Super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, its preparation method and application

Abstract

The present invention discloses a super-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness, its preparation method and applications. The super-slippery anti-fouling and drag-reducing composite coating includes: a base layer, a homogeneous heat-absorbing layer, a porous heat-absorbing layer and a thermoresponsive super-slippery layer formed in sequence on the surface of a substrate; wherein, the base layer includes a positively charged polymer, an adhesive and a filler; the homogeneous heat-absorbing layer includes a hydrophobic resin, a negatively charged polymer and light-absorbing particles; the porous heat-absorbing layer includes a hydrophobic resin and light-absorbing particles, and the porous heat-absorbing layer has a porous structure; the thermoresponsive super-slippery layer includes paraffin and temperature-responsive polymer microcapsules encapsulating an anti-fouling agent. The super-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness provided by the present invention has a strong bonding force with the substrate, and also has the functions of storing a thermoresponsive phase change material, anti-fouling property and super-slippery property; at the same time, the preparation method provided by the present invention has the advantages of wide application range and large-area coating.

Description

Technical Field

[0001] The present invention belongs to the technical field of marine coating protection, and particularly relates to a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, its preparation method and application. Background Art

[0002] In the field of marine environment applications, antifouling and drag-reducing functional coatings can effectively reduce energy loss and speed reduction caused by marine organism attachment and seawater friction. With the acceleration of the industrialization process and the improvement of energy conservation awareness, the shipping industry has an increasingly urgent need for antifouling and drag-reducing functional coatings. At present, many super-slippery antifouling materials have a single function, rarely have responsive properties, and lack comprehensive consideration of issues such as interfacial bonding to the substrate and controllable release of antifouling, which greatly restricts the service life of the materials. For example, in the patent with the publication number CN118325468A, it is proposed to coat a super-slippery antifouling mixture on the surface of the substrate to spontaneously form a super-slippery antifouling layer. In the absence of a substrate interface layer, the service life of this super-slippery antifouling layer is limited. Therefore, it is an urgent problem to provide a coating that can simultaneously solve the problems of interfacial bonding and controllable release of antifouling and achieve a stable and reliable antifouling super-slippery function with photothermal responsiveness. Summary of the Invention

[0003] The main object of the present invention is to provide a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, its preparation method and application, so as to overcome the deficiencies of the prior art.

[0004] To achieve the foregoing invention object, the technical solutions adopted by the present invention include:

[0005] An embodiment of the present invention provides a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, which includes: a base layer, a homogeneous heat-absorbing layer, a porous heat-absorbing layer, and a thermoresponsive super-slippery layer formed in sequence on the surface of a substrate;

[0006] Wherein, the base layer includes a positively charged polymer, an adhesive, and a filler; the homogeneous heat-absorbing layer includes a hydrophobic resin, a negatively charged polymer, and light-absorbing particles; the porous heat-absorbing layer includes a hydrophobic resin and light-absorbing particles, and the porous heat-absorbing layer has a porous structure; the thermoresponsive super-slippery layer includes paraffin and temperature-responsive polymer microcapsules encapsulating an antifouling agent; the positively charged polymer includes any one or a combination of two or more of poly(methacryloyloxyethyltrimethylammonium chloride), polyethyleneimine, polyaniline, and polyacrylamide; the negatively charged polymer includes any one or a combination of two or more of polyglutamic acid, sodium polystyrenesulfonate, and polyethersulfone.

[0007] An embodiment of the present invention also provides a preparation method of the foregoing super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, which includes:

[0008] Apply a first base liquid containing at least an adhesive, a positively charged polymer, a filler, and a diluent to the surface of a substrate and perform a first curing treatment to form a base layer;

[0009] Apply 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 perform a second curing treatment to form a homogeneous heat-absorbing layer;

[0010] Apply 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 perform a third curing treatment to form a porous heat-absorbing layer; wherein, the evaporation rate of the first solvent is greater than that of the second solvent;

[0011] Apply a fourth base liquid containing at least paraffin, temperature-responsive polymer microcapsules encapsulating an antifouling agent, and a third solvent to the surface of the porous heat-absorbing layer and perform a fourth curing treatment to form a thermally responsive super-slippery layer, thereby obtaining a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness.

[0012] An embodiment of the present invention also provides an application of the aforementioned super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness in the protection of ship hulls.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: The base layer in the super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness provided by the present invention has a multi-level microstructure, which can improve the bonding force between the coating and the substrate while synchronously enhancing the adhesion of the upper homogeneous heat-absorbing layer; the homogeneous heat-absorbing layer and the porous heat-absorbing layer are an upper and lower layer structure formed in-situ spontaneously by solvent induction, which can not only effectively absorb light and heat and increase the temperature of the coating, but also, after the porous heat-absorbing layer is filled with the primary thermally responsive phase change material, have the function of storing the thermally responsive phase change super-slippery antifouling material to avoid the rapid loss of the super-slippery antifouling substance; the thermally responsive super-slippery layer on the surface provides both antifouling and super-slippery properties at the same time; the preparation method adopted by the present invention has the advantages of wide applicability and large-area coating. Description of the Drawings

[0014] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0015] Figure 1 It is a schematic structural diagram of a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness in a typical implementation scheme of the present invention.

[0016] Description of the Drawings: 1 - Substrate, 2 - Base layer, 3 - Homogeneous heat absorption layer, 4 - Porous heat absorption layer, 5 - Thermoresponsive super-slippery layer. Detailed Description of the Invention

[0017] In view of the deficiencies of the prior art, through long-term research and a large number of practices, the technical solution of the present invention has been proposed. 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, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] Specifically, as an aspect of the technical solution of the present invention, a super-slippery anti-fouling and drag-reducing composite coating with photothermal responsiveness includes: a base layer, a homogeneous heat absorption layer, a porous heat absorption layer, and a thermoresponsive super-slippery layer formed in sequence on the surface of the substrate;

[0019] Among them, the base layer includes a positively charged polymer, an adhesive, and a filler; the homogeneous heat absorption layer includes a hydrophobic resin, a negatively charged polymer, and light-absorbing particles; the porous heat absorption layer includes a hydrophobic resin and light-absorbing particles, and the porous heat absorption layer has a porous structure; the thermoresponsive super-slippery layer includes paraffin and temperature-responsive polymer microcapsules encapsulating an anti-fouling agent; the positively charged polymer includes any one or a combination of two or more of poly(methacryloyloxyethyltrimethylammonium chloride), polyethyleneimine, polyaniline, and polyacrylamide; the negatively charged polymer includes any one or a combination of two or more of polyglutamic acid, sodium polystyrenesulfonate, and polyethersulfone.

[0020] In the present invention, a strong interfacial bonding force is generated between the base layer and the substrate and the homogeneous heat absorption layer. The light-absorbing particles in the homogeneous heat absorption layer and the porous heat absorption layer absorb light heat, triggering a phase transition of the thermotropic phase change material in the thermoresponsive layer, forming a mobile phase and infiltrating into the porous heat absorption layer and spontaneously forming a super-slippery plane. Further, the temperature-responsive microcapsules shrink, expanding the release of the anti-fouling agent.

[0021] In some preferred embodiments, the porous heat absorption layer has a pore structure formed in situ by solvent induction penetrating its upper and lower surfaces, and the pore diameter of the contained pores is 1 - 15 μm.

[0022] In some preferred embodiments, the thickness of the base layer is 20 - 60 μm.

[0023] In some preferred embodiments, the thickness of the homogeneous heat absorption layer is 0.3 - 0.5 mm.

[0024] In some preferred embodiments, the thickness of the porous heat absorption layer is 20 - 60 μm.

[0025] In some preferred embodiments, the thickness of the thermoresponsive super-slippery layer is 0.2 - 0.5 mm.

[0026] In some more specific embodiments, the schematic structural diagram of the super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness is as Figure 1 shown, including a substrate 1, a base layer 2, a homogeneous heat-absorbing layer 3, a porous heat-absorbing layer 4, and a thermoresponsive super-slippery layer 5.

[0027] Another aspect of the embodiments of the present invention also provides a preparation method of the aforementioned super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness, which includes:

[0028] 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;

[0029] 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;

[0030] 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 evaporation rate of the first solvent is greater than that of the second solvent;

[0031] Applying a fourth base liquid containing at least paraffin, temperature-responsive polymer microcapsules encapsulating an antifouling agent, and a third solvent to the surface of the porous heat-absorbing layer and performing a fourth curing treatment to form a thermoresponsive super-slippery layer, thereby obtaining a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness.

[0032] In some preferred embodiments, the preparation method specifically includes: applying the first base liquid to the surface of the substrate by spraying or brushing and curing at room temperature for 12 - 24 h to form the base layer.

[0033] In some preferred embodiments, the preparation method specifically includes: applying the second base liquid to the surface of the base layer by spraying and then leaving it at room temperature for 10 - 30 min to form a homogeneous heat-absorbing layer.

[0034] In some preferred embodiments, the preparation method specifically includes: applying the third base liquid to the surface of the homogeneous heat-absorbing layer by in-situ spraying and curing at room temperature for 12 - 24 h to form the porous heat-absorbing layer.

[0035] In some preferred embodiments, the preparation method specifically includes: applying the fourth base liquid to the surface of the porous heat-absorbing layer by brushing and curing at room temperature for 12 - 24 h to form the thermoresponsive super-slippery layer.

[0036] In some preferred embodiments, the mass ratio of the adhesive, positively charged polymer, filler, and diluent in the first base liquid is 10-20: 0.1-5: 1-5: 2-10.

[0037] In some preferred embodiments, the mass ratio of the hydrophobic resin, negatively charged polymer, light-absorbing particles, and first solvent in the second base liquid is 10-20: 0.1-5: 1-5: 2-10.

[0038] In some preferred embodiments, the mass ratio of the hydrophobic resin, light-absorbing particles, and second solvent in the third base liquid is 10-20: 1-5: 2-10.

[0039] In some preferred embodiments, the mass ratio of the paraffin wax, temperature-responsive polymer microcapsules encapsulated with antifouling agents, and third solvent in the fourth base liquid is 20-40: 1-5: 0-30.

[0040] 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.

[0041] In some preferred embodiments, the filler includes any one or a combination of two or more of kaolin, mica powder, silica, glass microspheres, and diatomite, and is not limited thereto.

[0042] In some preferred embodiments, the diluent includes any one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, and propylene glycol methyl ether, and is not limited thereto.

[0043] 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.

[0044] In some preferred embodiments, the light-absorbing particles include any one or a combination of two or more of graphene, polypyrrole, carbon black, and magnetite, and is not limited thereto.

[0045] In some preferred embodiments, the first solvent and the second solvent are each independently selected from any one or a combination of two or more of volatile alcohols, esters, ketones, benzenes, and ethers, and are not limited thereto.

[0046] In some preferred embodiments, the evaporation rate ratio of the first solvent to the second solvent is 2-4: 6-10.

[0047] In some preferred embodiments, the third solvent includes any one or a combination of two or more of alcohols, esters, ketones, benzene, and ethers, and is not limited thereto.

[0048] In some preferred embodiments, 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 is not limited thereto.

[0049] In some preferred embodiments, the method for preparing the temperature-responsive polymer microcapsules encapsulated with an antifouling agent includes:

[0050] Mixing an aqueous solution dispersing nucleating particles with an oil-phase solution containing a temperature-responsive polymer monomer, a crosslinking agent, and an initiator, and carrying out emulsion polymerization at 50-80 °C for 12-24 h, followed by centrifugation and drying to obtain microcapsules;

[0051] And adding the microcapsules into a solution containing an antifouling agent, mixing well, and carrying out stirring, centrifugation, and drying treatments to obtain the temperature-responsive polymer microcapsules encapsulated with an antifouling agent.

[0052] Further, the temperature-responsive polymer monomer includes N-isopropylacrylamide, and is not limited thereto.

[0053] Further, the antifouling agent includes any one or a combination of two or more of copper pyrithione, zinc pyrithione, and chitosan, and is not limited thereto.

[0054] Further, the crosslinking agent includes any one or a combination of two or more of N,N'-methylenebisacrylamide (MBA), divinylbenzene, and diisocyanate, and is not limited thereto.

[0055] Further, the initiator includes any one or a combination of two or more of potassium persulfate (KPS), azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (AIBME), and azodiisovaleronitrile, and is not limited thereto.

[0056] Further, the nucleating particles include any one or a combination of two or more of gaseous-phase hydrophobic SiO 2 , gaseous-phase hydrophilic SiO 2 , TiO 2 , Al 2 O 3 , and is not limited thereto.

[0057] Further, the volume ratio of the aqueous solution to the oil-phase solution is 1:4 to 1:2.

[0058] Another aspect of the embodiments of the present invention also provides the application of the aforementioned super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness in the protection of ship hulls.

[0059] The present invention proposes to combine a base layer, a light-absorbing heat layer, and a thermoresponsive anti-fouling super-slippery layer through a multi-layer structure design to achieve an anti-fouling super-slippery function with photothermal response. In the structural design of the coating, by utilizing the difference in the evaporation rates of different solvents, a light-absorbing heat layer with a porous structure is formed in-situ, which not only has a light-absorbing heat effect but also has the function of storing photothermal response materials. Thus, the goal of integrating cooperative photothermal responsiveness, anti-fouling property, and drag reduction function is achieved.

[0060] The present invention proposes to combine a base layer, a light-absorbing heat layer, and a thermoresponsive anti-fouling super-slippery layer through a multi-layer structure design to synchronously solve the problems of interfacial bonding and controllable release of anti-fouling, and achieve an anti-fouling super-slippery function with stable and reliable photothermal response. In the structural design of the coating, by utilizing the difference in the evaporation rates of different solvents, a light-absorbing heat layer with a porous structure is formed in-situ, which not only has a light-absorbing heat effect but also has the function of storing photothermal response materials. Thus, the goal of integrating cooperative photothermal responsiveness, anti-fouling property, and drag reduction function is achieved.

[0061] The technical solution of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. These embodiments are implemented on the premise of the technical solution of the invention, and detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0062] In the following embodiments, the experimental materials used can be obtained from conventional biochemical reagent companies without special instructions.

[0063] Example 1

[0064] (1) Mix 68 wt.% amino silicone resin, 2 wt.% polyacrylamide, 10 wt.% SiO 2 particles, and 20 wt.% ethyl acetate uniformly to obtain a first base liquid; brush this base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0065] (2) Dissolve 63 wt.% silicone resin, 2 wt.% polyglutamic acid, and 10 wt.% graphene oxide in ethyl acetate, and stir evenly by mechanical means to obtain a second base liquid; spray this base liquid in-situ on the surface of the above base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0066] (3) Dissolve 65 wt.% silicone resin and 10 wt.% graphene oxide in propylene glycol methyl ether, and stir evenly by mechanical means to obtain a third base liquid; spray this base liquid in-situ on the surface of the above homogeneous heat-absorbing layer and cure it at room temperature for 24 h to form a porous heat-absorbing layer;

[0067] (4) Dissolve 50 wt.% solid paraffin and 10 wt.% temperature-responsive polymer microcapsules encapsulating antifouling agents in ethyl acetate, and stir evenly by mechanical stirring to obtain the fourth base liquid; brush the base liquid in situ on the surface of the above-mentioned porous heat-absorbing layer, and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness;

[0068] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulating antifouling agents is as follows:

[0069] Disperse 1.5 g of gas-phase hydrophobic SiO 2 particles (30 nm) in 100 ml of deionized water to prepare an aqueous phase. Add 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene to prepare an oil phase. Then mix the aqueous and oil phases at a volume ratio of 1 / 3, and stir and react at a high speed at 50 °C for 12 h, centrifuge, and dry to obtain poly(N-isopropylacrylamide) microcapsule particles. Add 1 g of the above microcapsule particles to an ethanol solution of 2-pyridinethiol copper at 40 g / L, mix well, stir for 12 h, then centrifuge and dry to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0070] Example 2

[0071] (1) Mix 68 wt.% epoxy zinc-rich primer, 2 wt.% polyethyleneimine, 10 wt.% diatomite particles, and 20 wt.% toluene evenly to obtain the first base liquid; brush the base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0072] (2) Dissolve 60 wt.% fluorinated modified polyurethane resin, 2 wt.% polyglutamic acid, 5 wt.% polypyrrole powder, and 5 wt.% graphene oxide in toluene, and stir evenly by mechanical stirring to obtain the second base liquid; spray the base liquid in situ on the surface of the above base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0073] (3) Dissolve 60 wt.% fluorinated modified polyurethane resin, 5 wt.% polypyrrole powder, and 5 wt.% graphene oxide in propylene glycol methyl ether, and stir evenly by mechanical stirring to obtain the third base liquid; spray the base liquid in situ on the surface of the above homogeneous heat-absorbing layer and cure it at room temperature for 24 h to form a porous heat-absorbing layer;

[0074] (4) Dissolve 50 wt.% solid paraffin and 10 wt.% temperature-responsive polymer microcapsules encapsulated with antifouling agents in ethyl acetate, and stir evenly by mechanical stirring to obtain the fourth base liquid; brush the base liquid in situ on the surface of the above-mentioned porous heat-absorbing layer, and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness;

[0075] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulated with antifouling agents is as follows:

[0076] Disperse 1.5 g of gas-phase hydrophobic SiO2 particles (30 nm) in 100 ml of deionized water to obtain an aqueous phase, add 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene to prepare an oil phase, then mix the two phases of water and oil at a volume ratio of 1 / 3, stir and react at a high speed at 50 °C for 12 h, centrifuge, and dry to obtain poly(N-isopropylacrylamide) microcapsule particles. Add 1 g of the above microcapsule particles to an ethanol solution of 2-pyridinethiol copper at 40 g / L, mix well, stir for 12 h, then centrifuge and dry to obtain temperature-responsive polymer microcapsules encapsulated with antifouling agents.

[0077] Example 3

[0078] (1) Mix 63 wt.% polyurethane-modified epoxy resin, 2 wt.% polyacrylamide, 5 wt.% diatomite particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate evenly to obtain the first base liquid; brush the base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0079] (2) Dissolve 60 wt.% fluorinated modified polyurethane resin, 2 wt.% sodium polystyrenesulfonate, 3 wt.% iron tetroxide powder, 2 wt.% polypyrrole powder, and 5 wt.% graphene oxide in ethyl acetate, and stir evenly by mechanical stirring to obtain the second base liquid; spray the base liquid in situ on the surface of the above-mentioned base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0080] (3) Dissolve 60 wt.% fluorinated modified polyurethane resin, 3 wt.% iron tetroxide powder, 2 wt.% polypyrrole powder, and 5 wt.% graphene oxide in ethanol, and stir evenly by mechanical stirring to obtain the third base liquid; spray the base liquid in situ on the surface of the above-mentioned homogeneous heat-absorbing layer and cure it at room temperature for 18 h to form a porous heat-absorbing layer;

[0081] (4) Dissolve 50 wt.% solid paraffin and 10 wt.% temperature-responsive polymer microcapsules encapsulating antifouling agents in ethyl acetate, and mix them evenly by mechanical stirring to obtain the fourth base liquid; brush-coat this base liquid in situ on the surface of the above-mentioned porous heat-absorbing layer and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness.

[0082] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulating antifouling agents is as follows:

[0083] Disperse 1.5 g of gaseous hydrophobic SiO 2 particles (30 nm) in 100 ml of deionized water to prepare an aqueous phase. Add 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene to prepare an oil phase. Then mix the two phases of water and oil at a volume ratio of 1 / 3 and stir and react at a high speed at 50 °C for 12 h, centrifuge, and dry to obtain poly(N-isopropylacrylamide) microcapsule particles. Add 1 g of the above microcapsule particles to an ethanol solution of 2-pyridinethiol copper at 40 g / L, mix well, stir for 12 h, then centrifuge and dry to obtain temperature-responsive polymer microcapsules encapsulating antifouling agents.

[0084] Comparative Example 1 (compared with Example 3, lacking the base layer)

[0085] (1) Dissolve 60 wt.% fluorinated modified polyurethane resin, 2 wt.% sodium polystyrenesulfonate, 3 wt.% iron tetroxide powder, 2 wt.% polypyrrole powder, and 5 wt.% graphene oxide in ethyl acetate, and mix them evenly by mechanical stirring to obtain the second base liquid; spray-coat this base liquid in situ on the surface of the above-mentioned base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer.

[0086] (2) Dissolve 60 wt.% fluorinated modified polyurethane resin, 3 wt.% iron tetroxide powder, 2 wt.% polypyrrole powder, and 5 wt.% graphene oxide in ethanol, and mix them evenly by mechanical stirring to obtain the third base liquid; spray-coat this base liquid in situ on the surface of the above-mentioned homogeneous heat-absorbing layer and cure it at room temperature for 18 h to form a porous heat-absorbing layer.

[0087] (3) Dissolve 50 wt.% solid paraffin and 10 wt.% temperature-responsive polymer microcapsules encapsulating antifouling agents in ethyl acetate, and mix them evenly by mechanical stirring to obtain the fourth base liquid; brush-coat this base liquid in situ on the surface of the above-mentioned porous heat-absorbing layer and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness.

[0088] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulated with an antifouling agent is as follows:

[0089] Disperse 1.5 g of gaseous hydrophobic SiO2 particles (30 nm) in 100 ml of deionized water to obtain an aqueous phase. Add 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene to prepare an oil phase. Then mix the aqueous and oil phases at a volume ratio of 1 / 3, and carry out a high-speed stirring reaction at 50 °C for 12 h. Centrifuge and dry to obtain poly(N-isopropylacrylamide) microcapsule particles. Add 1 g of the above microcapsule particles to an ethanol solution of 2-pyridinethiol copper at 40 g / L, mix well, stir for 12 h, then centrifuge and dry to obtain the temperature-responsive polymer microcapsules encapsulated with an antifouling agent.

[0090] Performance characterization: The prepared composite coating has a weak bond with the substrate and is easy to fall off.

[0091] Comparative Example 2 (compared with Example 3, lacking a homogeneous and porous heat-absorbing layer structure)

[0092] (1) Mix 63 wt.% of polyurethane-modified epoxy resin, 2 wt.% of polyacrylamide, 5 wt.% of diatomite particles, 5 wt.% of glass microspheres, and 20 wt.% of ethyl acetate evenly to obtain a first base liquid; brush the base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0093] (2) Dissolve 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide in ethanol, and stir evenly by mechanical means to obtain a second base liquid; spray the base liquid in situ on the surface of the above base layer and cure it at room temperature for 18 h to form a heat-absorbing layer;

[0094] (3) Dissolve 50 wt.% of solid paraffin and 10 wt.% of the temperature-responsive polymer microcapsules encapsulated with an antifouling agent in ethyl acetate, and stir evenly by mechanical means to obtain a fourth base liquid; brush the base liquid in situ on the surface of the above heat-absorbing layer and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal response;

[0095] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulated with an antifouling agent is as follows:

[0096] Disperse 1.5 g of gaseous hydrophobic SiO 2An aqueous phase was prepared by dispersing particles (30 nm) in 100 ml of deionized water. An oil phase was prepared by adding 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene. Then, the aqueous and oil phases were mixed at a volume ratio of 1 / 3 and stirred vigorously at 50 °C for 12 h. After centrifugation and drying, poly(N-isopropylacrylamide) microcapsule particles were obtained. 1 g of the above microcapsule particles was added to an ethanol solution of copper pyrithione at 40 g / L and mixed thoroughly. After stirring for 12 h, the mixture was centrifuged and dried to obtain temperature-responsive polymer microcapsules encapsulating an antifouling agent.

[0097] Performance characterization: A homogeneous and porous endothermic layer structure was not formed, and the thermoresponsive super-slippery material only covered the surface of the endothermic layer, resulting in a deterioration of the thermoresponsiveness.

[0098] Comparative Example 3 (compared with Example 3, lacking temperature-responsive polymer capsules encapsulating an antifouling agent)

[0099] (1) 63 wt.% of polyurethane-modified epoxy resin, 2 wt.% of polyacrylamide, 5 wt.% of diatomite particles, 5 wt.% of glass microspheres, and 20 wt.% of ethyl acetate were mixed uniformly to obtain a first base liquid; the base liquid was brushed on the surface of the substrate and cured at room temperature for 8 h to form a base layer;

[0100] (2) 60 wt.% of fluorinated modified polyurethane resin, 2 wt.% of sodium polystyrene sulfonate, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide were dissolved in ethyl acetate and stirred mechanically to obtain a second base liquid; the base liquid was spray-coated in situ on the surface of the above base layer and cured at room temperature for 10 min to form a homogeneous endothermic layer;

[0101] (3) 60 wt.% of fluorinated modified polyurethane resin, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide were dissolved in ethanol and stirred mechanically to obtain a third base liquid; the base liquid was spray-coated in situ on the surface of the above homogeneous endothermic layer and cured at room temperature for 18 h to form a porous endothermic layer;

[0102] (4) 50 wt.% of solid paraffin was dissolved in ethyl acetate and stirred mechanically to obtain a fourth base liquid; the base liquid was brushed in situ on the surface of the above porous endothermic layer and cured at room temperature for 5 h to obtain a super-slippery composite coating with photothermal responsiveness.

[0103] Performance characterization: The antifouling property of the prepared composite coating deteriorated.

[0104] Comparative Example 4 (compared with Example 3, lacking the thermoresponsive super-slippery layer)

[0105] (1) Mix 63 wt.% of polyurethane-modified epoxy resin, 2 wt.% of polyacrylamide, 5 wt.% of diatomite particles, 5 wt.% of glass microspheres, and 20 wt.% of ethyl acetate evenly to obtain the first base liquid; brush this base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0106] (2) Dissolve 60 wt.% of fluorinated-modified polyurethane resin, 2 wt.% of sodium polystyrenesulfonate, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide in ethyl acetate and stir evenly by mechanical means to obtain the second base liquid; spray this base liquid in situ on the surface of the above base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0107] (3) Dissolve 60 wt.% of fluorinated-modified polyurethane resin, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide in ethanol and stir evenly by mechanical means to obtain the third base liquid; spray this base liquid in situ on the surface of the above homogeneous heat-absorbing layer and cure it at room temperature for 18 h to form a super-slippery composite coating.

[0108] Performance characterization: The prepared composite coating does not have super-slippery anti-fouling and drag reduction properties.

[0109] Comparative Example 5 (compared with Example 3, the temperature-responsive polymer microcapsules encapsulated with anti-fouling agent are replaced with the corresponding amounts of temperature-responsive polymer and anti-fouling agent)

[0110] (1) Mix 63 wt.% of polyurethane-modified epoxy resin, 2 wt.% of polyacrylamide, 5 wt.% of diatomite particles, 5 wt.% of glass microspheres, and 20 wt.% of ethyl acetate evenly to obtain the first base liquid; brush this base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0111] (2) Dissolve 60 wt.% of fluorinated-modified polyurethane resin, 2 wt.% of sodium polystyrenesulfonate, 3 wt.% of iron oxide powder, 2 wt.% of polypyrrole powder, and 5 wt.% of graphene oxide in ethyl acetate and stir evenly by mechanical means to obtain the second base liquid; spray this base liquid in situ on the surface of the above base layer and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0112] (3) Dissolve 60 wt.% fluorinated modified polyurethane resin, 3 wt.% iron oxide powder, 2 wt.% polypyrrole powder and 5 wt.% graphene oxide in ethanol, and stir evenly by mechanical stirring to obtain the third base liquid; spray the base liquid in situ on the surface of the above homogeneous heat-absorbing layer, and cure it at room temperature for 18 h to form a porous heat-absorbing layer;

[0113] (4) Dissolve 50 wt.% solid paraffin, 5 wt.% temperature-responsive polymer microcapsules, and 5 wt.% copper 2-pyridinethiolate in ethyl acetate, and stir evenly by mechanical stirring to obtain the fourth base liquid; brush the base liquid in situ on the surface of the above porous heat-absorbing layer, and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness;

[0114] Among them, the preparation method of the temperature-responsive polymer microcapsules is as follows:

[0115] Disperse 1.5 g of gas-phase hydrophobic SiO 2 particles (30 nm) in 100 ml of deionized water to prepare an aqueous phase, dissolve 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) in 50 ml of xylene to prepare an oil phase, then mix the water and oil phases at a volume ratio of 1 / 3, and stir and react at high speed at 50 °C for 12 h, centrifuge, and dry to obtain poly(N-isopropylacrylamide) microcapsule particles.

[0116] Performance characterization: The prepared composite coating has excellent initial antifouling performance and fast decay in the later stage.

[0117] Comparative Example 6 (compared with Example 3, lacking positively charged polymer (polyacrylamide) and negatively charged polymer (sodium polystyrenesulfonate))

[0118] (1) Mix 63 wt.% polyurethane-modified epoxy resin, 5 wt.% diatomite particles, 5 wt.% glass microspheres, and 20 wt.% ethyl acetate evenly to obtain the first base liquid; brush the base liquid on the surface of the substrate and cure it at room temperature for 8 h to form a base layer;

[0119] (2) Dissolve 60 wt.% fluorinated modified polyurethane resin, 3 wt.% iron oxide powder, 2 wt.% polypyrrole powder and 5 wt.% graphene oxide in ethyl acetate, and stir evenly by mechanical stirring to obtain the second base liquid; spray the base liquid in situ on the surface of the above base layer, and cure it at room temperature for 10 min to form a homogeneous heat-absorbing layer;

[0120] (3) Dissolve 60 wt.% fluorinated modified polyurethane resin, 3 wt.% iron oxide powder, 2 wt.% polypyrrole powder and 5 wt.% graphene oxide in ethanol, and stir evenly by mechanical stirring to obtain the third base liquid; spray the base liquid in situ on the surface of the above homogeneous heat-absorbing layer, and cure it at room temperature for 18 h to form a porous heat-absorbing layer;

[0121] (4) Dissolve 50 wt.% solid paraffin and 10 wt.% temperature-responsive polymer microcapsules encapsulated with antifouling agents in ethyl acetate, and stir evenly by mechanical stirring to obtain the fourth base liquid; brush the base liquid in situ on the surface of the above porous heat-absorbing layer, and cure it at room temperature for 5 h to obtain a super-slippery antifouling and drag-reducing composite coating with photothermal responsiveness;

[0122] Among them, the preparation method of the temperature-responsive polymer microcapsules encapsulated with antifouling agents is as follows:

[0123] Disperse 1.5 g of gas-phase hydrophobic SiO2 particles (30 nm) in 100 ml of deionized water to prepare an aqueous phase, and add 10 ml of N-isopropylacrylamide (NIPAM), 0.5 ml of N,N'-methylenebisacrylamide (MBA), and 0.2 ml of azobisisobutyronitrile (AIBN) to 50 ml of xylene to prepare an oil phase. Then mix the water and oil phases at a volume ratio of 1 / 3, and stir and react at 50 °C for 12 h, centrifuge, and dry to obtain poly(N-isopropylacrylamide) microcapsule particles. Add 1 g of the above microcapsule particles to an ethanol solution of 2-pyridinethiol copper at 40 g / L, mix well, stir for 12 h, then centrifuge and dry to obtain temperature-responsive polymer microcapsules encapsulated with antifouling agents.

[0124] Performance characterization: The bonding strength of the coating becomes poor and it is easy to fall off.

[0125] The composite coatings provided in the comparative examples and examples of the present invention were subjected to performance tests. Among them, the adhesion test standard is GB / T5210-2006, and the salt spray experiment test standard is GB / T10125-1997. The specific test results are shown in Table 1 below:

[0126] Table 1 Performance of the coatings prepared in Examples 1-3 and Comparative Examples 1-6

[0127] ;

[0128] In addition, with reference to the foregoing examples, tests were also carried out with other raw materials, process operations, and process conditions described in this specification, and relatively ideal results were obtained.

[0129] It should be understood that the technical solutions of the present invention are not limited to the limitations of the above specific embodiments. Any technical variations made according to the technical solutions of the present invention without departing from the spirit of the present invention and the scope protected by the claims 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; Wherein, the base layer comprises a positively charged polymer, an adhesive and a filler; the homogeneous heat absorption layer comprises a hydrophobic resin, a negatively charged polymer and light-absorbing particles; the porous heat absorption layer comprises a hydrophobic resin and light-absorbing particles, and the porous heat absorption layer has a porous structure; the thermally responsive super-slip layer comprises paraffin and temperature-responsive polymer microcapsules encapsulated with an antifouling agent; the positively charged polymer is selected from any one or a combination of two or more of polymethacryloyloxyethyltrimethylammonium chloride, polyethyleneimine, polyaniline, and polyacrylamide; the negatively charged polymer is selected from any one or a combination of two or more of polyglutamic acid, sodium polybenzenesulfonate, and polyethersulfone; the adhesive is selected from any one or a combination of two or more of modified epoxy resin, epoxy zinc-rich primer, and amino silicone resin; 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; The preparation method of the temperature-responsive polymer microcapsule encapsulating the antifouling agent comprises: The aqueous solution containing dispersed shaped core particles is mixed with an oily solution containing a temperature-responsive polymer monomer, a crosslinking agent, and an initiator, and emulsified polymerized at 50-80°C for 12-24 hours, and then centrifuged and dried to obtain microcapsules; wherein the temperature-responsive polymer monomer is selected from N-isopropylacrylamide; 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.

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 ultra-slip anti-fouling and drag-reducing composite coating according to claim 1, characterized in that: The antifouling agent is selected from any one of copper pyrithione, zinc pyrithione, and chitosan, or a combination of two or more thereof; And / or, the cross-linking agent is selected from any one or a combination of two or more of N,N'-methylenebisacrylamide, divinylbenzene, and diisocyanate; And / or, the initiator is selected from any one or a combination of two or more of potassium persulfate, azobisisobutyronitrile, dimethyl azobisisobutyrate, and azobisisoheptanenitrile; And / or, the nucleation particles are selected from 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.

5. 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 4, 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.

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, 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.

7. The preparation method according to claim 5, 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.

8. The preparation method according to claim 5, characterized in that: The filler is selected from any one of kaolin, mica powder, silicon dioxide, glass microbeads, and diatomaceous earth, or a combination of two or more thereof.

9. The preparation method according to claim 5, characterized in that: The diluent is selected from one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, butyl acetate, and propylene glycol methyl ether.

10. The preparation method according to claim 5, characterized in that: The light-absorbing particles are selected from one or a combination of two or more of graphene, polypyrrole, carbon black, and ferrosoferric oxide.

11. The preparation method according to claim 5, characterized in that: 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.

12. The preparation method according to claim 5, characterized in that: The volatilization rate ratio of the first solvent to the second solvent is 2-4: 6-10.

13. The preparation method according to claim 5, characterized in that: The third solvent is selected from any one or more combinations of alcohol, ester, ketone, benzene and ether.

14. The preparation method according to claim 5, characterized in that: The substrate is selected from any one of a steel substrate, an aluminum alloy substrate, and a copper alloy substrate, or a combination of two or more thereof.

15. Use of the ultra-slippery antifouling and drag-reducing composite coating with photothermal responsiveness according to any one of claims 1 to 4 in the protection of ship hulls.

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