Flexible antifouling and resistance-reducing composite coating with temperature responsiveness and preparation method and application of flexible antifouling and resistance-reducing composite coating

Abstract

The invention discloses a flexible anti-fouling and anti-drag composite coating with temperature responsiveness and a preparation method and application of the flexible anti-fouling and anti-drag composite coating. The flexible antifouling anti-drag composite coating comprises a substrate layer, a flexible buffer layer, an antifouling response layer and a hydrophobic surface layer which are sequentially formed on the surface of a base material, wherein the substrate layer comprises adhesive resin, a positively charged polymer and a particle filler; the flexible buffer layer comprises flexible polymer resin, a negatively charged polymer, a polymer drag reducer and an anti-ultraviolet additive; the hydrophobic surface layer comprises flexible polymer resin, a temperature-responsive polymer microcapsule encapsulated with an antifouling agent, a pore-foaming agent, an anti-ultraviolet additive and super-hydrophobic micro-nano particles. The flexible anti-fouling and anti-drag composite coating with temperature responsiveness provided by the invention has strong binding force with a base material, and also has anti-fouling property, corrosion protection property and anti-drag property; meanwhile, the preparation method provided by the invention has the advantages of wide application range, large-area coating and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of marine coating protection, and in particular relates to a temperature-responsive flexible antifouling and drag-reducing composite coating and a preparation method and application thereof. Background Art

[0002] With the acceleration of industrialization, antifouling and drag reduction have become urgent problems to be solved in many fields. Especially in the marine transportation and water treatment industries. The problem of biological attachment (such as attachment of mussels, algae and other organisms) on the surface of ships and marine structures is very common, and the increase in friction resistance caused by it has become the main reason for reduced operating efficiency and increased energy consumption. Therefore, the development of a new type of antifouling coating to cope with and adapt to different environmental conditions is the focus of continuous attention in the industry. At present, flexible drag reduction technology is a key research direction in drag reduction technology. Its drag reduction mechanism relies on the flexible effect to suppress and absorb the wave change of water pressure and delay the transition from laminar flow to turbulent flow, thereby achieving an effective drag reduction effect. However, in practical applications, it is difficult to cope with complex and changing environments by relying solely on flexible mechanisms, and it is also impossible to avoid the dilemma of being attached by marine organisms and losing drag reduction performance under long-term immersion in seawater. Through multi-layer structural design, a variety of special functional compounds are effectively integrated together to achieve the goal of integrated antifouling, drag reduction and hydrophobic functions with synergistic enhancement of chemical prevention and physical repulsion, which is an innovative idea. Therefore, this temperature-responsive antifouling and drag-reducing coating has broad application prospects and will bring major technological breakthroughs and economic benefits to the marine transportation and water treatment industries. Summary of the invention

[0003] The main purpose of the present invention is to provide a temperature-responsive flexible antifouling and drag-reducing composite coating and a preparation method and application thereof, so as to overcome the deficiencies of the prior art.

[0004] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes: The embodiment of the present invention provides a temperature-responsive flexible antifouling and drag-reducing composite coating, which comprises: a base layer, a flexible buffer layer, an antifouling response layer and a hydrophobic surface layer sequentially formed on the surface of a substrate; Among them, the base layer includes adhesive resin, positively charged polymer and particulate filler; the flexible buffer layer includes flexible polymer resin, negatively charged polymer, polymer drag reducer and anti-ultraviolet additive; the anti-fouling response layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent and anti-ultraviolet additive; the hydrophobic surface layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent, porogen, anti-ultraviolet additive and super-hydrophobic micro-nanoparticles; the positively charged polymer includes polyvinyl alcoholamine and / or polydimethylaminoethyl methacrylamide; the negatively charged polymer includes any one or a combination of two or more of polyvinyl alcohol acid, polyether sulfone and sodium polystyrene sulfonate.

[0005] The embodiment of the present invention also provides a method for preparing the aforementioned temperature-responsive flexible antifouling and drag-reducing composite coating, which comprises: Applying a first base liquid containing at least an adhesive resin, a positively charged polymer, a particle filler, and a diluent to the surface of the substrate and subjecting the substrate to a first curing treatment to form a base layer having a multi-level micro-nano structure; Applying a second base liquid containing at least a flexible polymer resin, a negatively charged polymer, a polymer drag reducer, an anti-ultraviolet additive and a solvent to the surface of the base layer and performing a second curing treatment to form a flexible buffer layer; Applying a third base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, an anti-ultraviolet additive and a solvent to the surface of the flexible buffer layer and subjecting the third base liquid to a third curing treatment to form an antifouling responsive layer; And, a fourth base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, a porogen, an anti-ultraviolet additive, super-hydrophobic micro-nanoparticles and a solvent is applied to the surface of the antifouling response layer and subjected to a fourth curing treatment to form a hydrophobic surface layer, thereby obtaining a flexible antifouling and drag-reducing composite coating with temperature responsiveness.

[0006] The embodiments of the present invention also provide the application of the aforementioned temperature-responsive flexible antifouling and drag-reducing composite coating in the intelligent protection of the surface of a hull, a pipeline, an offshore platform or an underwater structure.

[0007] An embodiment of the present invention also provides a method for reducing the navigation resistance of a navigation body, which comprises: coating at least the surface of the navigation body in contact with the liquid with the aforementioned temperature-responsive flexible anti-fouling and drag-reducing composite coating.

[0008] Compared with the prior art, the present invention has the following beneficial effects: First, the base layer of the present invention is uniquely designed. It not only has a high-strength interface bonding force and is firmly bonded to the substrate, but also utilizes the interaction between the positively charged polymer and the negatively charged polymer to produce a strong interface bonding with the flexible buffer layer, ensuring the stability and durability of the coating. Secondly, the introduction of the flexible buffer layer significantly improves the drag reduction performance with its excellent flexibility and mechanical buffering and deformation capabilities. The design of this layer enables the coating to better adapt and respond to the shear force of the water flow, thereby reducing resistance and improving the propulsion efficiency of the ship. Furthermore, the flexible antifouling response layer in the present invention mainly serves to store and release antifouling agents. Under thermal response conditions, the antifouling agent can slowly diffuse through the loose structure channel of the hydrophobic surface layer, effectively preventing dirt from attaching and keeping the surface clean. This design not only improves efficiency, but also extends service life. In addition, the hydrophobic surface layer and the antifouling response layer use the same flexible polymer resin, which ensures a strong interface bonding between the two, which is beneficial to the overall performance of the coating. At the same time, the hydrophobic structure naturally has the ability to reduce pollution attachment, further enhancing the antifouling performance of the coating. Finally, the four-layer structure of the present invention synergizes to achieve a multifunctional coating that integrates thermal response, antifouling and hydrophobicity. This design not only improves the drag reduction and antifouling performance of the coating, but also provides corrosion protection and physical barriers, fully protecting ship equipment. At the same time, the preparation method adopted by the present invention has the advantages of wide application range and suitable for large-area coating, providing an ideal solution for the upgrading of ship propulsion systems. In summary, the present invention has significant technical advantages and outstanding effects, and will bring significant energy conservation, emission reduction and economic benefits to the ship industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0010] Figure 1 It is a schematic diagram of the structure of a flexible antifouling and drag-reducing composite coating with temperature responsiveness in a typical embodiment of the present invention.

[0011] Description of the drawings: 1-substrate, 2-base layer, 3-flexible buffer layer, 4-antifouling response layer, 5-hydrophobic surface layer. DETAILED DESCRIPTION

[0012] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0013] Specifically, as one aspect of the technical solution of the present invention, a temperature-responsive flexible antifouling and drag-reducing composite coating includes: a base layer, a flexible buffer layer, an antifouling response layer and a hydrophobic surface layer sequentially formed on the surface of a substrate; Among them, the base layer includes adhesive resin, positively charged polymer and particulate filler; the flexible buffer layer includes flexible polymer resin, negatively charged polymer, polymer drag reducer and anti-ultraviolet additive; the anti-fouling response layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent and anti-ultraviolet additive; the hydrophobic surface layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent, porogen, anti-ultraviolet additive and super-hydrophobic micro-nanoparticles; the positively charged polymer includes polyvinyl alcoholamine and / or polydimethylaminoethyl methacrylamide; the negatively charged polymer includes any one or a combination of two or more of polyvinyl alcohol acid, polyether sulfone and sodium polystyrene sulfonate.

[0014] The function of the base layer in the present invention is not only to have a high-strength interface bonding force with the substrate, but also to generate a strong interface bonding force with the flexible buffer layer through the positively charged polymer and the negatively charged polymer; the flexible buffer layer provides mechanical buffering and deformation ability with excellent flexibility and elasticity, thereby improving the drag reduction performance; the flexible antifouling response layer mainly provides storage and release of the antifouling agent, and in the case of thermal response, the antifouling agent is slowly diffused and released through the loose structure channel of the hydrophobic surface layer; the hydrophobic surface layer and the antifouling response layer use the same flexible polymer resin to ensure strong interface bonding. On the one hand, a porous structure is formed in situ under the action of the porogen, providing a structural channel for the diffusion of the antifouling agent, and on the other hand, the hydrophobic structure naturally has the ability to reduce the attachment of pollution. Under the synergistic effect of the four-layer structure, a multifunctional coating integrating thermal response, antifouling and hydrophobicity is realized.

[0015] In some preferred embodiments, the thickness of the base layer is 20-60 μm.

[0016] In some preferred embodiments, the thickness of the flexible buffer layer is 0.1-0.5 mm.

[0017] In some preferred embodiments, the antifouling response layer has a thickness of 0.1 to 0.5 mm.

[0018] In some preferred embodiments, the hydrophobic surface layer has a thickness of 10 to 60 μm.

[0019] In some preferred embodiments, the method for preparing the temperature-responsive polymer microcapsules encapsulating the antifouling agent comprises: The temperature-responsive polymer monomer, antifouling agent, cross-linking agent, initiator and nucleating particles are emulsified and polymerized in a water-oil solution at 50-80° C. for 12-24 hours to prepare temperature-responsive polymer microcapsules encapsulating the antifouling agent.

[0020] Further, the temperature responsive polymer monomer includes N-isopropylacrylamide, but is not limited thereto.

[0021] Furthermore, the antifouling agent includes any one of copper pyrithione, zinc pyrithione, chitosan or a combination of two or more thereof, but is not limited thereto.

[0022] Further, the cross-linking agent includes any one or a combination of two or more of N,N'-methylenebisacrylamide (MBA), divinylbenzene, and diisocyanate, but is not limited thereto.

[0023] Further, the initiator includes any one or a combination of two or more of potassium persulfate (KPS), azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (AIBME), and azobisisoheptanenitrile, but is not limited thereto.

[0024] Furthermore, the nucleation particles include any one or a combination of two or more of gas-phase hydrophobic SiO2, gas-phase hydrophilic SiO2, TiO2, and Al2O3, and are not limited thereto.

[0025] In some more specific embodiments, the structural schematic diagram of the temperature-responsive flexible antifouling and drag-reducing composite coating is as follows: Figure 1 As shown, it includes a substrate 1, a base layer 2, a flexible buffer layer 3, an anti-fouling response layer 4, and a hydrophobic surface layer 5.

[0026] The present invention aims to invent a multi-layer composite structure coating that is both room temperature responsive and antifouling and elastic, with a flexible elastic resin providing a flexible drag reduction function, a room temperature responsive antifouling capsule providing antifouling properties, and a hydrophobic surface layer to achieve physical isolation and corrosion protection properties. The temperature responsive flexible antifouling and drag reduction functional coating provided has significant drag reduction and antifouling effects, and also has excellent bonding strength, durability, corrosion protection and other characteristics. At the same time, the preparation method used in the present invention has the advantages of wide application range and large-area coating.

[0027] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned temperature-responsive flexible antifouling and drag-reducing composite coating, which comprises: Applying a first base liquid containing at least an adhesive resin, a positively charged polymer, a particle filler, and a diluent to the surface of the substrate and subjecting the substrate to a first curing treatment to form a base layer having a multi-level micro-nano structure; Applying a second base liquid containing at least a flexible polymer resin, a negatively charged polymer, a polymer drag reducer, an anti-ultraviolet additive and a solvent to the surface of the base layer and performing a second curing treatment to form a flexible buffer layer; Applying a third base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, an anti-ultraviolet additive and a solvent to the surface of the flexible buffer layer and subjecting the third base liquid to a third curing treatment to form an antifouling responsive layer; And, a fourth base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, a porogen, an anti-ultraviolet additive, super-hydrophobic micro-nanoparticles and a solvent is applied to the surface of the antifouling response layer and subjected to a fourth curing treatment to form a hydrophobic surface layer, thereby obtaining a flexible antifouling and drag-reducing composite coating with temperature responsiveness.

[0028] In some preferred embodiments, the preparation method specifically comprises: applying the first base liquid to the surface of the substrate by spraying or brushing and curing it at room temperature for 12 to 24 hours to form the base layer.

[0029] In some preferred embodiments, the preparation method specifically comprises: applying the second base liquid to the surface of the base layer by spraying or brushing and curing it at room temperature for 4 to 12 hours to form a flexible buffer layer.

[0030] In some preferred embodiments, the preparation method specifically comprises: applying the third base liquid to the surface of the flexible buffer layer by spraying or brushing and curing it at room temperature for 12 to 24 hours to form the antifouling response layer.

[0031] In some preferred embodiments, the preparation method specifically comprises: applying the fourth base liquid to the surface of the antifouling response layer by spraying or brushing and curing it at room temperature for 12 to 24 hours to form the hydrophobic surface layer.

[0032] In some preferred embodiments, the mass ratio of the adhesive resin, the positively charged polymer, the particle filler and the diluent in the first base liquid is 10-50:0.5-5:0.5-5:0-30.

[0033] In some preferred embodiments, the mass ratio of the flexible polymer resin, the negatively charged polymer, the polymer drag reducer, the anti-ultraviolet additive and the solvent in the second base liquid is 20-50:0.5-5:0.5-5:0.5-5:0-30.

[0034] In some preferred embodiments, the mass ratio of the flexible polymer resin, the temperature-responsive polymer microcapsules encapsulating the antifouling agent, and the solvent in the third base liquid is 30-40:1-5:0-30.

[0035] In some preferred embodiments, the mass ratio of the flexible polymer resin, the temperature-responsive polymer microcapsules encapsulating the antifouling agent, the porogen, the anti-ultraviolet additive, the super-hydrophobic micro-nanoparticles and the solvent in the fourth base liquid is 20~50:0~5:0~5:0~2:0~5:0~30.

[0036] In some preferred embodiments, the adhesive resin includes any one or a combination of two or more of modified epoxy resin, epoxy zinc-rich primer, acrylic polyurethane paint, amino silicone resin, polyurethane, and fluorinated modified epoxy resin, and is not limited thereto.

[0037] In some preferred embodiments, the particulate filler includes any one or a combination of two or more of kaolin, talc, mica powder, zinc oxide, titanium dioxide, silicon dioxide, glass beads, and diatomaceous earth, but is not limited thereto.

[0038] In some preferred embodiments, the particle size of the particulate filler is 1-100 μm, but is not limited thereto.

[0039] In some preferred embodiments, the diluent includes any one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, propylene glycol methyl ether, and formamide, and is not limited thereto.

[0040] In some preferred embodiments, the flexible polymer resin includes any one or a combination of two or more of silicone resin, polyurethane, acrylic modified silicone resin, and polyurea, but is not limited thereto.

[0041] In some preferred embodiments, the polymer drag reducer includes any one or a combination of two or more of polyacrylamide, polyvinyl alcohol, sodium polyisoacrylate, and polyvinyl pyrrolidone, but is not limited thereto.

[0042] In some preferred embodiments, the anti-ultraviolet additive includes any one or a combination of two or more of 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazine-2-yl)-4,6-bis(2-methylmethylamino-ethyl)-phenol, 2-hydroxyphenols and their derivatives, and octyl salicylate, and is not limited thereto.

[0043] In some preferred embodiments, the solvent includes any one or a combination of two or more of toluene, xylene, ethyl acetate, acetone, ethanol, butanol, and butyl acetate, and is not limited thereto.

[0044] In some preferred embodiments, the substrate includes any one of a steel substrate, an aluminum alloy substrate, and a copper alloy substrate, or a combination of two or more thereof, and is not limited thereto.

[0045] In some preferred embodiments, the porogen includes any one of sodium chloride, lactose, sucrose, ammonium bicarbonate, sodium bicarbonate, or a combination of two or more thereof, and is not limited thereto.

[0046] In some preferred embodiments, the preparation method of the super-hydrophobic micro-nanoparticles comprises: mixing micro-nanoparticles, ammonia water, tetraethyl silicate, a hydrophobic treatment modifier and water for 6 to 24 hours to obtain the super-hydrophobic micro-nanoparticles; wherein the hydrophobic treatment modifier comprises any one of alkyl siloxanes, alkyl chlorosilanes, fluoroalkyl siloxanes, alkyl organosilanes, and perfluoroalkyl organosilanes, or a combination of two or more thereof, and is not limited thereto.

[0047] Another aspect of the embodiments of the present invention further provides the use of the aforementioned temperature-responsive flexible antifouling and drag-reducing composite coating in intelligent protection of the surface of a hull, a pipeline, an offshore platform or an underwater structure.

[0048] Another aspect of an embodiment of the present invention further provides a method for reducing the navigation resistance of a navigation body, which comprises: coating the aforementioned temperature-responsive flexible anti-fouling and drag-reducing composite coating on at least the surface of the navigation body in contact with the liquid.

[0049] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0050] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0051] Example 1 (1) 68 wt.% epoxy zinc-rich primer, 2 wt.% polyvinyl alcoholamine, and 7 wt.% kaolin were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of the steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic silicone resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of polyvinyl alcohol, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in xylene and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component highly elastic silicone resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L of zinc pyridinethione ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0052] (4) 30 wt.% of a single-component highly elastic silicone resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 1 wt.% of sodium chloride, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in situ brushed on the surface of the above antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% SiO2 nanoparticles (30nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% perfluoroalkyl chlorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super amphiphobic SiO2 nanoparticles.

[0053] Example 2 (1) 75 wt.% acrylic polyurethane paint, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% zinc oxide were dissolved in ethyl acetate and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of the steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component flexible polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of polyvinyl alcohol, and 1 wt.% of 2-(2H-benzotriazine-2-yl)-4,6-bis(2-methylmethylamino-ethyl)-phenol were dissolved in ethyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid was applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 60 wt.% of a single-component flexible polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-(2H-benzotriazine-2-yl)-4,6-bis(2-methylmethylamino-ethyl)-phenol were dissolved in ethyl acetate and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L of zinc pyridinethione ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0054] (4) 30 wt.% of a single-component highly elastic silicone resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of ammonium bicarbonate, 1 wt.% of 2-(2H-benzotriazine-2-yl)-4,6-bis(2-methylmethylamino-ethyl)-phenol, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in ethyl acetate and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in situ brushed on the surface of the above antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% diatomite nanoparticles (10 μm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% perfluoroalkyl organosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic diatomite nanoparticles.

[0055] Example 3 (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0056] (4) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0057] Comparative Example 1 (Compared with Example 3: without adding temperature-responsive polymer microcapsules) (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) dissolving 40 wt.% of a single-component high-elastic polyurethane resin and 2 wt.% of 2-hydroxy-4-methoxybenzophenone in xylene, and uniformly stirring the mixture mechanically to obtain a third base liquid; applying the base liquid in situ on the surface of the flexible buffer layer, and curing the base liquid at room temperature for 12 hours to form an antifouling response layer; (4) 30 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of super-hydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned anti-fouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible anti-fouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0058] Performance characterization: The prepared composite coating does not have temperature-responsive antifouling and antifouling properties.

[0059] Comparative Example 2 (Compared with Example 3: lack of hydrophobic surface layer) (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0060] Performance characterization: The prepared composite coating has temperature-responsive antifouling properties, but poor hydrophobic effect and weak salt spray resistance.

[0061] Comparative Example 3 (Compared with Example 3: lacking a flexible buffer layer) (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0062] (3) 30 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of super-hydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned anti-fouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible anti-fouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0063] Performance characterization: The prepared composite coating has temperature-responsive antifouling properties, but poor drag reduction effect.

[0064] Comparative Example 4 (Compared with Example 3: lacking a base layer) (1) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned base layer, and cured at room temperature for 8 hours to form a flexible buffer layer; (2) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0065] (3) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0066] Performance characterization: The prepared composite coating has temperature-responsive antifouling properties, but has poor bonding with the substrate and is easy to fall off.

[0067] Comparative Example 5 (Compared with Example 3: lack of flexible polymer resin) (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) dissolving 78 wt.% of amino silicone resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone in butyl acetate, and uniformly stirring the mixture mechanically to obtain a second base liquid; applying the base liquid in situ on the surface of the substrate, and curing the base liquid at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of amino silicone resin, 4 wt.% of temperature-responsive polymer microcapsules encapsulating antifouling agents, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0068] (4) 30 wt.% of amino silicone resin, 1 wt.% of temperature-responsive polymer microcapsules encapsulating antifouling agents, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in situ brushed on the surface of the above antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0069] Performance characterization: The prepared composite coating has temperature-responsive antifouling properties but no drag reduction effect.

[0070] Comparative Example 6 Compared with Example 3: the antifouling responsive layer lacks the temperature-responsive polymer microcapsules encapsulating the antifouling agent; (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) dissolving 40 wt.% of a single-component high-elastic polyurethane resin and 2 wt.% of 2-hydroxy-4-methoxybenzophenone in xylene, and uniformly stirring the mixture mechanically to obtain a third base liquid; applying the base liquid in situ on the surface of the flexible buffer layer, and curing the base liquid at room temperature for 12 hours to form a connecting layer; (4) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0071] The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0072] Performance: The antifouling life of the coating is short and the antifouling property of the coating is greatly weakened.

[0073] Comparative Example 7 Compared with Example 3: the hydrophobic surface layer lacks the temperature-responsive polymer microcapsules encapsulating the antifouling agent; (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0074] (4) 30 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of super-hydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned anti-fouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible anti-fouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0075] Performance: The coating has poor antifouling and responsiveness in its initial state, and the overall antifouling property is weakened:

[0076] Comparative Example 8 Compared with Example 3: lack of anti-ultraviolet additive; (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) dissolving 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, and 3 wt.% of sodium polyisoacrylate in butyl acetate, and uniformly stirring the mixture mechanically to obtain a second base liquid; applying the base liquid in situ on the surface of the above-mentioned base layer, and curing the base liquid at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin and 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0077] (4) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of sodium bicarbonate, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0078] Performance: The coating has poor UV resistance and is prone to yellowing and powdering.

[0079] Comparative Example 9 Compared with Example 3: the positively charged polymer (polydimethylaminoethyl methacrylamide) and the negatively charged polymer (sodium polystyrene sulfonate) are missing.

[0080] (1) 70 wt.% amino silicone resin and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of the steel substrate and cured at room temperature for 12 hours to form a base layer; (2) dissolving 78 wt.% of a single-component high-elastic polyurethane resin, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone in butyl acetate, and uniformly stirring the mixture mechanically to obtain a second base liquid; applying the base liquid in situ on the surface of the above-mentioned base layer, and curing the base liquid at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0081] (4) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 2 wt.% of sodium bicarbonate, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in-situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0082] Performance: The adhesion of the coating becomes poor and it is easy to fall off.

[0083] Comparative Example 10 Compared with Example 3: lack of porogen (sodium bicarbonate).

[0084] (1) 70 wt.% amino silicone resin, 2 wt.% polydimethylaminoethyl methacrylamide, and 7 wt.% glass microbeads were dissolved in xylene and mixed evenly to obtain a first base liquid; the base liquid was brushed on the surface of a steel substrate and cured at room temperature for 12 hours to form a base layer; (2) 78 wt.% of a single-component high-elastic polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of sodium polyisoacrylate, and 3 wt.% of 2-hydroxy-4-methoxybenzophenone are dissolved in butyl acetate and uniformly stirred mechanically to obtain a second base liquid; the base liquid is applied in situ on the surface of the above-mentioned base layer and cured at room temperature for 8 hours to form a flexible buffer layer; (3) 40 wt.% of a single-component high-elastic polyurethane resin, 4 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, and 2 wt.% of 2-hydroxy-4-methoxybenzophenone were dissolved in xylene and uniformly stirred mechanically to obtain a third base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned flexible buffer layer, and cured at room temperature for 12 hours to form an antifouling responsive layer; The preparation method of the temperature-responsive polymer microcapsules of the antifouling agent is as follows: 1.5g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100ml of deionized water to prepare the water phase, 10ml of N-isopropylacrylamide (NIPAM), 0.5ml of N,N'-methylenebisacrylamide (MBA), and 0.2ml of azobisisobutyronitrile (AIBN) were added to 50ml of xylene to prepare the oil phase, and then the water and oil phases were mixed at a volume ratio of 1 / 3, stirred at high speed for 12h at 50°C, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L chitosan ethanol solution and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0085] (4) 30 wt.% of a single-component high-elastic polyurethane resin, 1 wt.% of a temperature-responsive polymer microcapsule encapsulating an antifouling agent, 1 wt.% of 2-hydroxy-4-methoxybenzophenone, and 5 wt.% of superhydrophobic micro-nanoparticles are dissolved in xylene and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid is in situ brushed on the surface of the above-mentioned antifouling response layer, and cured at room temperature for 24 hours to obtain a temperature-responsive flexible antifouling and drag-reducing functional coating; The preparation method of super hydrophobic micro-nano particles is as follows: 5 wt.% TiO2 nanoparticles (50nm), 10 wt.% ammonia water, 5 wt.% deionized water, 4 wt.% tetraethyl silicate, and 2 wt.% n-octylperfluorosilane were added to anhydrous ethanol in sequence and reacted with continuous mechanical stirring for 8 hours. After the reaction, the solution was rotary evaporated to obtain super-amphiphobic TiO2 nanoparticles.

[0086] Performance: The coating fails to form a porous structure, the superhydrophobic performance deteriorates, the antifouling agent release channel becomes smaller, the antifouling agent is released slowly, and the antifouling property deteriorates.

[0087] The composite coatings provided in the comparative examples and embodiments of the present invention were subjected to performance tests, wherein the adhesion test standard was GB / T5210-2006, and the salt spray test standard was GB / T10125-1997. The specific test results are shown in Table 1 below: Table 1 Properties of the coatings prepared in Examples 1-3 and Comparative Examples 1-10 ; In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0088] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A temperature-responsive flexible antifouling and drag-reducing composite coating, characterized in that: include: A base layer, a flexible buffer layer, an antifouling response layer and a hydrophobic surface layer are sequentially formed on the surface of the substrate; Among them, the base layer includes adhesive resin, positively charged polymer and particulate filler; the flexible buffer layer includes flexible polymer resin, negatively charged polymer, polymer drag reducer and anti-ultraviolet additive; the anti-fouling response layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent and anti-ultraviolet additive; the hydrophobic surface layer includes flexible polymer resin, temperature-responsive polymer microcapsules encapsulating anti-fouling agent, porogen, anti-ultraviolet additive and super-hydrophobic micro-nanoparticles; the positively charged polymer includes polyvinyl alcoholamine and / or polydimethylaminoethyl methacrylamide; the negatively charged polymer includes any one or a combination of two or more of polyvinyl alcohol acid, polyether sulfone and sodium polystyrene sulfonate.

2. The flexible antifouling and drag-reducing composite coating according to claim 1, characterized in that: The thickness of the base layer is 20-60 μm; and / or the thickness of the flexible buffer layer is 0.1-0.5 mm; and / or the thickness of the antifouling response layer is 0.1-0.5 mm; and / or the thickness of the hydrophobic surface layer is 10-60 μm.

3. The flexible antifouling and drag-reducing composite coating according to claim 1, characterized in that: The preparation method of the temperature-responsive polymer microcapsule encapsulating the antifouling agent comprises: The temperature-responsive polymer monomer, antifouling agent, cross-linking agent, initiator and nucleating particles are emulsified and polymerized in a water-oil solution at 50-80° C. for 12-24 hours to prepare temperature-responsive polymer microcapsules encapsulating the antifouling agent.

4. The flexible antifouling and drag-reducing composite coating according to claim 3 is characterized in that: The temperature responsive polymer monomer includes N-isopropylacrylamide; And / or, the antifouling agent includes any one of copper pyrithione, zinc pyrithione, chitosan or a combination of two or more thereof; And / or, the cross-linking agent includes any one or a combination of two or more of N,N'-methylenebisacrylamide, divinylbenzene, and diisocyanate; And / or, the initiator includes any one or a combination of two or more of potassium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, and azobisisoheptanenitrile; And / or, the nucleation particles include any one or a combination of two or more of gas-phase hydrophobic SiO2, gas-phase hydrophilic SiO2, TiO2, and Al2O3.

5. The method for preparing a temperature-responsive flexible antifouling and drag-reducing composite coating according to any one of claims 1 to 4, characterized in that: include: Applying a first base liquid containing at least an adhesive resin, a positively charged polymer, a particle filler, and a diluent to the surface of the substrate and subjecting the substrate to a first curing treatment to form a base layer having a multi-level micro-nano structure; Applying a second base liquid containing at least a flexible polymer resin, a negatively charged polymer, a polymer drag reducer, an anti-ultraviolet additive and a solvent to the surface of the base layer and performing a second curing treatment to form a flexible buffer layer; Applying a third base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, an anti-ultraviolet additive and a solvent to the surface of the flexible buffer layer and subjecting the third base liquid to a third curing treatment to form an antifouling responsive layer; And, a fourth base liquid comprising at least a flexible polymer resin, a temperature-responsive polymer microcapsule encapsulating an antifouling agent, a porogen, an anti-ultraviolet additive, super-hydrophobic micro-nanoparticles and a solvent is applied to the surface of the antifouling response layer and subjected to a fourth curing treatment to form a hydrophobic surface layer, thereby obtaining a flexible antifouling and drag-reducing composite coating with temperature responsiveness.

6. The preparation method according to claim 5, characterized in that: Specifically include: Applying the first base liquid to the surface of the substrate by spraying or brushing and curing at room temperature for 12 to 24 hours to form the base layer; and / or, applying the second base liquid to the surface of the base layer by spraying or brushing and curing it at room temperature for 4 to 12 hours to form a flexible buffer layer; and / or, applying a third base liquid to the surface of the flexible buffer layer by spraying or brushing and curing the base liquid at room temperature for 12 to 24 hours to form the antifouling response layer; And / or, the fourth base liquid is applied to the surface of the antifouling response layer by spraying or brushing and cured at room temperature for 12 to 24 hours to form the hydrophobic surface layer.

7. The preparation method according to claim 5, characterized in that: The mass ratio of the adhesive resin, the positively charged polymer, the particle filler and the diluent in the first base liquid is 10-50: 0.5-5: 0.5-5: 0-30; and / or, the mass ratio of the flexible polymer resin, the negatively charged polymer, the polymer drag reducer, the anti-ultraviolet additive and the solvent in the second base liquid is 20-50:0.5-5:0.5-5:0.5-5:0-30; And / or, the mass ratio of the flexible polymer resin, the temperature-responsive polymer microcapsules encapsulating the antifouling agent, and the solvent in the third base liquid is 30-40:1-5:0-30; And / or, the mass ratio of the flexible polymer resin, the temperature-responsive polymer microcapsules encapsulating the antifouling agent, the porogen, the anti-ultraviolet additive, the super-hydrophobic micro-nanoparticles and the solvent in the fourth base liquid is 20-50:0-5:0-5:0-2:0-5:0-30.

8. The preparation method according to claim 5, characterized in that: The adhesive resin includes any one or a combination of two or more of modified epoxy resin, epoxy zinc-rich primer, acrylic polyurethane paint, amino silicone resin, polyurethane, and fluorinated modified epoxy resin; And / or, the particle filler includes any one or a combination of two or more of kaolin, talc, mica powder, zinc oxide, titanium dioxide, silicon dioxide, glass beads, and diatomaceous earth; and / or, the particle size of the particle filler is 1-100 μm; And / or, the diluent includes any one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, propylene glycol methyl ether, and formamide; And / or, the flexible polymer resin includes any one or a combination of two or more of silicone resin, polyurethane, acrylic modified silicone resin, and polyurea; And / or, the polymer drag reducer includes one or a combination of two or more of polyacrylamide, polyvinyl alcohol, sodium polyisoacrylate, and polyvinyl pyrrolidone; And / or, the anti-ultraviolet additive includes any one or a combination of two or more of 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazine-2-yl)-4,6-bis(2-methylmethylamino-ethyl)-phenol, 2-hydroxyphenols and their derivatives, and octyl salicylate; And / or, the solvent includes any one or a combination of two or more of toluene, xylene, ethyl acetate, acetone, ethanol, butanol, and butyl acetate; And / or, the substrate includes any one or a combination of two or more of a steel substrate, an aluminum alloy substrate, and a copper alloy substrate; And / or, the porogen includes any one or a combination of two or more of sodium chloride, lactose, sucrose, ammonium bicarbonate, and sodium bicarbonate; And / or, the preparation method of the super-hydrophobic micro-nano particles comprises: mixing micro-nano particles, ammonia water, tetraethyl silicate, a hydrophobic treatment modifier and water for 6 to 24 hours to obtain the super-hydrophobic micro-nano particles; wherein the hydrophobic treatment modifier comprises any one of alkyl siloxane, alkyl chlorosilane, fluoroalkyl siloxane, alkyl organosilane and perfluoroalkyl organosilane, or a combination of two or more thereof.

9. Application of the temperature-responsive flexible antifouling and drag-reducing composite coating according to any one of claims 1 to 4 in intelligent protection of the surface of a ship hull, a pipeline, an offshore platform or an underwater structure.

10. A method for reducing the navigation resistance of a navigation body, characterized in that: include: At least the surface of the navigation body in contact with the liquid is covered with a temperature-responsive flexible antifouling and drag-reducing composite coating as claimed in any one of claims 1 to 4.

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