Amphoteric hyperbranched antifouling resin as well as preparation method and application thereof

Abstract

The invention discloses amphoteric hyperbranched antifouling resin and a preparation method and application thereof, and belongs to the technical field of paints.The preparation method includes the steps that hydrolyzable self-polishing resin is prepared by designing a specific synthesis route, and silicone oil containing double bonds and perfluoropolyether components are introduced in the polymerization process; the preparation method comprises the following steps: adding a hydrophilic group and a hydrophobic group into a modified hyperbranched resin, simultaneously grafting the hydrophilic group and the hydrophobic group onto the resin to realize synthesis and preparation of the amphoteric hydrolyzable self-polishing resin, and then combining the amphoteric hydrolyzable self-polishing resin with the modified hyperbranched resin through chemical reaction to obtain the amphoteric hyperbranched antifouling resin. Compared with the existing self-polishing antifouling resin, the self-polishing antifouling resin has the advantages of good fouling resistance performance under a static condition, good mechanical property, high solid content and low VOC (Volatile Organic Compounds).

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to an amphoteric hyperbranched antifouling resin and a preparation method and application thereof. Background Art

[0002] Marine biofouling refers to the growth of molecules, microorganisms, plants and animals on the surface of ships and marine equipment when they are submerged in seawater. This can cause many hazards, such as aging of the ship surface, increasing driving resistance, interfering with the normal operation of marine equipment, increasing fuel consumption and maintenance costs, and even causing biological invasions. According to relevant data, biofouling causes losses of more than $15 billion to the entire marine industry each year.

[0003] The most common method to solve the problem of marine biofouling is to apply antifouling paint on the surface of the hull and equipment. Self-polishing antifouling paint is one of the most widely used types of paint in the field of marine engineering. It is based on the exchange of metal ions in the copolymer with sodium ions in seawater to release toxic ions for antifouling. At the same time, it realizes self-polishing through self-hydrolysis, strengthens antifouling ability and reduces driving resistance. However, traditional self-polishing antifouling paint has obvious defects. On the one hand, its excellent antifouling performance depends on the high-speed navigation of the ship. During the period when the ship is moored, the surface resin cannot be polished out in time, and the antifouling agent inside the coating cannot be released, resulting in insufficient static antifouling effect. On the other hand, the resin matrix used in traditional self-polishing antifouling paint is a long chain of linear acrylic resin. In order to ensure good dissolution of the resin, a large amount of organic solvents need to be used during the application process. With the improvement of environmental awareness, this environmentally unfriendly paint can no longer meet new environmental protection needs.

[0004] Hyperbranched resins have unique structural and performance advantages, such as low viscosity, high solubility, and good film-forming properties, and have potential application value in the field of antifouling materials. By introducing hydrophilic and hydrophobic groups, amphoteric resins are expected to solve the problem of poor static antifouling effect of antifouling resins. Studies have shown that amphoteric fluorine-containing or silicon-based copolymer coatings have certain antifouling capabilities, but existing research still has shortcomings. For example, some amphoteric polymers will leach from the polymer matrix after long-term contact with water, resulting in reduced antifouling efficiency and environmental problems.

[0005] In view of this, this application is filed. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an amphoteric hyperbranched antifouling resin and its preparation method and application. Compared with the existing self-polishing antifouling resin, the resin has the advantages of good fouling resistance performance under static conditions, good mechanical properties, high solid and low VOC.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0009] (1) dissolving methyl methacrylate, butyl acrylate, acryloxytrimethylsilane, hydroxyethyl methacrylate and an initiator in a solvent uniformly, reacting (reaction temperature is 65-75° C., reaction time is 8-16 h), adding perfluoropolyether acrylate and silicone acrylate, reacting (reaction temperature is 65-75° C., reaction time is 8-20 h), removing the solvent, and drying to obtain an amphoteric hydrolyzable self-polishing resin;

[0010] (2) dissolving an amphoteric hydrolyzable self-polishing resin and an isocyanate in a solvent, heating to 60 to 80° C. in a nitrogen atmosphere, keeping the temperature for 0.5 to 2 h, adding a modified hyperbranched resin, reacting (reaction temperature is 65 to 75° C., reaction time is 8 to 16 h), and obtaining a mixed solution; then adding a catalyst, stirring (stirring time is 8 to 24 h), and drying to obtain an amphoteric hyperbranched antifouling resin.

[0011] The synthesis principle of the hyperbranched antifouling resin of the present invention is as follows:

[0012]

[0013] The invention prepares a hydrolyzable self-polishing resin by designing a specific synthesis route, introduces a silicone oil containing double bonds and a perfluoropolyether component during the polymerization process, thereby simultaneously grafting a hydrophilic group and a hydrophobic group onto the resin, thereby realizing the synthesis and preparation of an amphoteric hydrolyzable self-polishing resin, and then combining the amphoteric hydrolyzable self-polishing resin with a modified hyperbranched resin through a chemical reaction to obtain an amphoteric hyperbranched antifouling resin. Compared with the existing self-polishing antifouling resin, the resin has the advantages of good fouling resistance performance under static conditions, good mechanical properties, high solid content and low VOC.

[0014] The amphiphilic hyperbranched antifouling resin of the present invention releases toxic ions to prevent marine organisms from attaching when the ship is sailing through the exchange of metal ions in the copolymer with sodium ions in seawater, and utilizes the copolymer to be hydrolyzed into a water-soluble polymer, which is washed, dissolved and fallen off by seawater, thereby achieving a coating with a self-polishing effect. At the same time, when the ship is stationary, it can effectively inhibit the attachment of marine organisms. The prepared amphiphilic hyperbranched antifouling resin has a three-dimensional polymer material with a highly branched structure and numerous external end groups, has less intermolecular entanglement, low viscosity, good solubility and excellent film-forming performance, and contains a polymer material with a hydrophilic group and a hydrophobic group, can form hydrophilic and hydrophobic microregions on the surface of the coating, and has a good antifouling effect.

[0015] As a preferred embodiment of the present invention, the mass ratio of methyl methacrylate, butyl acrylate, acryloxytrimethylsilane, hydroxyethyl methacrylate, initiator and solvent is (4-15): (14-18): (8-16): (1-4): (0.2-0.6): (50-200).

[0016] As a preferred embodiment of the present invention, the mass ratio of methyl methacrylate, perfluoropolyether acrylate and silicone acrylate is (4-15):(2-4):(0.1-0.5).

[0017] As a preferred embodiment of the present invention, the initiator includes at least one of azobisisobutyronitrile, dicumyl peroxide, tert-butyl peroxide, potassium persulfate, and ammonium persulfate;

[0018] The solvent in step (1) comprises at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclopentane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide.

[0019] As a preferred embodiment of the present invention, the mass ratio of the amphoteric hydrolyzable self-polishing resin, isocyanate, solvent, and modified hyperbranched resin is (10-20): (1-2): (60-200): (15-25);

[0020] The amount of the catalyst is 0.2-0.6 wt % of the mixed solution.

[0021] As a preferred embodiment of the present invention, the solvent in step (2) comprises at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclopentane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide;

[0022] The catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, and stannous octoate;

[0023] The isocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

[0024] As a preferred embodiment of the present invention, the preparation method of the modified hyperbranched resin is:

[0025] S1. Add triethylamine and acyl chloride solution to the terminal hydroxyl hyperbranched resin solvent in a solvent, react (temperature is room temperature, reaction time is 2 to 6 hours), filter, remove the solvent from the filtrate, and obtain a modified hyperbranched resin.

[0026] Wherein, the synthesis principle of the modified hyperbranched resin is as follows:

[0027]

[0028] As a preferred embodiment of the present invention, the mass ratio of the terminal hydroxyl hyperbranched resin, the solvent, triethylamine, and the acyl chloride compound is (15-25): (50-100): (1.5-2.5): (2-10);

[0029] The acyl chloride compound includes at least one of benzoyl chloride, acetyl chloride, benzenesulfonyl chloride and palmitoyl chloride;

[0030] The solvent in step S1 includes at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclopentane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide.

[0031] The acyl chloride compound solution comprises an acyl chloride compound and a solvent. The amount of the solvent is not limited, and the amount of the acyl chloride compound can satisfy the scope of the present invention.

[0032] The present invention also provides an amphoteric hyperbranched antifouling resin, which is prepared by the above-mentioned preparation method.

[0033] The invention also provides an application of an amphoteric hyperbranched antifouling resin in the preparation of coatings.

[0034] The beneficial effects of the present invention are as follows: the present invention prepares a hydrolyzable self-polishing resin by designing a specific synthesis route, introduces a silicone oil containing double bonds and a perfluoropolyether component during the polymerization process, thereby simultaneously grafting a hydrophilic group and a hydrophobic group onto the resin, thereby realizing the synthesis and preparation of an amphoteric hydrolyzable self-polishing resin, and then combining the amphoteric hydrolyzable self-polishing resin with a modified hyperbranched resin through a chemical reaction to obtain an amphoteric hyperbranched antifouling resin. Compared with the existing self-polishing antifouling resin, the resin has the advantages of good fouling resistance performance under static conditions, good mechanical properties, high solid content and low VOC. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0036] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0037] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0038] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0039] Unless otherwise specified, the components, raw materials or instruments used in the embodiments and comparative examples of the present invention are all commercially available raw materials or instruments, and the components and raw materials used in each parallel experiment are all of the same kind.

[0040] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0041] Example 1

[0042] A method for preparing an amphoteric hydrolyzable self-polishing resin comprises the following steps:

[0043] 10g of methyl methacrylate, 16g of butyl acrylate, 12g of acryloxytrimethylsilane, 0.4g of hydroxyethyl methacrylate and 0.4g of azobisisobutylnitrile were uniformly dissolved in 120mL of tetrahydrofuran, and the above solution was subjected to three quick freezing-vacuuming-thawing cycles to remove oxygen in the solution. The reaction was carried out at 70°C for 12h, and 3g of perfluoropolyether acrylate (from Fuzhou Taipuda New Materials Co., Ltd., with an average molecular weight of 2000) and 0.2g of silicone acrylate (from Shanghai MacLean Biochemical Technology Co., Ltd.) were added. The reaction was carried out at 70°C for 16h, and the solvent was removed by rotary evaporation. The product obtained by rotary evaporation was precipitated in n-hexane to remove impurities, and then placed in a vacuum oven and heated at 60°C to obtain an amphoteric hydrolyzable self-polishing resin.

[0044] Example 2

[0045] A method for preparing a hydrolyzable self-polishing resin comprises the following steps:

[0046] 10g of methyl methacrylate, 16g of butyl acrylate, 12g of acryloxytrimethylsilane, 0.4g of hydroxyethyl methacrylate and 0.4g of azobisisobutylnitrile were evenly dissolved in 120mL of tetrahydrofuran, and the above solution was subjected to three quick freezing-vacuuming-thawing cycles to remove oxygen in the solution. The reaction was carried out at 70°C for 12h, and the solvent was removed by rotary evaporation. The product obtained by rotary evaporation was precipitated in n-hexane to remove impurities, and then placed in a vacuum oven at 60°C for heating and drying to obtain a hydrolyzable self-polishing resin.

[0047] Example 3

[0048] A method for preparing a hydrolyzable self-polishing resin comprises the following steps:

[0049] 10g of methyl methacrylate, 16g of butyl acrylate, 12g of acryloxytrimethylsilane, 0.4g of hydroxyethyl methacrylate and 0.4g of azobisisobutylnitrile were uniformly dissolved in 120mL of tetrahydrofuran, and the above solution was subjected to three quick freezing-vacuuming-thawing cycles to remove oxygen in the solution. The reaction was carried out at 70°C for 12h, 0.2g of silicone acrylate was added, and the reaction was carried out at 70°C for 16h. The solvent was removed by rotary evaporation, and the product obtained by rotary evaporation was precipitated in n-hexane to remove impurities, and then placed in a vacuum oven at 60°C for heating and drying to obtain a hydrolyzable self-polishing resin.

[0050] Example 4

[0051] A method for preparing an amphoteric hydrolyzable self-polishing resin comprises the following steps:

[0052] 10g of methyl methacrylate, 16g of butyl acrylate, 12g of acryloxytrimethylsilane, 0.4g of hydroxyethyl methacrylate and 0.4g of azobisisobutylnitrile were uniformly dissolved in 120mL of tetrahydrofuran, and the above solution was subjected to three quick freezing-vacuuming-thawing cycles to remove oxygen in the solution. The reaction was carried out at 70°C for 12h, 3g of perfluoropolyether acrylate was added, and the reaction was carried out at 70°C for 16h. The solvent was removed by rotary evaporation, and the product obtained by rotary evaporation was precipitated in n-hexane to remove impurities, and then placed in a vacuum oven at 60°C for heating and drying to obtain a hydrolyzable self-polishing resin.

[0053] Example 5

[0054] A method for preparing a modified hyperbranched resin comprises the following steps:

[0055] 20 g of H304 hydroxyl-terminated hyperbranched resin was dissolved in 60 mL of DMF at room temperature, 2 g of triethylamine was added, and then a DMF solution of 0.035 mol of benzoyl chloride was added dropwise under stirring. After stirring for 4 h, the filtrate was collected by filtration, and the excess solvent was removed by rotary evaporation to obtain a modified hyperbranched resin.

[0056] Example 6

[0057] A method for preparing a modified hyperbranched resin comprises the following steps:

[0058] 20 g of H304 hydroxyl-terminated hyperbranched resin was dissolved in 60 mL of DMF at room temperature, 2 g of triethylamine was added, and then a DMF solution of 0.035 mol of acetyl chloride was added dropwise under stirring. After stirring for 4 h, the filtrate was collected by filtration, and the excess solvent was removed by rotary evaporation to obtain a modified hyperbranched resin.

[0059] Example 7

[0060] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0061] 10g of the amphoteric hydrolyzable self-polishing resin of Example 1 and 1g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, 0.5wt% of dibutyltin dilaurate was added in total, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0062] Example 8

[0063] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0064] 15g of the amphoteric hydrolyzable self-polishing resin of Example 1 and 1.5g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, 0.5wt% of dibutyltin dilaurate was added in total, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0065] Example 9

[0066] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0067] 20g of the amphoteric hydrolyzable self-polishing resin of Example 1 and 2g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, 0.5wt% of dibutyltin dilaurate was added in total, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0068] Example 10

[0069] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0070] 10g of the hydrolyzable self-polishing resin of Example 2 and 1g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, 0.5wt% of dibutyltin dilaurate was added in total, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0071] Embodiment 11

[0072] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0073] 10g of the hydrolyzable self-polishing resin of Example 3 and 1g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, a total amount of 0.5wt% of dibutyltin dilaurate was added, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0074] Example 12

[0075] A method for preparing an amphoteric hyperbranched antifouling resin comprises the following steps:

[0076] 10g of the hydrolyzable self-polishing resin of Example 4 and 1g of isophorone diisocyanate were dissolved in THF solvent, added to a three-necked flask, heated to 70°C and maintained for 1 hour under nitrogen protection to obtain a prepolymer containing excess free NCO. Subsequently, 20g of the modified hyperbranched resin of Example 5 was added, the temperature was raised to 80°C, and the reaction was performed for 9 hours. Then, a total amount of 0.5wt% of dibutyltin dilaurate was added, and the reaction solution was stirred at 80°C for 12h. Finally, the product obtained by the reaction was precipitated in n-hexane three times and dried under vacuum at 60°C to obtain the final product.

[0077] Comparative Example 1

[0078] A method for preparing a modified hyperbranched resin comprises the following steps:

[0079] 20 g of H304 hydroxyl-terminated hyperbranched resin was dissolved in 60 mL of DMF at room temperature, 2 g of triethylamine was added, and then 0.035 mol of DMF solution of benzenesulfonyl chloride was added dropwise under stirring. After stirring for 4 h, the filtrate was collected by filtration, and the excess solvent was removed by rotary evaporation to obtain a modified hyperbranched resin.

[0080] Comparative Example 2

[0081] A method for preparing a modified hyperbranched resin comprises the following steps:

[0082] 20 g of H304 hydroxyl-terminated hyperbranched resin was dissolved in 60 mL of DMF at room temperature, 2 g of triethylamine was added, and then a DMF solution of 0.035 mol of palmitoyl chloride was added dropwise under stirring. After stirring for 4 h, the filtrate was collected by filtration, and the excess solvent was removed by rotary evaporation to obtain a modified hyperbranched resin.

[0083] Test Example 1

[0084] The properties of the modified hyperbranched resins of Examples 5 and 6 and Comparative Examples 1 to 2 are shown in Table 1.

[0085] Film-forming property: Dissolve the resin in an appropriate amount of xylene and apply it on a clean metal plate. Volatilize the solvent at room temperature and let it dry to form a film. Observe the surface state of the dried film, such as whether it is flat and smooth, and whether there are defects such as bubbles, pinholes, sagging, and orange peel. If the film surface is uniform and has no obvious defects, it means that the film-forming property is good.

[0086] Viscosity: Tested using a rotational viscometer in accordance with GB / T 9751.1 standard method.

[0087] Table 1

[0088] Example 5 Example 6 Comparative Example 1 Comparative Example 2 Appearance Flat and transparent Flat and transparent / opaque Viscosity (mPa.s) 22.7 38.8 / / Film forming properties good good Unable to form film crystallization

[0089] It can be seen that the hyperbranched resin of the present invention has qualified appearance and film-forming property, the resin of comparative example 1 has poor film-forming property, and the crystalline appearance of the resin of comparative example 2 is opaque.

[0090] Test Example 2

[0091] The properties of the resins of Examples 7 to 12 are shown in Table 2.

[0092] Viscosity: The test is carried out using a rotational viscometer in accordance with the standard method of GB / T 9751.1 "Determination of viscosity of paints and varnishes using a rotational viscometer".

[0093] Adhesion: Test according to method 9.4.1 of GB / T 5210 “Adhesion test for paints and varnishes by pull-off method”.

[0094] Polishing rate: The polishing rate test was conducted on a polishing rate test device. The resin-coated sample was immersed in 4L of simulated seawater and placed 20cm from the center of a stirring paddle with a blade size of 10cm. Subsequently, the data was recorded after polishing for 15 days at a stirring speed of 1000r / min. To determine the mass loss, the sample was completely dried in an oven at 70°C for 10 hours before being weighed.

[0095] The calculation formula of mass loss is: Mass Loss = (M0-M n ) / S.

[0096] Where M0 represents the mass of the resin coating sample before the coating erosion test, M n It represents the mass of the coating resin film after 15 days of polishing, and S represents the area of ​​the coating sample.

[0097] Water contact angle: The static water contact angle of the resin coating is tested using a contact angle meter. Before the test, the dust on the surface is blown away with air, and then 5 μL of deionized water is placed on the surface of the coating for measurement.

[0098] Table 2

[0099]

[0100] As can be seen from Table 2, the amphiphilic hyperbranched antifouling resin of the present invention has the advantages of good fouling resistance performance under static conditions, good mechanical properties, high solid content and low VOC compared to the existing self-polishing antifouling resin.

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing an amphoteric hyperbranched antifouling resin, characterized in that: The following steps are involved: (1) dissolving methyl methacrylate, butyl acrylate, acryloxytrimethylsilane, hydroxyethyl methacrylate and an initiator in a solvent uniformly, reacting, adding perfluoropolyether acrylate and silicone acrylate, reacting, removing the solvent, and drying to obtain an amphoteric hydrolyzable self-polishing resin; (2) dissolving an amphoteric hydrolyzable self-polishing resin and an isocyanate in a solvent, heating and keeping the mixture warm under a nitrogen atmosphere, adding a modified hyperbranched resin, reacting the mixture to obtain a mixed solution; then adding a catalyst, stirring, and drying the mixture to obtain an amphoteric hyperbranched antifouling resin.

2. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The mass ratio of the methyl methacrylate, butyl acrylate, acryloxytrimethylsilane, hydroxyethyl methacrylate, initiator and solvent is (4-15): (14-18): (8-16): (1-4): (0.2-0.6): (50-200).

3. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The mass ratio of the methyl methacrylate, the perfluoropolyether acrylate and the silicone acrylate is (4-15):(2-4):(0.1-0.5).

4. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The initiator includes at least one of azobisisobutyronitrile, dicumyl peroxide, tert-butyl peroxide, potassium persulfate, and ammonium persulfate; The solvent in step (1) comprises at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclopentane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide.

5. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The mass ratio of the amphoteric hydrolyzable self-polishing resin, isocyanate, solvent, and modified hyperbranched resin is (10-20): (1-2): (60-200): (15-25); The amount of the catalyst is 0.2-0.6 wt % of the mixed solution.

6. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The solvent in step (2) comprises at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, sulfolane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide; The catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, and stannous octoate; The isocyanate includes at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

7. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 1, characterized in that: The preparation method of the modified hyperbranched resin is: S1. Add triethylamine and acyl chloride compound solution to the terminal hydroxyl hyperbranched resin solvent in a solvent, react, filter, remove the solvent from the filtrate, and obtain a modified hyperbranched resin.

8. The method for preparing the amphiphilic hyperbranched antifouling resin according to claim 7, characterized in that: The mass ratio of the terminal hydroxyl hyperbranched resin, the solvent, triethylamine, and the acyl chloride compound is (15-25): (50-100): (1.5-2.5): (2-10); The acyl chloride compound includes at least one of benzoyl chloride, acetyl chloride, benzenesulfonyl chloride and palmitoyl chloride; The solvent in step S1 includes at least one of tetrahydrofuran, chloroform, acetone, ethanol, methanol, propanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclopentane, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, 1,4-butyrolactone and dimethylacetamide.

9. An amphoteric hyperbranched antifouling resin, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the amphiphilic hyperbranched antifouling resin according to claim 9 in the preparation of coatings.

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