Super-smooth antifouling anti-drag composite coating with photo-thermal responsiveness and preparation method and application of super-smooth antifouling anti-drag composite coating

Abstract

The invention discloses a super-smooth antifouling anti-drag composite coating with photo-thermal responsiveness as well as a preparation method and application of the super-smooth antifouling anti-drag composite coating. The super-lubricity antifouling anti-drag composite coating comprises a substrate layer, a homogeneous heat absorption layer, a porous heat absorption layer and a thermal response super-lubricity layer which are sequentially formed on the surface of a base material. Wherein the substrate layer comprises a positively charged polymer, an adhesive and a filler; the homogeneous heat absorption layer comprises hydrophobic resin, a negatively charged polymer and light absorption particles; the porous heat absorption layer comprises hydrophobic resin and light absorption particles, and the porous heat absorption layer is of a porous structure; and the thermal response super-smooth layer comprises paraffin and a temperature response polymer microcapsule encapsulated with an antifouling agent. The photo-thermal responsive super-smooth antifouling resistance-reducing composite coating provided by the invention has strong binding force with a base material, and also has the function of storing a thermal response phase change material, antifouling property and super-smooth 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 specifically relates to an ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness, and a preparation method and application thereof. Background Art

[0002] In the field of marine environment applications, antifouling and drag-reducing functional coatings can effectively reduce the energy loss and speed reduction caused by the attachment of marine organisms and the friction of seawater. With the acceleration of the industrialization process and the improvement of energy conservation awareness, the demand for antifouling and drag-reducing functional coatings in the shipping industry is becoming increasingly urgent. At present, there are many super-slip antifouling materials with single functions, few of which have responsive performance, and lack comprehensive consideration of issues such as the interface bonding of the substrate and the controlled release of antifouling, which greatly restricts the service life of the material. For example, the patent with publication number CN118325468A proposes to coat the super-slip antifouling mixture on the surface of the substrate to spontaneously form a super-slip antifouling layer. In the absence of a substrate interface layer, the service life of the super-slip antifouling layer is limited. Therefore, it is an urgent problem to provide a coating that simultaneously solves the problems of interface bonding and anti-fouling controlled release, and realizes an anti-fouling super-slip function with a stable and reliable photothermal response. Summary of the invention

[0003] The main purpose of the present invention is to provide an ultra-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness and a preparation method and application thereof, so as to overcome the shortcomings 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 an ultra-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness, which comprises: a base layer, a homogeneous heat absorption layer, a porous heat absorption layer and a thermal responsive ultra-slip layer sequentially formed on the surface of a substrate; Among them, the base layer includes positively charged polymers, adhesives and fillers; the homogeneous heat absorption layer includes hydrophobic resins, negatively charged polymers and light-absorbing particles; the porous heat absorption layer includes hydrophobic resins and light-absorbing particles, and the porous heat absorption layer has a porous structure; the thermally responsive super-slip layer includes paraffin and temperature-responsive polymer microcapsules encapsulated with antifouling agents; the positively charged polymer includes any one of polymethacryloyloxyethyltrimethylammonium chloride, polyethyleneimine, polyaniline, and polyacrylamide, or a combination of two or more thereof; the negatively charged polymer includes any one of polyglutamic acid, sodium polybenzenesulfonate, and polyethersulfone, or a combination of two or more thereof.

[0005] The embodiment of the present invention also provides a method for preparing the aforementioned ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness, which comprises: Applying a first base liquid containing at least an adhesive, a positively charged polymer, a filler, and a diluent to the surface of the substrate and performing a first curing treatment to form a base layer; Applying a second base liquid containing at least a hydrophobic resin, a negatively charged polymer, light-absorbing particles, and a first solvent to the surface of the base layer and performing a second curing treatment to form a homogeneous heat-absorbing layer; Applying a third base liquid containing at least a hydrophobic resin, light-absorbing particles, and a second solvent to the surface of the homogeneous heat-absorbing layer and performing a third curing treatment to form a porous heat-absorbing layer; wherein the volatilization rate of the first solvent is greater than the volatilization rate of the second solvent; A fourth base liquid containing at least paraffin, temperature-responsive polymer microcapsules encapsulating an antifouling agent, and a third solvent is applied to the surface of the porous heat-absorbing layer, and subjected to a fourth curing treatment to form a thermally responsive super-slippery layer, thereby obtaining an ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness.

[0006] The embodiment of the present invention also provides the use of the aforementioned ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness in the protection of ship hulls.

[0007] Compared with the prior art, the beneficial effects of the present invention are as follows: the base layer in the photothermal responsive super-slippery anti-fouling and drag-reducing composite coating provided by the present invention has a multi-level microstructure, which can improve the bonding strength between the coating and the substrate while simultaneously improving the adhesion of the upper homogeneous heat absorption layer; the homogeneous heat absorption layer and the porous heat absorption layer are two-layer structures spontaneously formed in situ by solvent induction, which can not only effectively absorb light and heat and increase the temperature of the coating, but also the porous heat absorption layer has the function of storing the thermally responsive phase change super-slippery anti-fouling material after completing the initial thermally responsive phase change material filling, thereby avoiding the rapid loss of the super-slippery anti-fouling substance; the thermally responsive super-slippery layer on the surface provides anti-fouling and super-slip properties at the same time; the preparation method adopted by the present invention has the advantages of a wide range of applicability and large-area coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] 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.

[0009] Figure 1 It is a schematic diagram of the structure of an ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness in a typical embodiment of the present invention.

[0010] Description of the drawings: 1-substrate, 2-base layer, 3-homogeneous heat absorption layer, 4-porous heat absorption layer, 5-thermal responsive super-slip layer. DETAILED DESCRIPTION

[0011] In view of the defects of the prior art, after long-term research and extensive practice, the technical solution of the present invention is proposed. The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. 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.

[0012] Specifically, as one aspect of the technical solution of the present invention, a super-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness comprises: a base layer, a homogeneous heat absorption layer, a porous heat absorption layer and a thermal responsive super-slip layer sequentially formed on the surface of a substrate; Among them, the base layer includes positively charged polymers, adhesives and fillers; the homogeneous heat absorption layer includes hydrophobic resins, negatively charged polymers and light-absorbing particles; the porous heat absorption layer includes hydrophobic resins and light-absorbing particles, and the porous heat absorption layer has a porous structure; the thermally responsive super-slip layer includes paraffin and temperature-responsive polymer microcapsules encapsulated with antifouling agents; the positively charged polymer includes any one of polymethacryloyloxyethyltrimethylammonium chloride, polyethyleneimine, polyaniline, and polyacrylamide, or a combination of two or more thereof; the negatively charged polymer includes any one of polyglutamic acid, sodium polybenzenesulfonate, and polyethersulfone, or a combination of two or more thereof.

[0013] In the present invention, a strong interfacial bonding force is generated by the base layer, the substrate and the homogeneous heat absorption layer, and the light-absorbing particles in the homogeneous heat absorption layer and the porous heat absorption layer absorb light and heat, thereby inducing a phase transition of the thermal phase change material in the thermal response layer, forming a mobile phase and infiltrating the porous heat absorption layer to spontaneously form an ultra-slippery plane, further causing the temperature-responsive microcapsules to shrink and expanding the release of the antifouling agent.

[0014] In some preferred embodiments, the porous heat absorption layer has a pore structure penetrating the upper and lower surfaces thereof and generated in situ by solvent induction, and the pore size of the pores contained is 1-15 μm.

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

[0016] In some preferred embodiments, the thickness of the homogeneous heat absorption layer is 0.3-0.5 mm.

[0017] In some preferred embodiments, the thickness of the porous heat absorption layer is 20-60 μm.

[0018] In some preferred embodiments, the thickness of the thermally responsive super-slip layer is 0.2-0.5 mm.

[0019] In some more specific embodiments, the structural schematic diagram of the ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness is as follows: Figure 1 As shown, it includes a substrate 1, a base layer 2, a homogeneous heat absorption layer 3, a porous heat absorption layer 4, and a thermally responsive super-slip layer 5.

[0020] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned ultra-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness, which comprises: Applying a first base liquid containing at least an adhesive, a positively charged polymer, a filler, and a diluent to the surface of the substrate and performing a first curing treatment to form a base layer; Applying a second base liquid containing at least a hydrophobic resin, a negatively charged polymer, light-absorbing particles, and a first solvent to the surface of the base layer and performing a second curing treatment to form a homogeneous heat-absorbing layer; Applying a third base liquid containing at least a hydrophobic resin, light-absorbing particles, and a second solvent to the surface of the homogeneous heat-absorbing layer and performing a third curing treatment to form a porous heat-absorbing layer; wherein the volatilization rate of the first solvent is greater than the volatilization rate of the second solvent; A fourth base liquid containing at least paraffin, temperature-responsive polymer microcapsules encapsulating an antifouling agent, and a third solvent is applied to the surface of the porous heat-absorbing layer, and subjected to a fourth curing treatment to form a thermally responsive super-slippery layer, thereby obtaining an ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness.

[0021] 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.

[0022] In some preferred embodiments, the preparation method specifically comprises: applying the second base liquid to the surface of the base layer by spraying, and leaving it at room temperature for 10 to 30 minutes to form a homogeneous heat absorption layer.

[0023] In some preferred embodiments, the preparation method specifically includes: applying the third base liquid to the surface of the homogeneous heat absorption layer by in-situ spraying and curing it at room temperature for 12 to 24 hours to form the porous heat absorption layer.

[0024] In some preferred embodiments, the preparation method specifically includes: applying the fourth base liquid to the surface of the porous heat absorption layer by brushing and curing it at room temperature for 12 to 24 hours to form the thermally responsive super-slippery layer.

[0025] In some preferred embodiments, the mass ratio of the adhesive, the positively charged polymer, the filler and the diluent in the first base liquid is 10-20:0.1-5:1-5:2-10.

[0026] In some preferred embodiments, the mass ratio of the hydrophobic resin, the negatively charged polymer, the light absorbing particles and the first solvent in the second base liquid is 10-20:0.1-5:1-5:2-10.

[0027] In some preferred embodiments, the mass ratio of the hydrophobic resin, the light absorbing particles and the second solvent in the third base liquid is 10-20:1-5:2-10.

[0028] In some preferred embodiments, the mass ratio of the paraffin wax, the temperature-responsive polymer microcapsules encapsulating the antifouling agent, and the third solvent in the fourth base liquid is 20-40:1-5:0-30.

[0029] In some preferred embodiments, the adhesive includes any one or a combination of two or more of modified epoxy resin, epoxy zinc-rich primer, amino silicone resin, and polyurethane-modified epoxy resin, and is not limited thereto.

[0030] In some preferred embodiments, the filler includes any one or a combination of two or more of kaolin, mica powder, silicon dioxide, glass microspheres, and diatomaceous earth, but is not limited thereto.

[0031] In some preferred embodiments, the diluent includes one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, and propylene glycol methyl ether, but is not limited thereto.

[0032] In some preferred embodiments, the hydrophobic resin is selected from any one or a combination of two or more of silicone resin, fluorinated modified epoxy resin, fluorinated modified polyurethane resin, and fluorocarbon resin, and is not limited thereto.

[0033] In some preferred embodiments, the light absorbing particles include one or a combination of two or more of graphene, polypyrrole, carbon black, and ferrosoferric oxide, but are not limited thereto.

[0034] In some preferred embodiments, the first solvent and the second solvent are independently selected from any one or a combination of two or more of volatile alcohols, esters, ketones, benzene, and ethers, and are not limited thereto.

[0035] In some preferred embodiments, the volatilization rate ratio of the first solvent to the second solvent is 2-4: 6-10.

[0036] In some preferred embodiments, the third solvent includes any one of alcohol, ester, ketone, benzene, ether or a combination of two or more thereof, but is not limited thereto.

[0037] 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.

[0038] In some preferred embodiments, the method for preparing the temperature-responsive polymer microcapsules encapsulating the antifouling agent comprises: The aqueous phase solution containing dispersed shaped core particles is mixed with the oil phase solution containing temperature-responsive polymer monomer, crosslinking agent and initiator, and emulsified polymerized at 50-80°C for 12-24h, and then centrifuged and dried to obtain microcapsules; Furthermore, the microcapsules are added into a solution containing an antifouling agent and mixed thoroughly, and then stirred, centrifuged and dried to obtain temperature-responsive polymer microcapsules encapsulating the antifouling agent.

[0039] Further, the temperature responsive polymer monomer includes N-isopropylacrylamide, but is not limited thereto.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Furthermore, the volume ratio of the aqueous phase solution to the oil phase solution is 1:4 to 1:2.

[0045] Another aspect of the embodiments of the present invention further provides the use of the aforementioned ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness in the protection of ship hulls.

[0046] The present invention proposes to combine the base layer, the photothermal absorption layer, and the thermal response antifouling super-slip layer through a multi-layer structural design to achieve an antifouling super-slip function with photothermal response. In the structural design of the coating, the difference in the volatilization rate of different solvents is used to form an in-situ photothermal absorption layer with a porous structure, which not only has a photothermal absorption effect, but also has the function of storing photothermal response materials. In this way, the goal of integrating synergistic photothermal responsiveness, antifouling and drag reduction functions is achieved.

[0047] The present invention proposes to combine the base layer, the photothermal absorption layer, and the thermal response antifouling super-slip layer through a multi-layer structural design, and simultaneously solve the problems of interface bonding and antifouling controllable release, so as to achieve an antifouling super-slip function with stable and reliable photothermal response. In the structural design of the coating, the difference in the volatilization rate of different solvents is used to form an in-situ photothermal absorption layer with a porous structure, which not only has a photothermal absorption effect, but also has the function of storing photothermal response materials. In this way, the goal of integrating synergistic photothermal responsiveness, antifouling and drag reduction functions is achieved.

[0048] 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.

[0049] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0050] Example 1 (1) 68 wt.% amino silicone resin, 2 wt.% polyacrylamide, 10 wt.% SiO2 particles, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) dissolving 63 wt.% of silicone resin, 2 wt.% of polyglutamic acid, and 10 wt.% of graphene oxide in ethyl acetate, and uniformly stirring the mixture mechanically to obtain a second base liquid; spraying the base liquid in situ on the surface of the substrate layer, and curing the base liquid at room temperature for 10 min to form a homogeneous heat absorption layer; (3) dissolving 65 wt.% of silicone resin and 10 wt.% of graphene oxide in propylene glycol methyl ether, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 24 hours to form a porous heat absorption layer; (4) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating an antifouling agent 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 porous heat-absorbing layer and cured at room temperature for 5 hours to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0051] Example 2 (1) 68 wt.% epoxy zinc-rich primer, 2 wt.% polyethyleneimine, 10 wt.% diatomaceous earth particles, and 20 wt.% toluene are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) dissolving 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of polyglutamic acid, 5 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in toluene, and uniformly stirring the mixture mechanically to obtain a second base liquid; spraying the base liquid in situ on the surface of the substrate layer, and curing the base liquid at room temperature for 10 min to form a homogeneous heat absorption layer; (3) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 5 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in propylene glycol methyl ether, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 24 hours to form a porous heat absorption layer; (4) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating an antifouling agent 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 porous heat-absorbing layer and cured at room temperature for 5 hours to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0052] Example 3 (1) 63 wt.% polyurethane modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomaceous earth particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polybenzene sulfonate, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 10 min to form a homogeneous heat absorption layer; (3) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in ethanol, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 18 hours to form a porous heat absorption layer; (4) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating an antifouling agent 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 porous heat-absorbing layer and cured at room temperature for 5 hours to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0053] Comparative Example 1 (Compared with Example 3, lacking a base layer) (1) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polybenzene sulfonate, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed on the surface of the above-mentioned base layer in situ, and cured at room temperature for 10 min to form a uniform heat absorption layer; (2) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in ethanol, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 18 hours to form a porous heat absorption layer; (3) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating antifouling agents were dissolved in ethyl acetate and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid was in-situ brushed on the surface of the porous heat-absorbing layer and cured at room temperature for 5 h to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0054] Performance characterization: The prepared composite coating has weak bonding with the substrate and is easy to fall off.

[0055] Comparative Example 2 (Compared with Example 3, lacking a homogeneous and porous heat-absorbing layer structure) (1) 63 wt.% polyurethane modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomaceous earth particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethanol and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 18 h to form a heat absorption layer; (3) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating antifouling agents were dissolved in ethyl acetate and uniformly stirred mechanically to obtain a fourth base liquid; the base liquid was in-situ brushed on the surface of the above-mentioned heat absorption layer and cured at room temperature for 5 hours to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0056] Performance characterization: No uniform and porous heat absorption layer structure is formed, the thermally responsive ultra-slippery material only covers the surface of the heat absorption layer, and the thermal responsiveness becomes poor.

[0057] Comparative Example 3 (Compared with Example 3, the temperature-responsive polymer capsule encapsulating the antifouling agent is missing) (1) 63 wt.% polyurethane modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomaceous earth particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polybenzene sulfonate, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 10 min to form a homogeneous heat absorption layer; (3) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in ethanol, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 18 hours to form a porous heat absorption layer; (4) Dissolve 50 wt.% of solid paraffin in ethyl acetate and stir evenly by mechanical stirring to obtain a fourth base liquid; apply the base liquid in situ on the surface of the porous heat absorption layer and cure it at room temperature for 5 hours to obtain an ultra-slip composite coating with photothermal responsiveness.

[0058] Performance characterization: The antifouling property of the prepared composite coating deteriorates.

[0059] Comparative Example 4 (Compared with Example 3, lacking a thermally responsive super-slip layer) (1) 63 wt.% polyurethane modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomaceous earth particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polybenzene sulfonate, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 10 min to form a homogeneous heat absorption layer; (3) 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethanol and uniformly stirred by mechanical stirring to obtain a third base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned homogeneous heat absorption layer and cured at room temperature for 18 hours to form an ultra-slip composite coating.

[0060] Performance characterization: The prepared composite coating does not have super-slip, anti-fouling and drag-reducing properties.

[0061] Comparative Example 5 (Compared with Example 3, the temperature-responsive polymer microcapsules encapsulating the antifouling agent are replaced with corresponding amounts of the temperature-responsive polymer and the antifouling agent) (1) 63 wt.% polyurethane modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomaceous earth particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate are mixed evenly to obtain a first base liquid; the base liquid is applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polybenzene sulfonate, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 10 min to form a homogeneous heat absorption layer; (3) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in ethanol, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 18 hours to form a porous heat absorption layer; (4) 50 wt.% of solid paraffin, 5 wt.% of temperature-responsive polymer microcapsules, and 5 wt.% of 2-pyridinethione copper 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 porous heat-absorbing layer and cured at room temperature for 5 hours to obtain an ultra-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness; Wherein, the preparation method of temperature-responsive polymer microcapsules is: 1.5 g of gas-phase hydrophobic SiO2 particles (30 nm) were dispersed in 100 ml of deionized water to prepare the water phase, and 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) were added to 50 ml of xylene to prepare the oil phase. The water and oil phases were then mixed in a volume ratio of 1 / 3, and the mixture was stirred at high speed at 50°C for 12 h. The mixture was centrifuged and dried to obtain poly (N-isopropylacrylamide) microcapsule particles.

[0062] Performance characterization: The antifouling performance of the prepared composite coating is excellent initially, but decays rapidly in the later stage.

[0063] Comparative Example 6 (Compared with Example 3, lacking positively charged polymer (polyacrylamide) and negatively charged polymer (sodium polybenzene sulfonate)) (1) 63 wt.% of polyurethane modified epoxy resin, 5 wt.% of diatomaceous earth particles, 5 wt.% of glass microspheres, and 20 wt.% of ethyl acetate were mixed evenly to obtain a first base liquid; the base liquid was applied to the surface of the substrate by brushing, and cured at room temperature for 8 hours to form a base layer; (2) 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide are dissolved in ethyl acetate and uniformly stirred by mechanical stirring to obtain a second base liquid; the base liquid is sprayed in situ on the surface of the above-mentioned base layer and cured at room temperature for 10 min to form a homogeneous heat absorption layer; (3) Dissolving 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of ferroferric oxide powder, 2 wt.% of polypyrrole powder and 5 wt.% of graphene oxide in ethanol, and uniformly stirring the mixture mechanically to obtain a third base liquid; spraying the base liquid in situ on the surface of the homogeneous heat absorption layer, and curing the base liquid at room temperature for 18 hours to form a porous heat absorption layer; (4) 50 wt.% of solid paraffin and 10 wt.% of temperature-responsive polymer microcapsules encapsulating an antifouling agent 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 porous heat-absorbing layer and cured at room temperature for 5 hours to obtain an ultra-slip antifouling and drag-reducing composite coating with photothermal responsiveness; The preparation method of the temperature-responsive polymer microcapsules encapsulating 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℃, centrifuged, and dried to obtain poly(N-isopropylacrylamide) microcapsule particles. 1g of the above microcapsule particles was added to 40g / L ethanol solution of 2-pyridinethione copper and mixed thoroughly, stirred for 12h, centrifuged, and dried to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0064] Performance characterization: The adhesion of the coating becomes poor and it is easy to fall off.

[0065] 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 1-6 ; In addition, referring to the above-mentioned embodiments, experiments were carried out with other raw materials, process operations and process conditions described in this specification, and relatively ideal results were obtained.

[0066] 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 super-slip anti-fouling and drag-reducing composite coating with photothermal responsiveness, characterized in that: include: A base layer, a homogeneous heat absorption layer, a porous heat absorption layer and a thermally responsive super-slip layer are sequentially formed on the surface of the substrate; Among them, the base layer includes positively charged polymers, adhesives and fillers; the homogeneous heat absorption layer includes hydrophobic resins, negatively charged polymers and light-absorbing particles; the porous heat absorption layer includes hydrophobic resins and light-absorbing particles, and the porous heat absorption layer has a porous structure; the thermally responsive super-slip layer includes paraffin and temperature-responsive polymer microcapsules encapsulated with antifouling agents; the positively charged polymer includes any one of polymethacryloyloxyethyltrimethylammonium chloride, polyethyleneimine, polyaniline, and polyacrylamide, or a combination of two or more thereof; the negatively charged polymer includes any one of polyglutamic acid, sodium polybenzenesulfonate, and polyethersulfone, or a combination of two or more thereof.

2. The ultra-slip anti-fouling and drag-reducing composite coating according to claim 1, characterized in that: The porous heat absorption layer has a pore structure penetrating the upper and lower surfaces thereof and generated in situ by solvent induction, and the pores contained in the pores have a pore diameter of 1 to 15 μm.

3. The ultra-slip anti-fouling 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 homogeneous heat absorption layer is 0.3-0.5 mm; and / or the thickness of the porous heat absorption layer is 20-60 μm; and / or the thickness of the thermally responsive super-slip layer is 0.2-0.5 mm.

4. The method for preparing the ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness according to any one of claims 1 to 3, characterized in that: include: Applying a first base liquid containing at least an adhesive, a positively charged polymer, a filler, and a diluent to the surface of the substrate and performing a first curing treatment to form a base layer; Applying a second base liquid containing at least a hydrophobic resin, a negatively charged polymer, light-absorbing particles, and a first solvent to the surface of the base layer and performing a second curing treatment to form a homogeneous heat-absorbing layer; Applying a third base liquid containing at least a hydrophobic resin, light-absorbing particles, and a second solvent to the surface of the homogeneous heat-absorbing layer and performing a third curing treatment to form a porous heat-absorbing layer; wherein the volatilization rate of the first solvent is greater than the volatilization rate of the second solvent; A fourth base liquid containing at least paraffin, temperature-responsive polymer microcapsules encapsulating an antifouling agent, and a third solvent is applied to the surface of the porous heat-absorbing layer, and subjected to a fourth curing treatment to form a thermally responsive super-slippery layer, thereby obtaining an ultra-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness.

5. The preparation method according to claim 4, 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, and leaving it at room temperature for 10 to 30 minutes to form a homogeneous heat absorption layer; and / or, applying the third base liquid to the surface of the homogeneous heat absorption layer by in-situ spraying and curing at room temperature for 12 to 24 hours to form the porous heat absorption layer; And / or, applying the fourth base liquid to the surface of the porous heat absorption layer by brushing and curing it at room temperature for 12 to 24 hours to form the thermally responsive super-slippery layer.

6. The preparation method according to claim 4, characterized in that: The mass ratio of the adhesive, the positively charged polymer, the filler and the diluent in the first base liquid is 10-20: 0.1-5: 1-5: 2-10; and / or, the mass ratio of the hydrophobic resin, the negatively charged polymer, the light absorbing particles and the first solvent in the second base liquid is 10-20:0.1-5:1-5:2-10; And / or, the mass ratio of the hydrophobic resin, the light-absorbing particles and the second solvent in the third base liquid is 10-20: 1-5: 2-10; And / or, the mass ratio of paraffin wax, temperature-responsive polymer microcapsules encapsulating antifouling agent, and the third solvent in the fourth base liquid is 20-40:1-5:0-30.

7. The preparation method according to claim 4, characterized in that: The adhesive includes any one or a combination of two or more of modified epoxy resin, epoxy zinc-rich primer, amino silicone resin, and polyurethane modified epoxy resin; And / or, the filler includes any one or a combination of two or more of kaolin, mica powder, silicon dioxide, glass microspheres, and diatomaceous earth; And / or, the diluent includes one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, and propylene glycol methyl ether; And / or, the hydrophobic resin is selected from any one or a combination of two or more of silicone resin, fluorinated modified epoxy resin, fluorinated modified polyurethane resin, and fluorocarbon resin; And / or, the light absorbing particles include one or a combination of two or more of graphene, polypyrrole, carbon black, and ferrosoferric oxide; And / or, the first solvent and the second solvent are independently selected from any one or a combination of two or more of volatile alcohols, esters, ketones, benzene and ethers; And / or, the volatilization rate ratio of the first solvent to the second solvent is 2-4: 6-10; And / or, the third solvent includes any one or more combinations of alcohol, ester, ketone, benzene, and ether; And / or, 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.

8. The preparation method according to claim 4, characterized in that: The preparation method of the temperature-responsive polymer microcapsule encapsulating the antifouling agent comprises: The aqueous phase solution containing dispersed shaped core particles is mixed with the oil phase solution containing temperature-responsive polymer monomer, crosslinking agent and initiator, and emulsified polymerized at 50-80°C for 12-24h, and then centrifuged and dried to obtain microcapsules; Furthermore, the microcapsules are added into a solution containing an antifouling agent and mixed thoroughly, and then stirred, centrifuged and dried to obtain temperature-responsive polymer microcapsules encapsulating the antifouling agent.

9. The preparation method according to claim 8, 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; And / or, the volume ratio of the aqueous phase solution to the oil phase solution is 1:4 to 1:

2.

10. Use of the ultra-slippery antifouling and drag-reducing composite coating with photothermal responsiveness according to any one of claims 1 to 3 in the protection of ship hulls.

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