Zwitterionic environment-friendly marine antifouling coating and preparation method thereof

Abstract

The application discloses a zwitterionic environmentally-friendly marine antifouling paint and a preparation method thereof. The zwitterionic environmentally-friendly marine antifouling paint comprises the following raw materials in parts by weight: 40-80 parts of moisture-curable acrylic resin, 5-30 parts of zwitterionic block silicone oil polymer, 2-50 parts of inorganic nano bactericide, 10-20 parts of curing agent, 0.1-8 parts of pigment and filler, and 0.1-5 parts of auxiliary agent. The zwitterionic environmentally-friendly marine antifouling paint can significantly improve the mechanical properties and antifouling performance of the prepared paint by selecting a specific zwitterionic block silicone oil polymer, and the whole paint has the characteristics of environmental friendliness, multiple antifouling, long-acting, and low cost by assisting other raw materials.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to an amphoteric ion-based environmentally friendly marine antifouling coating and its preparation method. Background Technology

[0002] Currently, commercially available marine antifouling coatings primarily use two types of film-forming resins: self-polishing resins (mainly acrylic siloxane resins) and silicone resins. Self-polishing resins gradually degrade during use, resulting in vastly different lifespans under varying service conditions. Acrylic siloxane resins, based on silicone resins, generate carboxyl groups through the hydrolysis of trialkoxysilane groups under weakly alkaline seawater conditions, increasing the hydrophilicity of the polymer molecules. This allows the polymer to enter the seawater under the influence of water flow, shortening the diffusion distance of the antifouling agent to the coating / seawater interface and ensuring a relatively long-term concentration of bactericide near the coating surface, thus achieving an antifouling effect. However, these coatings commonly use high levels of Cu2O antifouling agents, resulting in poor environmental friendliness. Furthermore, marine antifouling coatings are a type of fouling-releasing coating; due to the low surface energy, the adhesion of fouling organisms to the coating surface is low, allowing for automatic removal of macroscopic fouling organisms at certain speeds. While silicone resin antifouling coatings offer excellent environmental friendliness, their poor static antifouling performance, weak mechanical properties, and poor recoatability limit their application range. Therefore, new environmentally friendly marine antifouling coatings urgently need further development.

[0003] Currently, the main directions of environmentally friendly marine antifouling coatings include: (1) hydrophilization, which introduces hydrophilic polymers, zwitterions and other hydrophilic components into the coating, mainly to reduce the attachment of macroscopic organisms by inhibiting the formation of conditioned membranes and biofilms. However, too many hydrophilic groups lead to serious deterioration of the underwater mechanical properties of the coating, while too few hydrophilic groups cannot effectively inhibit the formation of conditioned membranes and biofilms; (2) non-toxic antifouling agents, including the application of natural antifouling agents and artificially synthesized non-toxic antifouling agents. However, these antifouling agents are released quickly in seawater, are easily degraded, and have a short antifouling lifespan; (3) biomimetic micro-nano structure surface antifouling, but such antifouling surfaces are not easy to prepare on a large scale, and are easily worn and difficult to regenerate. Therefore, the existing environmentally friendly marine antifouling coatings face difficulties in practical application.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The purpose of this invention is to provide an amphoteric ion-based environmentally friendly marine antifouling coating and its preparation method. The amphoteric ion-based environmentally friendly marine antifouling coating of this invention has the characteristics of being environmentally friendly, providing multiple antifouling effects, having a long-lasting effect, and being inexpensive. It solves the problems of poor adhesion of self-polishing antifouling coatings, low static antifouling agent leaching rate, single antifouling mechanism, and short effective antifouling cycle of water-degradable antifouling coatings in the prior art.

[0006] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0007] The first aspect of this invention provides an amphoteric ion-based environmentally friendly marine antifouling coating, the amphoteric ion-based environmentally friendly marine antifouling coating comprising the following raw materials in parts by weight:

[0008] The mixture consists of 40-80 parts of moisture-curable acrylic resin, 5-30 parts of zwitterionic block silicone oil polymer, 2-50 parts of inorganic nano-bactericide, 10-20 parts of curing agent, 0.1-8 parts of pigments and fillers, and 0.1-5 parts of additives.

[0009] Preferably, the inorganic nano-bactericide is selected from at least one of nano-zinc oxide, cuprous oxide, copper sulfate, and copper hydroxide.

[0010] Preferably, the curing agent is an isocyanate curing agent.

[0011] Preferably, the pigment or filler is at least one selected from kaolin, titanium dioxide, silicon dioxide, mica powder, dolomite, calcium carbonate, barium sulfate, and aluminum hydroxide.

[0012] Preferably, the additives include a silane coupling agent and an adhesion promoter; the adhesion promoter is TEGOAddBond DS1300.

[0013] Preferably, the zwitterionic block silicone oil polymer is prepared by the following method:

[0014] (1) Hydroxyethyl acrylate (HEA), triethylamine, and tetrahydrofuran (THF) were mixed to obtain a mixture. Under ice bath and magnetic rotation conditions, a mixture of 2-bromoisobutyryl bromide (BIBB) and tetrahydrofuran (THF) was added dropwise to the mixture to initiate the reaction. After the reaction was complete, the mixture was naturally heated to room temperature and left overnight. The solvent was then removed by suction filtration and rotary evaporation. The mixture was then washed, dried, and purified using DCM and saturated brine, respectively, to obtain compound 1. The structural formula of compound 1 is as follows: ;

[0015] (2) Under nitrogen protection, compound 1 and PDMS were mixed and stirred overnight to obtain compound 2, the structural formula of which is: ;

[0016] (3) Under stirring conditions, nitrogen gas was introduced into the methanol aqueous solution to remove oxygen. SBMA, 2,2'-bipyridine and compound 2 were added to the methanol aqueous solution and nitrogen gas was introduced for a period of time. Then, copper bromide was added and the reaction was stirred at room temperature under nitrogen protection. After the reaction was completed, the precipitate was centrifuged, collected, purified and dried to obtain the zwitterionic block silicone oil polymer.

[0017] Preferably, in step (3), the mass ratio of SBMA, 2,2'-bipyridine and compound 2 is 1:(0.05~0.09):(0.2~0.4).

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned zwitterionic environmentally friendly marine antifouling coating, the method comprising the following steps:

[0019] (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture;

[0020] (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

[0021] Compared with the prior art, the beneficial effects of the present invention include at least the following:

[0022] The zwitterionic-based environmentally friendly marine antifouling coating of this invention significantly improves the mechanical and antifouling properties of the coating by selecting specific zwitterionic block silicone oil polymers. With the assistance of other raw materials, the coating is characterized by being environmentally friendly, providing multiple layers of antifouling protection, having a long-lasting effect, and being inexpensive. This solves the problems of poor adhesion of self-polishing antifouling coatings, low static antifouling agent leaching rate, single antifouling mechanism, and short effective antifouling cycle of water-degradable antifouling coatings in the prior art. Attached Figure Description

[0023] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn to scale.

[0024] Figure 1 This is a SEM image of the zwitterionic environmentally friendly marine antifouling coating used in the experimental examples of this invention, at a scale bar of 100 μm.

[0025] Figure 2 This is a SEM image of the zwitterionic environmentally friendly marine antifouling coating used in the experimental examples of this invention, at a scale bar of 20 μm.

[0026] Figure 3 The test results show the contact angle of the environmentally friendly marine antifouling coating layer in the experimental example of this invention;

[0027] Figure 4 This is the test result of the surface contact angle of the zwitterionic environmentally friendly marine antifouling coating layer in the experimental example of this invention. Detailed Implementation

[0028] The embodiments of the technical solution of the present invention will be described in detail below with reference to the examples. The following embodiments are only used to illustrate the technical solution of the present invention more clearly, and are therefore only examples, and should not be used to limit the scope of protection of the present invention.

[0029] It should be noted that, unless otherwise stated, the technical or scientific terms used in this application should have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0030] This invention provides an amphoteric ion-based environmentally friendly marine antifouling coating, which comprises the following raw materials in parts by weight:

[0031] The mixture consists of 40-80 parts of moisture-curable acrylic resin, 5-30 parts of zwitterionic block silicone oil polymer, 2-50 parts of inorganic nano-bactericide, 10-20 parts of curing agent, 0.1-8 parts of pigments and fillers, and 0.1-5 parts of additives.

[0032] In one embodiment, the inorganic nano-bactericide is selected from at least one of nano-zinc oxide, cuprous oxide, copper sulfate, and copper hydroxide.

[0033] In one embodiment, the curing agent is an isocyanate curing agent.

[0034] In one embodiment, the pigment or filler is at least one selected from kaolin, titanium dioxide, silicon dioxide, mica powder, dolomite, calcium carbonate, barium sulfate, and aluminum hydroxide.

[0035] In one embodiment, the additives include a silane coupling agent and an adhesion promoter; the adhesion promoter is TEGO AddBond DS1300.

[0036] In one embodiment, the zwitterionic block silicone oil polymer is prepared by the following method:

[0037] (1) Hydroxyethyl acrylate (HEA), triethylamine, and tetrahydrofuran (THF) were mixed to obtain a mixture. Under ice bath and magnetic rotation conditions, a mixture of 2-bromoisobutyryl bromide (BIBB) and tetrahydrofuran (THF) was added dropwise to the mixture to carry out the reaction. After the reaction was completed, the mixture was naturally heated to room temperature and left overnight. The solvent was then removed by suction filtration and rotary evaporation. The mixture was then washed, dried, and purified by DCM and saturated brine to obtain compound 1. The structural formula of compound 1 is:

[0038] (2) Under nitrogen protection, compound 1 and PDMS (aminopropyl dimethylsiloxane) were mixed and stirred overnight to obtain compound 2, the structural formula of which is: ;

[0039] (3) Under stirring conditions, nitrogen gas was introduced into the methanol aqueous solution to remove oxygen. SBMA (methacryloyl ethyl sulfobetaine), 2,2'-bipyridine and compound 2 were added to the methanol aqueous solution and nitrogen gas was introduced for a period of time. Then, copper bromide was added and the reaction was stirred at room temperature under nitrogen protection. After the reaction was completed, the precipitate was centrifuged, collected, purified and dried to obtain the zwitterionic block silicone oil polymer.

[0040] In one embodiment, in step (3), the mass ratio of SBMA, 2,2'-bipyridine and compound 2 is 1:(0.05~0.09):(0.2~0.4).

[0041] Another embodiment of the present invention provides a method for preparing the above-mentioned zwitterionic environmentally friendly marine antifouling coating, the method comprising the following steps:

[0042] (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture;

[0043] (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

[0044] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0045] The raw materials used in the following embodiments are as follows:

[0046] Isocyanate curing agents: Bayhydur 2655, Bayhydur XP 2547, and Bayhydur ultra 305, sourced from Covestro Polymers (China) Co., Ltd.

[0047] Moisture-curable acrylic resins: Bayhydrol A 2470, Bayhydrol A 2695, Bayhydrol A 2601, Bayhydrol A 2846, sourced from Covestro Polymers (China) Co., Ltd.

[0048] Silane coupling agent: KH570, sourced from Guangzhou Jianshuang Technology Chemical Co., Ltd.;

[0049] Adhesion promoter: TEGO AddBond DS1300;

[0050] PDMS: Aladdin reagent, catalog number P477941-100g;

[0051] SBMA: Aladdin Reagent, catalog number M164461-500g.

[0052] Example 1

[0053] This embodiment describes a method for preparing a zwitterionic block silicone oil polymer, which includes the following steps:

[0054] (1) Synthesis of compound 1:

[0055] In a three-necked flask, add 25 ml HEA, 33 ml triethylamine, and 250 ml anhydrous THF. Add a magnetic stir bar and set the rotation speed to 500 rpm. Place the flask in an ice bath. Connect the three-necked flask to a constant pressure funnel. Add 35 ml BIBB and 50 ml THF mixture to the constant pressure funnel. Add the BIBB and THF mixture dropwise to the flask under ice bath conditions. After the addition is complete, react in an ice bath for 2 hours. Then, allow the temperature to rise naturally to room temperature and react overnight.

[0056] Post-processing: First, filter to remove the lower precipitate impurities; evaporate the solvent under vacuum at 50°C; add 500 ml DCM, wash three times, wash three times with saturated brine, and dry with anhydrous sodium sulfate for 1 hour to obtain a pale yellow oily substance. Then, purify by column chromatography with a mobile phase of EA∶PE = 1∶4 to obtain compound 1; the reaction formula is as follows:

[0057] ;

[0058] (2) Preparation of compound 2:

[0059] In a three-hole flask, compound 1 and PDMS (molar ratio 2:1) were weighed, a stir bar was added, and the mixture was stirred overnight at room temperature under nitrogen protection to obtain compound 2. The reaction formula is as follows:

[0060] ;

[0061] (3) Take 150 ml of methanol and 150 ml of deionized water as a solvent, bubble nitrogen gas under the liquid surface for 10 min, and start stirring at the same time to make the nitrogen gas bubbles fully contact the solution to remove dissolved oxygen in the solution. Add 50 g of SBMA monomer, 3.5 g of 2,2'-bipyridine and 15.3 g of compound 2, and continue bubbling to remove oxygen for 15 min. Finally, add 1.5 g of CuBr, and stir the reaction at room temperature for 48 h under nitrogen protection to end the reaction. The white product precipitates at the bottom of the bottle, and the solution is sky blue.

[0062] Post-processing: Transfer the material from the reaction flask to a centrifuge tube and centrifuge to separate the solids; dissolve the bottom solid in water, precipitate with methanol, and wash repeatedly until the reaction product is colorless and transparent. Dry under reduced pressure in an oven at 80°C to obtain a transparent plastic-like solid, which is the zwitterionic block silicone oil polymer. The reaction formula is as follows: .

[0063] Example 2

[0064] This embodiment is an amphoteric ion-based environmentally friendly marine antifouling coating, which comprises the following raw materials in parts by weight:

[0065] The mixture consisted of 40 parts of a moisture-curable acrylic resin, 5 parts of the zwitterionic block silicone oil polymer prepared in Example 1, 2 parts of an inorganic nano-bactericide, 10 parts of a curing agent, 0.1 parts of pigments and fillers, and 0.1 parts of additives.

[0066] The inorganic nano-bactericide is nano-zinc oxide;

[0067] The curing agent is an isocyanate curing agent;

[0068] The pigment and filler are kaolin.

[0069] The additives include equal masses of silane coupling agent and adhesion promoter.

[0070] The preparation method of the above-mentioned zwitterionic environmentally friendly marine antifouling coating includes the following steps:

[0071] (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture;

[0072] (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

[0073] Example 3

[0074] This embodiment is an amphoteric ion-based environmentally friendly marine antifouling coating, which comprises the following raw materials in parts by weight:

[0075] The mixture contains 80 parts of a moisture-curable acrylic resin, 30 parts of the zwitterionic block silicone oil polymer prepared in Example 1, 50 parts of an inorganic nano-bactericide, 20 parts of a curing agent, 8 parts of pigments and fillers, and 5 parts of additives.

[0076] The inorganic nano-bactericide is nano-zinc oxide;

[0077] The curing agent is an isocyanate curing agent;

[0078] The pigment and filler are kaolin.

[0079] The additives include equal masses of silane coupling agent and adhesion promoter.

[0080] The preparation method of the above-mentioned zwitterionic environmentally friendly marine antifouling coating includes the following steps:

[0081] (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture;

[0082] (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

[0083] Example 4

[0084] This embodiment is an amphoteric ion-based environmentally friendly marine antifouling coating, which comprises the following raw materials in parts by weight:

[0085] The mixture consists of 60 parts of a moisture-curable acrylic resin, 20 parts of the zwitterionic block silicone oil polymer prepared in Example 1, 20 parts of an inorganic nano-bactericide, 15 parts of a curing agent, 5 parts of pigments and fillers, and 3 parts of additives.

[0086] The inorganic nano-bactericide is nano-zinc oxide;

[0087] The curing agent is an isocyanate curing agent;

[0088] The pigment and filler are kaolin.

[0089] The additives include equal masses of silane coupling agent and adhesion promoter.

[0090] The preparation method of the above-mentioned zwitterionic environmentally friendly marine antifouling coating includes the following steps:

[0091] (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture;

[0092] (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

[0093] Compare with Example 1

[0094] This comparative example is an environmentally friendly marine antifouling coating, which comprises the following raw materials in parts by weight:

[0095] The mixture consists of 60 parts of moisture-curable acrylic resin, 20 parts of inorganic nano-bactericide, 15 parts of curing agent, 5 parts of pigments and fillers, and 3 parts of additives.

[0096] The inorganic nano-bactericide is nano-zinc oxide;

[0097] The curing agent is an isocyanate curing agent;

[0098] The pigment and filler are kaolin.

[0099] The additives include equal masses of silane coupling agent and adhesion promoter.

[0100] The preparation method of the above-mentioned environmentally friendly marine antifouling coating includes the following steps:

[0101] (a) The wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide are mixed to obtain a mixture;

[0102] (b) Add a curing agent to the mixture and mix well to obtain the environmentally friendly marine antifouling coating.

[0103] Experimental Example 1

[0104] Obtain the zwitterionic environmentally friendly marine antifouling coating prepared in Example 4;

[0105] A layer of water-based acrylic polyurethane varnish (source: purchased water-based epoxy resin paint for marine use, item number: Shanghai Huteli water-based epoxy primer) was applied to a tinplate sheet with a pre-coated primer (the primer was sourced from purchased two-component water-based acrylic polyurethane varnish, source: Shanghai Huteli acrylic polyurethane topcoat transparent gloss varnish); then, the zwitterionic environmentally friendly marine antifouling coating prepared in Example 4 was applied as the experimental group.

[0106] Tinplate sheets were used as a control group;

[0107] Electron microscopy was performed on the zwitterionic environmentally friendly marine antifouling coating layer of the experimental group, and the results are as follows: Figures 1-2 As shown; Figure 1 This is a SEM image with a scale of 100 μm. Figure 2 This is a SEM image with a scale bar of 20 μm;

[0108] Depend on Figures 1-2 It can be seen that the surface of the zwitterionic environmentally friendly marine antifouling coating is relatively uniform, and the zwitterionic environmentally friendly marine antifouling coating and varnish can be mixed evenly.

[0109] A layer of water-based acrylic polyurethane varnish (source: purchased water-based epoxy resin paint for marine use, item number, source: Shanghai Huteli water-based epoxy primer) was applied to a tinplate sheet with a pre-coated primer (the primer was sourced from purchased two-component water-based acrylic polyurethane varnish, source: Shanghai Huteli acrylic polyurethane topcoat transparent gloss varnish); then the environmentally friendly marine antifouling coating prepared in Comparative Example 1 was applied by scraping.

[0110] The hydrophilicity of the coatings in environmentally friendly marine antifouling coatings and zwitterionic environmentally friendly marine antifouling coatings was tested, and the results are as follows: Figures 3-4 As shown; Figure 3 Contact angle test for environmentally friendly marine antifouling coating layers; Figure 4 Contact angle test for zwitterionic environmentally friendly marine antifouling coating;

[0111] Depend on Figures 3-4 It can be seen that the contact angle of the coating decreases and the hydrophilicity is enhanced after doping with zwitterionic compounds.

[0112] The experimental and control groups were placed in the sea for 3 months, and the bacterial count, diatom count, and juvenile shellfish attachment count were measured. Compared with the control group, the bacterial count in the experimental group was reduced by 86%, the diatom count was reduced by 88%, and the juvenile shellfish attachment count was reduced by 90%.

[0113] 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 therein. Such 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, and they should all be covered within the scope of the claims and specification of the present invention.

Claims

1. An environmentally friendly zwitterionic-based marine antifouling coating, characterized by, The zwitterionic environmentally friendly marine antifouling coating comprises the following raw materials in parts by weight: The mixture consists of 40-80 parts of moisture-curable acrylic resin, 5-30 parts of zwitterionic block silicone oil polymer, 2-50 parts of inorganic nano-bactericide, 10-20 parts of curing agent, 0.1-8 parts of pigments and fillers, and 0.1-5 parts of additives.

2. The zwitterionic-based environmentally friendly marine antifouling coating according to claim 1, characterized in that, The inorganic nano-bactericide is selected from at least one of nano-zinc oxide, cuprous oxide, copper sulfate, and copper hydroxide.

3. The zwitterionic-based environmentally friendly marine antifouling coating according to claim 1, characterized in that, The curing agent is an isocyanate curing agent.

4. The zwitterionic-based environmentally friendly marine antifouling coating according to claim 1, characterized in that, The pigments and fillers are at least one of kaolin, titanium dioxide, silicon dioxide, mica powder, dolomite, calcium carbonate, barium sulfate, and aluminum hydroxide.

5. The zwitterionic environmentally friendly marine antifouling coating according to claim 1, characterized in that, The additives include silane coupling agents and adhesion promoters; the adhesion promoter is TEGO AddBond DS1300.

6. The zwitterionic environmentally friendly marine antifouling coating according to claim 1, characterized in that, The zwitterionic block silicone oil polymer is prepared by the following method: (1) Hydroxyethyl acrylate (HEA), triethylamine, and tetrahydrofuran (THF) were mixed to obtain a mixture. Under ice bath and magnetic rotation conditions, a mixture of 2-bromoisobutyryl bromide (BIBB) and tetrahydrofuran (THF) was added dropwise to the mixture to initiate the reaction. After the reaction was complete, the mixture was naturally heated to room temperature and left overnight. The solvent was then removed by suction filtration and rotary evaporation. The mixture was then washed, dried, and purified using DCM and saturated brine, respectively, to obtain compound 1. The structural formula of compound 1 is as follows: ; (2) Under nitrogen protection, compound 1 and PDMS were mixed and stirred overnight to obtain compound 2, the structural formula of which is: ; (3) Under stirring conditions, nitrogen gas was introduced into the methanol aqueous solution to remove oxygen. SBMA, 2,2'-bipyridine and compound 2 were added to the methanol aqueous solution and nitrogen gas was introduced for a period of time. Then, copper bromide was added and the reaction was stirred at room temperature under nitrogen protection. After the reaction was completed, the precipitate was centrifuged, collected, purified and dried to obtain the zwitterionic block silicone oil polymer.

7. The zwitterionic environmentally friendly marine antifouling coating according to claim 6, characterized in that, In step (3), the mass ratio of SBMA, 2,2'-bipyridine and compound 2 is 1:(0.05~0.09):(0.2~0.4).

8. The method for preparing the zwitterionic environmentally friendly marine antifouling coating according to any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: (a) Mix zwitterionic block silicone oil polymer, wet-curable acrylic resin, additives, pigments and fillers, and inorganic nano-bactericide to obtain a mixture; (b) Add a curing agent to the mixture and mix well to obtain the zwitterionic environmentally friendly marine antifouling coating.

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