A functionalized antifouling nanoparticle and its preparation method, and an energy-saving, drag-reducing, environmentally friendly antifouling coating and its preparation method.

Abstract

This invention relates to the field of coating technology, and particularly to a functionalized antifouling nanoparticle and its preparation method, as well as an energy-saving, drag-reducing, and environmentally friendly antifouling coating and its preparation method. The preparation method of the antifouling nanoparticle includes the following steps: polyethylene glycol methyl ether acrylate and a first silane coupling agent are heated and reacted for a certain time to obtain a functionalized silane coupling agent; a lactone and N,N-dialkyl-3-aminopropyltrimethoxysilane are stirred and mixed in solvent B to react and obtain silane-coupled betaine; the functionalized silane coupling agent, silane-coupled betaine, and a second silane coupling agent are added to a dispersion formed by a catalyst and zinc oxide nanoparticles and heated to react, thereby obtaining the antifouling nanoparticles. The antifouling nanoparticles obtained by this invention can be used in coating systems to prepare antifouling coatings. This antifouling coating formulation does not contain antifouling agents, is environmentally friendly, and the resulting coating has good antifouling effect. Furthermore, after being washed by seawater for a period of time, the surface of the coating becomes smoother, effectively reducing water flow resistance.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a functionalized antifouling nanoparticle and its preparation method, and an energy-saving, drag-reducing, and environmentally friendly antifouling coating and its preparation method. Background Technology

[0002] Antifouling coatings can save fuel and reduce carbon emissions for ships, and have broad and promising application prospects.

[0003] Currently, the mainstream antifouling coating for ships is a single-component hydrolyzed antifouling coating with a large amount of cuprous oxide and its auxiliary antifouling agents. This type of antifouling coating accounts for approximately 90% of the ship antifouling coating market. This hydrolyzed antifouling coating contains a large amount of antifouling agent in its formulation, which increases the cost of the coating and the burden on the marine environment. Furthermore, the dissolution of the antifouling agent increases the roughness of the coating surface, thus increasing the ship's fuel consumption. For example:

[0004] Some foreign patents, such as US9045650B2, EP1308484A1, and EP1476509B1, employ different technical means to improve the performance of antifouling coatings. However, the disclosed coating solutions all contain a large amount of copper-based antifouling agents. After dissolution and polishing, the surface roughness of the coating remains relatively large, and the large amount of copper-based antifouling agents increases the cost of the coating and the burden on the marine environment.

[0005] In Chinese invention patent CN103131289B, a matrix resin with self-polishing properties and low surface properties is obtained by copolymerizing organosilicon acrylate and fluorinated (meth)acrylate. This coating is hydrophobic and oleophobic; however, antifouling coatings prepared with this resin matrix also contain a large amount of antifouling agent. Furthermore, the antifouling coating prepared with a grafted biocide prepared in Chinese invention patent CN 109762098B also contains a large amount of copper-free antifouling agent in its formulation. In summary, in this field, seeking a single-component, hydrolyzable, low / no-antifouling agent antifouling coating is of great significance.

[0006] Existing research provides hydrolytic antifouling coatings, whose components contain various toxic antifouling agents. After being washed away and dissolved by seawater for a period of time, the surface of the antifouling coating below the waterline of the ship becomes relatively rough. It can only partially help ships save fuel and is still detrimental to the marine environment and energy conservation and drag reduction. Furthermore, the dissolved antifouling agents increase the cost of the coating and the burden on the marine environment, requiring further improvement. Summary of the Invention

[0007] To address the shortcomings of the prior art mentioned in the background section, this invention provides functionalized antifouling nanoparticles and their preparation method, as well as an energy-saving, drag-reducing, and environmentally friendly antifouling coating and its preparation method.

[0008] The preparation method of this functionalized antifouling nanoparticle includes the following steps:

[0009] Under a protective atmosphere, polyethylene glycol methyl ether acrylate and a first silane coupling agent are heated in solvent A at 25–60 °C for a certain time to prepare a functionalized silane coupling agent.

[0010] Under a protective atmosphere, lactone and N,N-dialkyl-3-aminopropyltrimethoxysilane were stirred and mixed in solvent B and reacted for a certain period of time to prepare silane-coupled betaine.

[0011] The catalyst and zinc oxide nanoparticles were dispersed in solvent C to form a dispersion. Under a protective atmosphere, functionalized silane coupling agent, silane coupling betaine, and second silane coupling agent were added to the dispersion and heated at 40-60°C for a certain period of time to obtain the antifouling nanoparticles M-SiO2-ZnONPs.

[0012] In some embodiments, in the step of synthesizing functionalized silane coupling agent, the mass ratio of the first silane coupling agent, polyethylene glycol methyl ether acrylate, and solvent A is (5-20):(10-50):(15-45);

[0013] In the step of synthesizing silane-coupled betaine, the mass ratio of lactone, N,N-dialkyl-3-aminopropyltrimethoxysilane, and solvent B is (5-30):(1-25):(10-40);

[0014] In the step of synthesizing antifouling nanoparticles, the mass ratio of zinc oxide nanoparticles, functionalized silane coupling agent, second silane coupling agent, silane-coupled betaine, catalyst, and solvent C is (5-40):(5-20):(5-30):(5-20):(1-5):(15-50).

[0015] In some embodiments, in the step of synthesizing functionalized silane coupling agent, solvent A and polyethylene glycol methyl ether acrylate are stirred evenly, and the mixture is heated to 25-60°C under a protective atmosphere. Then, the first silane coupling agent is added, and the mixture is heated at 25-60°C for 6-48 hours to obtain the functionalized silane coupling agent.

[0016] In the synthesis of silane-coupled betaine, lactone, N,N-dialkyl-3-aminopropyltrimethoxysilane and solvent B are mixed and reacted under a protective atmosphere for 6 to 24 hours. The reaction product is then filtered, washed and dried to obtain silane-coupled betaine.

[0017] In some embodiments, solvent A is any one of alcohol solvents and ketone solvents, wherein the alcohol solvent is any one of ethanol, n-butanol, isobutanol, polyethylene glycol, propylene glycol, or a combination of any two thereof; the ketone solvent is any one of acetone, butanone, or a combination of any two thereof; the first silane coupling agent is any one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, or a combination of any two thereof; and the molecular weight of polyethylene glycol methyl ether acrylate is 300 to 2000.

[0018] In some embodiments, the lactone is one or a combination of carboxylate lactone, 1,3-sulfonate propiolactone, and 1,4-sulfonate butyrolactone; the N,N-dialkyl-3-aminopropyltrimethoxysilane is any one or a combination of any two of N,N-dimethyl-3-aminopropyltrimethoxysilane and N,N-diethyl-3-aminopropyltrimethoxysilane; the solvent B is any one or a combination of any two of alcohol solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, and ether solvents, wherein the alcohol solvent is any one or a combination of any two of ethanol, n-butanol, and propylene glycol; the aromatic hydrocarbon solvent is any one or a combination of any two of toluene and xylene; the ketone solvent is any one or a combination of any two of methyl ethyl ketone, butanone, and cyclohexanone; the ester solvent is any one or a combination of any two of butyl acetate and ethyl acetate; and the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.

[0019] In some embodiments, in the step of synthesizing antifouling nanoparticles, solvent C, catalyst and zinc oxide nanoparticles are mixed and ultrasonically dispersed to form a dispersion. Under a protective atmosphere, the dispersion is heated to 40-60°C, and then functionalized silane coupling agent, silane coupling betaine and second silane coupling agent are added. The mixture is heated and reacted at 40-60°C for 3-6 hours. The reaction product is subjected to solid-liquid treatment and solid product washing treatment to obtain the antifouling nanoparticles M-SiO2-ZnONPs.

[0020] In some embodiments, solvent C is any one of alcohol solvents and ketone solvents, wherein the alcohol solvent is any one of ethanol, n-butanol, isobutanol, propylene glycol, or a combination of any two thereof, and the ketone is any one of acetone, butanone, or a combination of any two thereof; the diameter of the zinc oxide nanoparticles is 10-100 nanometers; the catalyst is any one of benzyltrimethylammonium chloride, tert-butylamine, triethylamine, or a combination of any combination of multiple thereof; and the second silane coupling agent is any one of methyltrimethoxysilane, octylmethoxysilane, dodecyltrimethoxysilane, methylethoxysilane, tetraethoxysilane, or a combination of any two thereof.

[0021] The present invention also provides a functionalized antifouling nanoparticle, which is prepared by the method described above for preparing functionalized antifouling nanoparticles.

[0022] The present invention also provides an energy-saving, drag-reducing, and environmentally friendly antifouling coating, the components of which include antifouling nanoparticles and a main-chain silicon-zinc condensate solution; the mass ratio of the main-chain silicon-zinc condensate solution to the antifouling nanoparticles is (30-90):(0.1-30); wherein the antifouling nanoparticles are prepared by the preparation method of functionalized antifouling nanoparticles as described above.

[0023] The present invention also provides a method for preparing the energy-saving, drag-reducing, environmentally friendly antifouling coating as described above, which includes the following steps: adding a main-chain silicon-zinc condensate solution to a dispersion tank, adding antifouling nanoparticles M-SiO2-ZnONPs at a mixing speed of 500-1000 rpm, and then dispersing at high speed to obtain the coating.

[0024] Based on the above, compared with the prior art, the present invention has the following beneficial effects:

[0025] The antifouling nanoparticles M-SiO2-ZnO NPs prepared by this invention can be used in coating systems to prepare antifouling coatings. The resulting antifouling coating formulation does not contain antifouling agents, is environmentally friendly, and has antibacterial properties. It can effectively inhibit the adsorption of organic matter, and the resulting coating has a good antifouling effect. Furthermore, the surface of the coating becomes smoother after being washed by seawater for a period of time, which can greatly reduce the resistance of water flow and is beneficial for energy saving and drag reduction.

[0026] Other features and beneficial effects of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects of the invention and other beneficial effects may be realized and obtained by means of the structures and / or components pointed out in the description and claims. Attached Figure Description

[0027] Figure 1 A schematic diagram of the structure of the functionalized antifouling nanoparticles M-SiO2-ZnO NPs provided by the present invention;

[0028] Figure 2 This is a schematic diagram of the structure of the coating obtained by the coating provided by the present invention under the action of seawater.

[0029] Figure label:

[0030] 100 Antifouling nanoparticles M-SiO2-ZnONPs, 200 Main-chain silicon-zinc condensate, 300 Hydration layer, 110 ZnO nanoparticles, 120 Modified SiO2 nanoparticles, 121 SiO2 core, 122 Functionalized silane coupling agent segment, 123 Silane-coupled betaine segment. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. The technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0032] In the description of this invention, it should be noted that all terms used in this invention (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, and should not be construed as limiting the invention; it should be further understood that the terms used in this invention should be understood to have the same meaning as those in the context of this specification and in the relevant field, and should not be understood in an idealized or overly formal sense, except as expressly defined in this invention.

[0033] The present invention also provides an example of the preparation method of functionalized antifouling nanoparticles and energy-saving, drag-reducing, and environmentally friendly antifouling coatings:

[0034] First, nano-SiO2-ZnO (Ⅰ, Ⅱ, and Ⅲ) antifouling particles doped with special groups are prepared, and then mixed and dispersed with a main-chain silicon-zinc condensate solution to obtain an energy-saving, drag-reducing, and environmentally friendly antifouling coating.

[0035] The preparation method consists of four steps:

[0036] I. Synthesis of Functionalized Silane Coupling Agents (FSCA):

[0037] Solvent A and polyethylene glycol methyl ether acrylate (mPEGA) were added to a four-necked flask and stirred until homogeneous. The flask was then heated to 25–60°C under a nitrogen atmosphere. Subsequently, the first silane coupling agent (NSCA) was added dropwise to the flask and the heating was maintained for 6–48 hours. After the addition was complete, the modified functionalized silane coupling agent was obtained. The mass ratio of the first silane coupling agent, polyethylene glycol methyl ether acrylate, and solvent A was (5–20):(10–50):(15–45).

[0038] Wherein, solvent A is any one of alcohol solvents and ketone solvents, wherein the alcohol solvent is any one of ethanol, n-butanol, isobutanol, polyethylene glycol, propylene glycol, or a combination of any two thereof; the ketone solvent is any one of acetone, butanone, or a combination of any two thereof; the first silane coupling agent NSCA is any one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, or a combination of any two thereof; and the molecular weight of polyethylene glycol methyl ether acrylate is 300-2000.

[0039] II. Synthesis of silane-coupled betaine (SIB):

[0040] Add lactone, N,N-dialkyl-3-aminopropyltrimethoxysilane (NAPTMS) and solvent B to a four-necked flask, stir the reaction under a nitrogen atmosphere for 6–24 hours, filter, wash and dry to obtain silane-coupled betaine; the mass ratio of lactone, N,N-dialkyl-3-aminopropyltrimethoxysilane and solvent B is (5–30):(1–25):(10–40).

[0041] Wherein, the lactone is one or a combination of carboxylate lactone, 1,3-sulfonate propiolactone, and 1,4-sulfonate butyrolactone; the N,N-dialkyl-3-aminopropyltrimethoxysilane is any one or a combination of any two of N,N-dimethyl-3-aminopropyltrimethoxysilane and N,N-diethyl-3-aminopropyltrimethoxysilane; the solvent B is any one or a combination of any two of alcohol solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, and ether solvents, wherein the alcohol solvent is any one or a combination of any two of ethanol, n-butanol, and propylene glycol; the aromatic hydrocarbon solvent is any one or a combination of any two of toluene and xylene; the ketone solvent is any one or a combination of any two of methyl ethyl ketone, butanone, and cyclohexanone; the ester solvent is any one or a combination of any two of butyl acetate and ethyl acetate; and the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.

[0042] III. Synthesis of Functionalized Antifouling Nanoparticles M-SiO2-ZnO NPs:

[0043] Solvent C, catalyst, and zinc oxide nanoparticles (ZnO NPs) were placed in a four-necked flask and ultrasonically dispersed for 20 minutes. The flask was then heated to 40–60°C under a nitrogen atmosphere. FSCA, SIB, and a second silane coupling agent (SCA) were then uniformly added dropwise to the flask, and the mixture was kept heated for 3–6 hours. The mixture was repeatedly centrifuged and washed three times to obtain functionalized particles MS iO2-ZnO NPs. The mass ratio of zinc oxide nanoparticles, functionalized silane coupling agent, second silane coupling agent, silane-coupled betaine, catalyst, and solvent C was (5–40):(5–20):(5–30):(5–20):(1–5):(15–50).

[0044] Wherein, solvent C is any one of alcohol solvents and ketone solvents, wherein the alcohol solvent is any one of ethanol, n-butanol, isobutanol, propylene glycol, or a combination of any two thereof, and the ketone is any one of acetone, butanone, or a combination of any two thereof; the diameter of the zinc oxide nanoparticles is 10-100 nanometers; the catalyst is any one of benzyltrimethylammonium chloride, tert-butylamine, triethylamine, or a combination of any combination of multiple thereof; and the second silane coupling agent SCA is any one of methyltrimethoxysilane, octylmethoxysilane, dodecyltrimethoxysilane, methylethoxysilane, tetraethoxysilane, or a combination of any two thereof.

[0045] IV. Preparation of Antifouling Coatings

[0046] Add a main-chain silicon-zinc condensate solution to a dispersion tank, add M-SiO2-ZnONPs at 500-1000 rpm, and then disperse at high speed for 30 minutes to obtain the desired coating.

[0047] The mass ratio of the main-chain silicon-zinc condensate solution to the antifouling nanoparticles is (30-90):

[0048] (0.1~30); The main-chain silicon-zinc condensate solution uses the main-chain silicon-zinc condensate solution disclosed in patent ZL201910042379.5.

[0049] The present invention also provides the following embodiments and comparative examples.

[0050] 1. The raw material formulation (unit: parts by weight) for the preparation process of the embodiment is shown in Table 1 below:

[0051] Table 1

[0052]

[0053]

[0054] The specific preparation process of Examples 1-4 above is as follows:

[0055] I. Synthesis of Functionalized Silane Coupling Agents (FSCA):

[0056] Solvent A and polyethylene glycol methyl ether acrylate (mPEGA) were added to a four-necked flask and stirred until homogeneous. The flask was then heated to 25°C under a nitrogen atmosphere. Subsequently, the first silane coupling agent (NSCA) was uniformly added dropwise to the flask, and the heating was maintained for 48 hours. After the addition was completed, the modified functionalized silane coupling agent was obtained.

[0057] The selected solvent A is n-butanol, NSCA is aminopropyltriethoxysilane, and mPEGA has a molecular weight of 1000.

[0058] II. Synthesis of silane-coupled betaine (SIB):

[0059] Add lactone, N,N-dialkyl-3-aminopropyltrimethoxysilane (NAPTMS) and solvent B to a four-necked flask, stir the mixture at room temperature under a nitrogen atmosphere for 24 hours, filter, wash and dry to obtain silane-coupled betaine.

[0060] The selected lactone is 1,4-sulfonate butyrolactone, solvent B is ethanol, and NAPTMS is N,N-diethyl-3-aminopropyltrimethoxysilane.

[0061] III. Synthesis of Functionalized Antifouling Nanoparticles M-SiO2-ZnO NPs:

[0062] Solvent C, catalyst, and zinc oxide nanoparticles (ZnO NPs) were placed in a four-necked flask and ultrasonically dispersed for 20 minutes. The flask was then heated to 40°C under a nitrogen atmosphere. FSCA, SIB, and silane coupling agent (SCA) were then uniformly added dropwise to the flask, and the mixture was kept heated for 6 hours. The reaction product was repeatedly centrifuged and washed three times to obtain functionalized particles M-SiO2-ZnO NPs.

[0063] The solvent C used is butanone, the particle diameter of ZnO NPs is 30 nanometers, the catalyst is tert-butylamine, and SCA is methyltrimethoxysilane.

[0064] IV. Preparation of Antifouling Coatings

[0065] A main-chain silicon-zinc condensate solution was added to a dispersion tank, and M-SiO2-ZnO NPs were added at 800 rpm. The mixture was then dispersed at high speed for 30 minutes to obtain the desired coating.

[0066] The main-chain silicon-zinc condensate solution used was prepared according to the content disclosed in patent ZL201910042379.5. Specifically, the main-chain silicon-zinc condensate solution prepared in Example 1 of the patent was used, which has a weight-average molecular weight of 25,000, a viscosity of 3,800 mPa·s, and a solid content of 48.5%.

[0067] 2. Comparative Example

[0068] Comparative Example 1

[0069] The only difference between this comparative example and Example 3 is that:

[0070] In step IV, the comparative example uses a copper-containing antifouling agent to replace the functionalized antifouling nanoparticles by mass and adds them to the main-chain silicon-zinc condensate matrix to prepare a coating; wherein the copper-containing antifouling agent is cuprous oxide.

[0071] Comparative Example 2

[0072] Marine antifouling paint prepared from polymer #52 in patent US6767978B2.

[0073] Comparative Example 3

[0074] The only difference between this comparative example and the embodiment is that:

[0075] In step III, this comparative example only uses SCA to modify zinc oxide nanoparticles. In Example 1, SIB, SCA, and FSCA are all replaced by SCA of equal mass (i.e., the amount of SCA used in this comparative example is the total mass of SIB, SCA, and FSCA in Example 1). Other steps and preparation conditions are the same as in Example 1.

[0076] Comparative Example 4

[0077] The only difference between this comparative example and the embodiment is that:

[0078] In step III, all SCA in Example 1 was replaced with FSCA of equal mass, and the other steps and preparation conditions were the same as in Example 1.

[0079] The coatings prepared in the above examples and comparative examples were subjected to benchmark tests, and the test results are shown in Table 2-3 below:

[0080] Table 2. Antifouling results of the antifouling coating (shallow sea siding, 4 months)

[0081] Test Project Example 1 Example 2 Example 3 Example 4 score 91 92 93 93 Test Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 score 80 88 75 85

[0082] The test was conducted according to the national standard GB / T 5370-2007 "Test Method for Shallow Sea Immersion of Antifouling Paint Samples". The higher the score, the better the antifouling performance.

[0083] Table 3. Test results of coating performance in different embodiments (after 4 months of seawater abrasion).

[0084] Test Project Example 1 Example 2 Example 3 Example 4 Surface roughness (μm) 1.5 1.4 1.7 1.9 drag reduction 7.0 7.2 7.3 7.5 Test Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Surface roughness (μm) 3.8 4.9 1.7 2.0 drag reduction 4.8 3.7 6.9 7.0

[0085] The surface roughness of the coating samples was measured using a confocal 3D profilometer. The drag reduction rate was measured by comparing the torque values ​​of different embodiments, comparative examples and reference coating system 839. The drag reduction rate was tested in accordance with the national standard GBT7791-2014.

[0086] Analysis of the data results from the examples and comparative examples shows that:

[0087] (1) Comparison between Comparative Examples 1-2 and Examples

[0088] Compared with Comparative Example 1 (using a traditional copper-containing antifouling agent) and Comparative Example 2 (commercially available foreign acrylic silicone antifouling coating), the antifouling coating formed by the coating in the examples has a smaller and smoother surface roughness after being eroded by seawater, and the seawater resistance is reduced to a greater extent, which is beneficial for energy saving and drag reduction.

[0089] Furthermore, compared to Comparative Example 1, which uses a traditional copper-containing antifouling agent, the antifouling coating of this application embodiment does not contain antifouling agents and is environmentally friendly.

[0090] (1) Comparison between Comparative Examples 3-4 and Examples

[0091] Compared to the examples, the antifouling coating formed by the coating in Comparative Example 3 had the worst antifouling effect;

[0092] Compared to the examples, the antifouling effect of the coating formed by the coating in Comparative Example 4 was 85 points according to the standard score, indicating a decrease in antifouling performance. Although Comparative Example 4 uses SIB, FSCA and zinc oxide nanoparticles to react and form microspheres, it still needs to add an appropriate amount of untreated SCA, as in Examples 1-4 in Table 3, to better load onto the nano zinc oxide and help the crosslinking reaction form uniform nanoparticles. The nanoparticles added to the coating can be uniformly released in seawater, resulting in better antifouling. Comparative Example 4 does not add the corresponding untreated SCA, so the antifouling effect is only average.

[0093] In summary, the functionalized antifouling nanoparticles and the energy-saving, drag-reducing, and environmentally friendly antifouling coatings made from these functionalized antifouling nanoparticles provided by this invention include at least the following design concepts, mechanisms of action, and beneficial effects:

[0094] 1. Design concept and mechanism of action

[0095] Figure 1The antifouling nanoparticles M-SiO2-ZnONPs 100 are formed by loading modified SiO2 nanoparticles 120 onto ZnO nanoparticles 110. The modified SiO2 nanoparticles 120 consist of three parts: SiO2 core 121, functionalized silane coupling agent segment 122, and silane-coupled betaine segment 123. The SiO2 core 121 is a nano-silica core, on which functionalized silane coupling agent segment 122 and silane-coupled betaine segment 123 are placed. Functionalized silane coupling agent segment 122 is a polyethylene glycol (PEG) segment, and silane-coupled betaine segment 123 is an amphoteric segment.

[0096] Figure 2 The coating consists of antifouling nanoparticles M-SiO2-ZnONPs 100 and main-chain silicon-zinc condensate 200. When the coating is immersed in seawater, the functionalized silane coupling agent segment 122 binds water molecules through the hydroxyl groups in the molecule, while the silane-coupled betaine segment 123 binds water molecules through electrostatic force. The functionalized silane coupling agent segment 122 and the silane-coupled betaine segment 123 synergistically form a stronger hydration layer. This hydration layer provides an energy barrier for the material surface, inhibiting the attachment of typical fouling organisms such as bacteria, diatoms, urspores, and barnacle larvae, and exhibits a good inhibitory effect.

[0097] 2. Beneficial effects:

[0098] The antifouling nanoparticles provided by this invention are incorporated into a coating based on a main-chain silicon-zinc condensate. The antifouling coating formulation does not contain antifouling agents, and the coating formed by the coating can form a hydration layer doped with nano-M-SiO2-ZnO NPs in water. The antifouling coating prepared using these antifouling nanoparticles M-SiO2-ZnO NPs has antibacterial properties and can effectively inhibit the adsorption of organic matter. The coating formed by this coating has good antifouling effect, is environmentally friendly, and the surface of the coating becomes smoother after being washed by seawater for a period of time, which can greatly reduce the resistance of water flow and is beneficial to energy saving and drag reduction.

[0099] In summary, the antifouling coating prepared using the antifouling nanoparticles MS iO2-ZnO NPs in this application produces the following positive effects:

[0100] (1) The antifouling coating of the present invention does not contain antifouling agents and is environmentally friendly.

[0101] (2) The antifouling coating of the present invention has a good antifouling effect (4 months).

[0102] (3) The antifouling coating of the present invention has a smoother surface after being washed by seawater, which can greatly reduce the resistance of seawater to it.

[0103] It should be noted that:

[0104] In this article, “~” is used to represent the range of values, and the range of values ​​represented by this expression includes two endpoint values.

[0105] The specific parameters or commonly used reagents in the above embodiments are specific or preferred embodiments under the concept of this invention, and are not intended to limit it; those skilled in the art can make adaptive adjustments within the concept and protection scope of this invention. Furthermore, unless otherwise specified, the raw materials used can also be commercially available products in the art, or prepared by conventional methods in the art.

[0106] Furthermore, those skilled in the art should understand that although many problems exist in the prior art, each embodiment or technical solution of the present invention can be improved in only one or a few aspects, without necessarily solving all the technical problems listed in the prior art or the background art simultaneously. Those skilled in the art should understand that any content not mentioned in a claim should not be construed as a limitation on that claim.

[0107] Although terms such as polyethylene glycol methyl ether acrylate and silane coupling agent are frequently used in this document, the possibility of using other terms is not excluded. These terms are used merely for the convenience of describing and explaining the essence of the invention; interpreting them as any additional limitation would contradict the spirit of the invention. The terms "first," "second," etc. (if present) in the description and claims of the embodiments of the invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence.

[0108] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing functionalized antifouling nanoparticles, characterized in that, The method comprises the following steps: under a protective atmosphere, the polyethylene glycol methyl ether acrylate and the first silane coupling agent are heated and reacted in solvent A at 25-60℃ for a certain period of time to obtain a functionalized silane coupling agent; under a protective atmosphere, the lactone and N,N-dialkyl-3-aminopropyl trimethoxysilane are stirred and mixed in solvent B for a certain period of time to obtain a silane coupling betaine; under a protective atmosphere, the functionalized silane coupling agent, the silane coupling betaine and the second silane coupling agent are added into the dispersion liquid, and heated and reacted at 40-60℃ for a certain period of time to obtain the anti-fouling nanoparticles M-SiO2-ZnONPs.

2. The method for preparing functionalized antifouling nanoparticles according to claim 1, characterized in that: In the step of synthesizing the functionalized silane coupling agent, the mass ratio of the first silane coupling agent, the polyethylene glycol methyl ether acrylate and solvent A is (5-20):(10-50):(15-45); In the step of synthesizing the silane coupling betaine, the mass ratio of the lactone, N,N-dialkyl-3-aminopropyl trimethoxysilane and solvent B is (5-30):(1-25):(10-40); In the step of synthesizing the anti-fouling nanoparticles, the mass ratio of the zinc oxide nanoparticles, the functionalized silane coupling agent, the second silane coupling agent, the silane coupling betaine, the catalyst and solvent C is (5-40):(5-20):(5-30):(5-20):(1-5):(15-50).

3. The method according to claim 1, wherein: In the step of synthesizing the functionalized silane coupling agent, the polyethylene glycol methyl ether acrylate and solvent A are stirred uniformly, and then the mixture is heated to 25-60℃ under a protective atmosphere, and then the first silane coupling agent is added and heated at 25-60℃ for 6-48 hours to obtain the functionalized silane coupling agent; In the step of synthesizing the silane coupling betaine, the lactone, N,N-dialkyl-3-aminopropyl trimethoxysilane and solvent B are mixed, and then stirred and reacted for 6-24 hours under a protective atmosphere, and then the reaction product is filtered, washed and dried to obtain the silane coupling betaine.

4. The method according to claim 1, wherein: the solvent A is any one of an alcohol solvent and a ketone solvent, wherein the alcohol solvent is any one or a combination of two of ethanol, n-butanol, isobutyl alcohol, polyethylene glycol and propylene glycol; and the ketone solvent is any one or a combination of two of acetone and butanone; the first silane coupling agent is any one or a combination of two of aminopropyl triethoxysilane and aminopropyl trimethoxysilane; the polyethylene glycol methyl ether acrylate has a molecular weight of 300-2000.

5. The method according to claim 1, wherein: the lactone is one or a combination of carboxylic acid lactone, 1,3-sulfonic acid propiolactone and 1,4-sulfonic acid butyrolactone. The N,N-dialkyl-3-aminopropyl trimethoxysilane is any one of N,N-dimethyl-3-aminopropyl trimethoxysilane, N,N-diethyl-3-aminopropyl trimethoxysilane or a combination of any two thereof; The solvent B is any one of an alcohol solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, an ether solvent or a combination of any two thereof, wherein the alcohol solvent is any one of ethanol, n-butanol, propylene glycol or a combination of any two thereof; the aromatic hydrocarbon solvent is any one of toluene, xylene or a combination of any two thereof, the ketone solvent is any one of methyl ethyl ketone, cyclohexanone or a combination of any two thereof, the ester solvent is any one of butyl acetate, ethyl acetate or a combination of any two thereof; and the ether solvent is one of propylene glycol methyl ether, propylene glycol ethyl ether.

6. The method of claim 1, wherein the functionalized anti-fouling nanoparticles are prepared by the method comprising the steps of: In the step of synthesizing the anti-fouling nanoparticles, the solvent C, the catalyst and the zinc oxide nanoparticles are mixed to form a dispersion liquid by ultrasonic dispersion; the dispersion liquid is heated to 40-60°C under a protective atmosphere, and then the functionalized silane coupling agent, the silane coupling betaine and the second silane coupling agent are added and heated at 40-60°C for 3-6 hours; the reaction product is subjected to solid-liquid treatment and washing treatment of the solid product to obtain the anti-fouling nanoparticles M-SiO2-ZnONPs.

7. The method for preparing functionalized antifouling nanoparticles according to claim 1, characterized in that: The solvent C is any one of an alcohol solvent, a ketone solvent, wherein the alcohol solvent is any one of ethanol, n-butanol, isobutyl alcohol, propylene glycol or a combination of any two thereof, and the ketone is any one of acetone, butanone or a combination of any two thereof; The diameter of the zinc oxide nanoparticles is 10-100 nanometers; The catalyst is any one or a combination of benzyltrimethylammonium chloride, t-butylamine and triethylamine; The second silane coupling agent is any one or a combination of methyltrimethoxysilane, octylmethoxysilane, dodecyltrimethoxysilane, methyl ethoxysilane and tetraethoxysilane.

8. A functionalized antifouling nanoparticle, characterized in that: The functionalized anti-fouling nanoparticles are prepared by the method of any one of claims 1-7.

9. An energy-saving, drag-reducing, environmentally friendly antifouling paint, characterized by: The components thereof include the anti-fouling nanoparticles and the main chain type silicon-zinc polycondensate solution; The mass ratio of the main chain type silicon-zinc polycondensate solution to the anti-fouling nanoparticles is (30-90):(0.1-30); The anti-fouling nanoparticles are prepared by the method of any one of claims 1-7.

10. A method for preparing the energy-saving, drag-reducing, environmentally friendly antifouling paint according to claim 9, characterized by, The method comprises the following steps: The main chain type silicon-zinc polycondensate solution is added to a dispersion tank, the anti-fouling nanoparticles M-SiO2-ZnONPs are added at a mixing speed of 500-1000 rpm, and then high-speed dispersion is performed to prepare the coating.

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