 , meeting the surface antifouling requirements of marine devices and facilities. The cuprous oxide antifouling materials used in Comparative Examples 1 and 2 lack the protection of silane groups, so they seep out quickly in the early stage. After 90 days, the copper ion seepage rate is less than 10μg·cm -2 ·d -1 , failing to meet the surface antifouling requirements for marine installations and facilities. In Comparative Example 3, insufficient 1,2-butanediol molecules were adsorbed on the surface of the cuprous oxide nanoparticles to participate in the etherification reaction with the epoxy-terminated allyl polyether in step 2). Consequently, less organosilicon polymer bound to the surface of the modified cuprous oxide nanoparticles resulted in limited protection for cuprous oxide and mediocre copper ion release.

[0081] The antifouling material obtained in Comparative Example 4 performed moderately well because only a portion of the cuprous oxide was reduced to copper and most of the cuprous oxide was still protected by the quaternary ammonium salt molecules.

[0082] Those skilled in the art should note that the embodiments described in the present invention are merely exemplary and that various other substitutions, changes, and improvements may be made within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A method for preparing a modified cuprous oxide antifouling material, characterized in that: The following steps are involved: (1): A divalent copper salt solution and a diol mixture are uniformly mixed at room temperature, with a molar ratio of diol to divalent copper salt of 0.5 to 1:

1. The mixture is then transferred to a hydrothermal reactor, sealed, heated to 160 to 180°C, and reacted for 30 to 60 minutes. The resulting product is centrifuged and filtered, and washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles. (2): The cuprous oxide nanoparticles prepared in step (1) are dispersed in deionized water, and ultrasonically dispersed to make them uniform. The pH value of the dispersion is adjusted to 11.0 with a sodium hydroxide solution, and the temperature is raised to 60-80°C. A certain amount of an epoxy-terminated allyl polyether aqueous solution is added dropwise at regular intervals, and the mass ratio of the epoxy-terminated allyl polyether to the cuprous oxide nanoparticles is 2-4:

1. The reaction is carried out for 4-6 hours. After the reaction is completed, the mixture is cooled to room temperature, and the precipitate is filtered and soaked in acetone, and then filtered and dried to obtain terminal olefin-modified cuprous oxide nanoparticles; (3): The terminal olefin-modified cuprous oxide nanoparticles and the initiator potassium persulfate prepared in step (2) are ultrasonically dispersed in distilled water, dimethyldiallyl ammonium chloride is added to a three-necked flask, the temperature is raised to 60-80°C and the reaction is carried out for 15-30 minutes, and then the initiator potassium persulfate, terminal vinyl silicon and distilled water are added to make the mass ratio of dimethyldiallyl ammonium chloride, terminal vinyl silicon and terminal olefin-modified cuprous oxide nanoparticles be (2-4): (2-4): 1, the reaction is carried out for 15-30 minutes, and the reaction is kept warm for 4-6 hours, cooled naturally to room temperature, and washed 3 times with ethanol and deionized water to obtain the modified cuprous oxide antifouling material.

2. The preparation method according to claim 1, wherein In the step (1), the divalent copper salt is one of copper nitrate, copper acetate and copper chloride.

3. The preparation method according to claim 1, wherein In the step (1), the diol is one of butanediol, pentanediol and hexanediol.

4. The preparation method according to claim 1, wherein In the step (1), the concentration of the divalent copper salt solution is 0.5 mol / L.

5. The preparation method according to claim 1, wherein In the step (2), the structural formula of the epoxy-terminated allyl polyether is as follows: ， Where m is 4~8 and n is 4~8.

6. The preparation method according to any one of claims 1 to 5, characterized in that Prepare as follows: Step 1): 200 ml of a 0.5 mol / L aqueous solution of copper nitrate trihydrate and 4.51 g of 0.05 mol of 1,2-butanediol were uniformly mixed at room temperature, transferred to a hydrothermal reactor, sealed, heated to 160° C., and reacted for 60 minutes; the resulting product was centrifuged and filtered, and washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles; Step 2): 5 g of cuprous oxide nanoparticles prepared in step 1) were dispersed in 100 mL of deionized water and uniformly dispersed by ultrasonication. The pH value of the dispersion was adjusted to 11.0 with a 2 mol / L sodium hydroxide solution, and the temperature was raised to 60° C. 11 mL of a 0.5 mol / L aqueous solution of an epoxy-terminated allyl polyether (m=4, n=4, molecular weight 522) was added dropwise four times every 1 h, with a total of 11.48 g of epoxy-terminated allyl polyether added, and the reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a precipitate, soaked with acetone, and then filtered and dried to obtain terminal olefin-modified cuprous oxide nanoparticles. Step 3): 5g of terminal olefin-modified cuprous oxide nanoparticles and 0.1g of initiator potassium persulfate prepared in step 2) were ultrasonically dispersed in 34.8g of distilled water, 15g of dimethyldiallylammonium chloride was added to a three-necked flask, the temperature was raised to 80°C and the reaction was carried out for 15min, and then 0.1g of initiator potassium persulfate, 15g of terminal vinyl silicon and 30g of distilled water were added and the reaction was carried out for 15min; finally, the reaction was kept warm for 4h, naturally cooled to room temperature, and washed 3 times with ethanol and deionized water to obtain a modified cuprous oxide antifouling material with a particle size D50 of 116nm and D90 of 211nm.

7. The preparation method according to any one of claims 1 to 5, characterized in that Prepare as follows: Step 1): 200 ml of a 0.5 mol / L aqueous solution of copper acetate monohydrate and 7.81 g (0.075 mol) of 1,2-pentanediol were uniformly mixed at room temperature, transferred to a sealed hydrothermal reactor, heated to 180° C., and reacted for 30 minutes; the resulting product was centrifuged and filtered, and washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles; Step 2): 5 g of cuprous oxide nanoparticles prepared in step 1) were dispersed in 100 mL of deionized water, and the cuprous oxide nanoparticles were evenly dispersed by ultrasound; the pH value of the dispersion was adjusted to 11.0 with a 2 mol / L sodium hydroxide solution; the temperature was raised to 80° C., and 10 mL of a 0.5 mol / L aqueous solution of an epoxy-terminated allyl polyether (m=4, n=8, molecular weight 754) was added dropwise four times every 1 hour, with a total of 15.08 g of the epoxy-terminated allyl polyether being added, and the reaction was carried out for 4 hours; after the reaction was completed, the mixture was cooled to room temperature, the precipitate was filtered, soaked with acetone, and then filtered and dried to obtain terminal olefin-modified cuprous oxide nanoparticles; Step 3): 5g of terminal olefin-modified cuprous oxide nanoparticles and 0.1g of initiator potassium persulfate prepared in step 2) were ultrasonically dispersed in 44.8g of distilled water, 10g of dimethyldiallylammonium chloride was added to a three-necked flask, the temperature was raised to 60°C and the reaction was continued for 30min, and then 0.1g of initiator potassium persulfate, 10g of terminal vinyl silicon and 30g of distilled water were added and the reaction was continued for 30min; finally, the reaction was kept warm for 5h, naturally cooled to room temperature, and washed 3 times with ethanol and deionized water to obtain a modified cuprous oxide antifouling material with a particle size D50 of 121nm and D90 of 234nm.

8. The preparation method according to any one of claims 1 to 5, characterized in that Prepare as follows: Step 1): 200 ml of a 0.5 mol / L aqueous solution of copper chloride dihydrate and 11.82 g of 0.1 mol of 1,2-hexanediol were uniformly mixed at room temperature, transferred to a hydrothermal reactor, sealed, heated to 170° C., and reacted for 45 minutes; the resulting product was centrifuged and filtered, and washed three times with anhydrous ethanol and deionized water to obtain cuprous oxide nanoparticles; Step 2): Disperse 5 g of cuprous oxide nanoparticles prepared in step 1) in 100 mL of deionized water, and uniformly disperse the cuprous oxide nanoparticles by ultrasonication; adjust the pH of the dispersion to 11.0 with a 2 mol / L sodium hydroxide solution; raise the temperature to 80° C., and dropwise add 10 mL of a 0.5 mol / L aqueous solution of epoxy-terminated allyl polyether (m=8, n=8, molecular weight 930) four times every 1 hour, for a total of 18.60 g of epoxy-terminated allyl polyether, and react for 4 hours; after the reaction is completed, cool to room temperature, filter the precipitate, soak it in acetone, filter it again, and dry it to obtain terminal olefin-modified cuprous oxide nanoparticles; Step 3): 5g of terminal olefin-modified cuprous oxide nanoparticles and 0.1g of initiator potassium persulfate prepared in step 2) were ultrasonically dispersed in 34.8g of distilled water, 20g of dimethyldiallylammonium chloride was added to a three-necked flask, the temperature was raised to 60°C and the reaction was continued for 30min, and then 0.1g of initiator potassium persulfate, 20g of terminal vinyl silicon and 20g of distilled water were added and the reaction was continued for 30min; finally, the reaction was kept warm for 6h, naturally cooled to room temperature, and washed 3 times with ethanol and deionized water to obtain a modified cuprous oxide antifouling material with a particle size D50 of 124nm and D90 of 228nm.

9. A modified cuprous oxide antifouling material, characterized in that The modified cuprous oxide antifouling material prepared by the method according to any one of claims 1 to 8 has a particle size D50 < 150 nm and a particle size D90 < 250 nm.

10. Use of the modified cuprous oxide antifouling material according to claim 9 in marine antifouling coatings.

Images