A lignin nanobottle-based photothermal superhydrophobic deicing coating composition, coating and preparation method and application

Abstract

The application discloses a lignin nanobottle-based photothermal super-hydrophobic deicing coating composition, a coating and a preparation method and application thereof, and belongs to the technical field of coating materials. The coating composition comprises, in mass fractions, 1-20 parts of matured modified lignin nanobottle, 1-10 parts of aminopropyl-terminated polydimethylsiloxane, 1-10 parts of trimesaldehyde, 10-100 parts of hexadecyl trimethylsilane, 10-70 parts of methyl trimethoxysilane and 3000-3500 parts of a solvent. The lignin nanobottle is modified by maturation to enhance the stability and photothermal performance, the aminopropyl-terminated polydimethylsiloxane and the trimesaldehyde are subjected to Schiff base reaction to form an imine bond cross-linked hydrophobic supramolecular polymer, so that the coating has excellent self-healing property and the stability of the coating is enhanced. The various components cooperate with each other, greatly improve the hydrophobic property, weather resistance and deicing property of the coating, and prolong the service life of the coating.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating materials, and particularly relates to a lignin nano-bottle-based light-heat super-hydrophobic de-icing coating composition, a coating layer, and a preparation method and application thereof. BACKGROUND

[0002] The information disclosed in this Background section is for the purpose of increasing the understanding of the background of the present application and does not necessarily pinpoint the prior art that is already known to those skilled in the art.

[0003] In recent years, super-hydrophobic materials have attracted much attention in the field of anti- / de-icing due to their excellent anti-wetting ability and low ice adhesion. Super-hydrophobic coatings can achieve anti-icing effect by reducing the contact area of water droplets on the surface, delaying the freezing of water droplets or reducing the adhesion of water droplets. However, due to the poor weather resistance of the material in the actual complex environment (such as temperature change, ultraviolet radiation, mechanical damage, etc.), the performance of most super-hydrophobic coatings decays quickly, which is difficult to meet the long-term stability requirements in actual application. Moreover, the existing super-hydrophobic materials have poor environmental friendliness, often relying on fluorides or chemically synthesized polymer coatings, which is in conflict with the current green and sustainable development concept. Therefore, it is of great significance to develop super-hydrophobic coatings with excellent weather resistance and environmental friendliness.

[0004] Lignin has a photo-thermal effect, which can absorb light energy and convert it into heat energy under light. Therefore, in the prior art, lignin is used to prepare super-hydrophobic coatings to assist de-icing, and the photo-thermal function and super-hydrophobic anti-icing performance work together to help achieve the dual goals of "active anti-icing" and "passive de-icing", and reduce external energy consumption. For example, H,1H,2H,2H-perfluorooctyltrichlorosilane is used to modify lignin, and silane-modified lignin, nano-silica, polydimethylsiloxane, epoxy resin, curing agent, etc. are used to prepare lignin super-hydrophobic coatings. The coating relies on fluorides to reduce the surface energy of lignin, improve the hydrophobicity of the coating, and improve the anti-icing effect. However, it does not have self-healing properties. In the actual application process, fluorine-containing silane-modified lignin (low surface energy material) is easily stimulated to decompose by temperature, light, and strong oxidizing agents, etc., and has poor weather resistance. Its surface structure is also easily damaged under physical actions such as mechanical friction or wear, thereby affecting the adhesion and wettability of the coating, and leading to a decrease or loss of waterproof and de-icing performance.

[0005] In summary, it is of great significance to develop a lignin-based super-hydrophobic de-icing coating with high weather resistance and self-repairing properties. SUMMARY

[0006] In order to solve the problems in the prior art, the present application aims to provide a lignin nanobottle-based photothermal super-hydrophobic deicing coating composition, a coating and a preparation method and application thereof.The lignin nanobottle-based photothermal super-hydrophobic deicing coating provided by the present application has excellent self-repairing performance, weather resistance and deicing performance, and solves the problems of poor weather resistance and low deicing efficiency of lignin-based super-hydrophobic coatings in the prior art.

[0007] In order to achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0008] In a first aspect of the present application, a lignin nanobottle-based photothermal super-hydrophobic deicing coating composition is provided, which comprises, in terms of mass fraction, 1-20 parts of matured modified lignin nanobottle, 1-10 parts of aminopropyl-terminated polydimethylsiloxane, 1-10 parts of trimesaldehyde, 10-100 parts of hexadecyltrimethylsiloxane, 10-70 parts of methyltrimethoxysilane and 3000-3500 parts of a solvent.

[0009] In some embodiments of the present application, the matured modified lignin nanobottle is prepared by heating the lignin nanobottle.

[0010] Preferably, the lignin nanobottle solution is dried after being matured at 80-200 DEG C for 2-20 hours to obtain the matured modified lignin nanobottle.

[0011] In some embodiments of the present application, the solvent comprises at least one of tetrahydrofuran, ethanol and acetone.

[0012] In some embodiments of the present application, the lignin nanobottle-based photothermal super-hydrophobic deicing coating composition comprises, in terms of mass fraction, 5-15 parts of matured modified lignin nanobottle, 2-8 parts of aminopropyl-terminated polydimethylsiloxane, 2-8 parts of trimesaldehyde, 30-100 parts of hexadecyltrimethylsiloxane, 30-70 parts of methyltrimethoxysilane and 3300-3400 parts of a solvent.

[0013] In some embodiments of the present application, the lignin nanobottle-based photothermal super-hydrophobic deicing coating composition comprises, in terms of mass fraction, 10-15 parts of matured modified lignin nanobottle, 5-8 parts of aminopropyl-terminated polydimethylsiloxane, 2-5 parts of trimesaldehyde, 80-100 parts of hexadecyltrimethylsiloxane, 50-70 parts of methyltrimethoxysilane and 3300-3400 parts of a solvent.

[0014] The solvent is a mixture of tetrahydrofuran and ethanol in a volume ratio of 0.9-1.1:0.9-1.1.

[0015] In a second aspect of the present application, a preparation method of the lignin nanobottle-based photothermal super-hydrophobic deicing coating composition is provided, which comprises the following steps:

[0016] adding the aminopropyl-terminated polydimethylsiloxane and the trimesaldehyde into a solvent, stirring to obtain a first slurry;

[0017] adding the matured modified lignin nanocapsule, the cetyltrimethylsiloxane and the methyltrimethoxysilane into a solvent to obtain a second slurry;

[0018] mixing the first slurry and the second slurry to obtain the lignin nanocapsule-based photothermal superhydrophobic deicing coating.

[0019] In some embodiments of the present application, the preparation method of the matured modified lignin nanocapsule is: heating and maturing the lignin nanocapsule to obtain.

[0020] Preferably, the lignin nanocapsule solution is dried after being matured at 80-200℃ for 2-20h.

[0021] Further preferably, the drying is freeze-drying.

[0022] In some embodiments of the present application, the solvent of the first slurry includes any one of tetrahydrofuran, ethanol and acetone, and is preferably tetrahydrofuran.

[0023] In some embodiments of the present application, the solvent of the second slurry includes any one of tetrahydrofuran, ethanol and acetone, and is preferably ethanol.

[0024] In some embodiments of the present application, the first slurry and the second slurry are mixed in equal volume.

[0025] In a third aspect of the present application, a lignin nanocapsule-based photothermal superhydrophobic deicing coating is provided, which is prepared by spraying the lignin nanocapsule-based photothermal superhydrophobic deicing coating composition described above or prepared by the preparation method described above to the surface of an aluminum alloy substrate and then curing to obtain.

[0026] In a fourth aspect of the present application, the lignin nanocapsule-based photothermal superhydrophobic deicing coating described above is applied in deicing.

[0027] The present application has the following beneficial effects:

[0028] The present application provides a lignin nanobottle-based photothermal superhydrophobic deicing coating composition, comprising a cured modified lignin nanobottle, an aminopropyl-terminated polydimethylsiloxane, and triformylphenyl, etc. The lignin nanobottle is modified by curing to enhance the stability and photothermal performance, and the aminopropyl-terminated polydimethylsiloxane and triformylphenyl form an imine bond cross-linked hydrophobic supramolecular polymer through Schiff base reaction, ensuring that the coating has excellent self-healing performance and enhances the stability of the coating. The various components cooperate with each other to greatly improve the hydrophobic performance, weather resistance, and deicing performance of the coating, and prolong the service life of the coating. The lignin nanobottle-based photothermal superhydrophobic deicing coating provided by the present application does not rely on fluorides, and is green, environmentally friendly, and pollution-free.

[0029] The lignin nanobottle-based photothermal superhydrophobic deicing coating composition provided by the present application has a simple preparation process, is green and environmentally friendly, and is suitable for large-scale production.

[0030] The superhydrophobic coating prepared by spraying the lignin nanobottle-based photothermal superhydrophobic deicing coating composition on the surface of an aluminum alloy substrate has excellent self-repairing performance and weather resistance, and increases the range of practical applications. It has very excellent deicing performance, and can extend the icing time from 50s to 1683s at-20℃, and only needs 12s to make the ice slide to achieve the purpose of deicing. BRIEF DESCRIPTION OF DRAWINGS

[0031] The drawings accompanying the specification of the present application form a part thereof, serve to provide further understanding of the present application, and together with the description of the exemplary embodiments of the present application and the explanation thereof, explain the present application, and do not constitute an improper limitation of the present application.

[0032] Figure 1 Wear test hydrophobic angle and contact angle of the lignin nanobottle-based photothermal superhydrophobic deicing coating obtained in Example 4 of the present application;

[0033] Figure 2 Passive deicing process of the lignin nanobottle-based photothermal superhydrophobic deicing coating obtained in Example 4 of the present application;

[0034] Figure 3 Active deicing process of the lignin nanobottle-based photothermal superhydrophobic deicing coating obtained in Example 4 of the present application;

[0035] Figure 4 Contact angle diagram of the lignin nanobottle-based photothermal superhydrophobic deicing coating obtained in Example 4 of the present application. DETAILED DESCRIPTION

[0036] In view of the poor weather resistance, hydrophobicity, photothermal performance, and self-healing performance of the superhydrophobic coating in the prior art, which seriously affects the service life and deicing effect of the hydrophobic deicing coating, the present application provides a lignin nanobottle-based photothermal superhydrophobic deicing coating, a preparation method and application thereof.

[0037] In a first typical embodiment of the present application, a lignin nanobottle-based photothermal superhydrophobic deicing coating composition is provided, comprising, in mass parts: 1-20 parts of aged modified lignin nanobottle, 1-10 parts of aminopropyl-terminated polydimethylsiloxane, 1-10 parts of trimesaldehyde, 10-100 parts of hexadecyltrimethylsiloxane, 10-70 parts of methyltrimethoxysilane, and 3000-3500 parts of solvent.

[0038] The present application uses aged modified lignin nanobottle to prepare a superhydrophobic deicing coating. Lignin molecules will undergo irreversible condensation under high temperature stimulation, enhancing the stability and photothermal performance of the lignin nanobottle, and improving the weather resistance and deicing performance of the coating. Under the action of temperature, the β-O-4 ether bond and C-C bond break, as well as the hydroxyl and -OCH3 lignin molecule groups break, resulting in the formation of more free radicals in the lignin nanobottle. In addition, a large number of adjacent intramolecular and intermolecular free radicals simultaneously produce chemical crosslinking through α-5, β-5, and β-β bonds, enhancing the stability and photothermal performance of the lignin nanobottle.

[0039] The present application adds aminopropyl-terminated polydimethylsiloxane and trimesaldehyde to the lignin nanobottle-based photothermal superhydrophobic deicing coating composition. These two components form imine bond crosslinked hydrophobic supramolecular polymers through Schiff base reaction. The imine bond is a dynamic covalent bond with high bond energy and dynamic reversibility, which can ensure that the coating has excellent self-healing and mechanical robustness.

[0040] The present application cooperates various components to synergistically improve various properties of the coating, making the coating have excellent weather resistance, self-repairing performance, and deicing performance, and prolonging the service life of the superhydrophobic coating material.

[0041] In some embodiments of this embodiment, the aged modified lignin nanobottle is obtained by heating and aging the lignin nanobottle, and is preferably obtained by drying the lignin nanobottle solution after aging at 80-200℃ for 2-20h. The temperature affects the aging modification degree of the lignin nanobottle. If the temperature is too low, the degree of covalent crosslinking between lignin molecules is low, resulting in low stability of the lignin nanobottle. If the temperature is too high, the structure of the lignin nanobottle will be damaged, reducing its stability. Within the above temperature range, the obtained aged modified lignin nanobottle has good stability and photothermal performance.

[0042] In some embodiments of this embodiment, the aging is performed at 80-180℃ for 2-12h. Within the above range, as the temperature and time increase, the micro-nano structure, photothermal performance, stability, and hydrophobicity of the obtained aged modified lignin nanobottle are all enhanced.

[0043] In some embodiments of the embodiment, the lignin nanobottle-based photothermal superhydrophobic deicing coating composition comprises, in mass fraction: 5-15 parts of the cured modified lignin nanobottle, 2-8 parts of the aminopropyl-terminated polydimethylsiloxane, 2-8 parts of the trimesaldehyde, 30-100 parts of the hexadecyl trimethylsilane, 30-70 parts of the methyl trimethoxysilane, and 3300-3400 parts of the solvent. Specifically, the cured modified lignin nanobottle can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts, etc., the aminopropyl-terminated polydimethylsiloxane can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, etc., the trimesaldehyde can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, etc., the hexadecyl trimethylsilane can be 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, or 100 parts, etc., the methyl trimethoxysilane can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts, etc., and the solvent can be 3300 parts, 3310 parts, 3320 parts, 3330 parts, 3340 parts, 3350 parts, 3360 parts, 3370 parts, 3380 parts, 3390 parts, or 3400 parts, etc.

[0044] In some embodiments of the embodiment, the lignin nanobottle-based photothermal superhydrophobic deicing coating composition comprises, in mass fraction: 5-15 parts of the cured modified lignin nanobottle, 2-8 parts of the aminopropyl-terminated polydimethylsiloxane, 2-8 parts of the trimesaldehyde, 30-100 parts of the hexadecyl trimethylsilane, 30-70 parts of the methyl trimethoxysilane, and 3300-3400 parts of the solvent. Specifically, the cured modified lignin nanobottle can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts, etc., the aminopropyl-terminated polydimethylsiloxane can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, etc., the trimesaldehyde can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, etc., the hexadecyl trimethylsilane can be 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, or 100 parts, etc., the methyl trimethoxysilane can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts, etc., and the solvent can be 3300 parts, 3310 parts, 3320 parts, 3330 parts, 3340 parts, 3350 parts, 3360 parts, 3370 parts, 3380 parts, 3390 parts, or 3400 parts, etc.

[0045] The solvent is a mixture of tetrahydrofuran and ethanol in a volume ratio of 0.9-1.1:0.9-1.1.

[0046] The coating layer prepared by using the lignin nanobottle-based photothermal superhydrophobic deicing coating composition has excellent weather resistance, self-repairing performance, and deicing performance.

[0047] In a second typical embodiment of the present application, a preparation method of the lignin nanobottle-based photothermal superhydrophobic deicing coating composition is provided, which comprises:

[0048] The aminopropyl-terminated polydimethylsiloxane and the trimesaldehyde are added into the solvent and stirred to obtain a first slurry;

[0049] The cured modified lignin nanobottle, the hexadecyl trimethylsilane, and the methyl trimethoxysilane are added into the solvent to obtain a second slurry;

[0050] Mixing the first slurry and the second slurry to obtain the lignin nanobottle-based photothermal superhydrophobic deicing coating.

[0051] In some embodiments of the embodiment, the preparation method of the matured modified lignin nanobottle is: heating and maturing the lignin nanobottle to obtain.

[0052] In some embodiments of the embodiment, the lignin nanobottle solution is dried after being matured at 80-200℃ for 2-20h to obtain.

[0053] In some embodiments of the embodiment, the drying is freeze-drying.

[0054] In some embodiments of the embodiment, the solvent of the first slurry comprises any one of tetrahydrofuran, ethanol and acetone, and is preferably tetrahydrofuran.

[0055] In some embodiments of the embodiment, the stirring is: the stirring speed is 300-800rpm, and is more preferably 400-600rpm; the stirring time is 1-5h, and is more preferably 1-2h. The appropriate stirring speed and stirring time are conducive to the full reaction of the aminopropyl-terminated polydimethylsiloxane and the triformylphloroglucin to generate more imine bonds to improve the self-healing performance of the coating. At the same time, the appropriate stirring speed and stirring time are conducive to the complete reaction of the lignin nanobottle and the hexadecyltrimethylsiloxane and the methyltrimethoxysilane to improve the hydrophobicity of the matured modified lignin nanobottle.

[0056] In some embodiments of the embodiment, the solvent of the second slurry comprises any one of tetrahydrofuran, ethanol and acetone, and is preferably ethanol.

[0057] In some embodiments of the embodiment, the first slurry and the second slurry are mixed in equal volumes.

[0058] The third typical embodiment of the present application provides a lignin nanobottle-based photothermal superhydrophobic deicing coating, which is obtained by spraying the lignin nanobottle-based photothermal superhydrophobic deicing coating composition prepared by the above preparation method or the above preparation method to the surface of an aluminum alloy substrate and then curing.

[0059] In some embodiments of the embodiment, the curing is heating curing, the temperature is 60-110℃, and is preferably 80-100℃; the heating time is 0.5-6h, and is preferably 3-5h.

[0060] The lignin nanobottle-based photothermal superhydrophobic deicing coating provided by the present application has self-healing, strong weather resistance, photothermal performance and a green and fluorine-free preparation process, and has high deicing effect, long service life and higher safety in actual process.

[0061] In a fourth exemplary embodiment of the present application, there is provided a use of the lignin nanobottle-based photothermal superhydrophobic deicing coating described above in deicing.

[0062] It can be understood that the deicing is to coat the lignin nanobottle-based photothermal superhydrophobic deicing coating on the surface of the aluminum alloy substrate to be protected, so as to reduce the adverse effects of icing on the normal operation of the aluminum alloy substrate or equipment. For example, the lignin nanobottle-based photothermal superhydrophobic deicing coating can be applied to the power transmission line to achieve active and passive deicing, thereby ensuring the safe operation of the power grid.

[0063] In order for those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in conjunction with specific examples.

[0064] The raw materials used in the following examples and comparative examples are all conventional commercially available products, which can be purchased. Among them, the lignin nanobottle is prepared by the method of Example 1 in the patent "CN118530473A A kind of high uniformity lignin nanobottle and its preparation method and application".

[0065] Example 1

[0066] A method for preparing a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0067] (1) 75 mL of 1 mg / mL lignin nanobottle solution is placed in a 100 mL high-pressure reactor at 100°C for 6 hours of curing modification, and the lignin nanobottle solution after curing modification is freeze-dried to obtain a cured modified lignin nanobottle powder.

[0068] (2) 76.8 mg of aminopropyl-terminated polydimethylsiloxane and 33.2 mg of triformylphloroglucinol are added to 20 mL of tetrahydrofuran to prepare solution A by stirring reaction.

[0069] (3) 15 mg of cured modified lignin nanobottle, 150 μL of hexadecyltrimethylsiloxane and 100 μL of methyltrimethylsiloxane are added to 3 mL of ethanol, and stirred to prepare solution B.

[0070] (4) Mix 2 mL of solution A and 2 mL of solution B, and stir to prepare a superhydrophobic coating, with a stirring speed of 400 rpm and a stirring time of 1 hour.

[0071] (5) Pour the superhydrophobic coating into the spray gun at a spraying amount of 1 mL / cm 2 , spray the coating on the surface of the aluminum alloy substrate at 0.1 MPa, with a sample distance of 15 cm, and finally dry the solvent at 105°C to obtain a lignin nanobottle-based photothermal superhydrophobic deicing coating.

[0072] Example 2

[0073] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0074] (1) 75 mL of 1 mg / mL lignin nanobottle solution is placed in a 100 mL high-pressure reaction kettle for 180°C curing modification for 12 h. After the lignin nanobottle solution after curing modification is freeze-dried, a lignin nanobottle powder after curing modification is obtained.

[0075] (2) 76.8 mg of aminopropyl-terminated polydimethylsiloxane and 33.2 mg of trimesaldehyde are added to 20 mL of tetrahydrofuran to prepare solution A by stirring reaction.

[0076] (3) 9 mg of lignin nanobottle after curing modification, 150 μL of hexadecyltrimethylsiloxane, and 100 μL of methyltrimethylsiloxane are added to 3 mL of ethanol, and solution B is prepared by stirring and mixing.

[0077] (4) 2 mL of solution A and 2 mL of solution B are mixed to prepare a superhydrophobic coating by stirring, and the stirring speed is 400 rpm and the stirring time is 1 h.

[0078] (5) The superhydrophobic coating is poured into a spray gun at a spraying amount of 1 mL / cm 2 , and the coating is sprayed on the surface of an aluminum alloy substrate under the conditions of 0.1 MPa and a spray pen sample distance of 15 cm, and finally the solvent is volatilized at 105°C to obtain a lignin nanobottle-based photothermal superhydrophobic deicing coating.

[0079] Example 3

[0080] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0081] (1) 75 mL of 1 mg / mL lignin nanobottle solution is placed in a 100 mL high-pressure reaction kettle for 180°C curing modification for 6 h. After the lignin nanobottle solution after curing modification is freeze-dried, a lignin nanobottle powder after curing modification is obtained.

[0082] (2) 33.2 mg of aminopropyl-terminated polydimethylsiloxane and 76.8 mg of trimesaldehyde are added to 20 mL of tetrahydrofuran to prepare solution A by stirring reaction.

[0083] (3) 21 mg of lignin nanobottle after curing modification, 50 μL of hexadecyltrimethylsiloxane, and 50 μL of methyltrimethylsiloxane are added to 3 mL of ethanol, and solution B is prepared by stirring and mixing.

[0084] (4) 2 mL of solution A and 2 mL of solution B are mixed to prepare a super-hydrophobic coating, the stirring speed is 400 rpm, and the stirring time is 1 h.

[0085] (5) The super-hydrophobic coating is poured into a spray gun according to a spraying amount of 1 mL / cm 2 , sprayed on the surface of an aluminum alloy substrate under the condition of 0.1 MPa and a spray pen sample distance of 15 cm, and finally the solvent is volatilized at 105°C to obtain a lignin nanobottle-based photothermal super-hydrophobic deicing coating.

[0086] Example 4

[0087] A preparation method of a lignin nanobottle-based photothermal super-hydrophobic deicing coating, comprising the following steps:

[0088] (1) 75 mL of a 1 mg / mL lignin nanobottle solution is placed in a 100 mL high-pressure reaction kettle and modified at 180°C for 12 h, and the modified lignin nanobottle solution is freeze-dried to obtain modified lignin nanobottle powder.

[0089] (2) 76.8 mg of an aminopropyl-terminated polydimethylsiloxane and 33.2 mg of triformylphloroglucinol are added to 20 mL of tetrahydrofuran to prepare solution A by stirring and reaction.

[0090] (3) 21 mg of modified lignin nanobottle, 150 μL of hexadecyltrimethylsiloxane, and 100 μL of methyltrimethylsiloxane are added to 3 mL of ethanol to prepare solution B by stirring and mixing.

[0091] (4) 2 mL of solution A and 2 mL of solution B are mixed to prepare a super-hydrophobic coating, the stirring speed is 400 rpm, and the stirring time is 1 h.

[0092] (5) The super-hydrophobic coating is poured into a spray gun according to a spraying amount of 1 mL / cm 2 , sprayed on the surface of an aluminum alloy substrate under the condition of 0.1 MPa and a spray pen sample distance of 15 cm, and finally the solvent is volatilized at 105°C to obtain a lignin nanobottle-based photothermal super-hydrophobic deicing coating.

[0093] Example 5

[0094] A preparation method of a lignin nanobottle-based photothermal super-hydrophobic deicing coating, comprising the following steps:

[0095] (1) 75 mL of a 1 mg / mL lignin nanobottle solution is placed in a 100 mL high-pressure reaction kettle and modified at 180°C for 12 h, and the modified lignin nanobottle solution is freeze-dried to obtain modified lignin nanobottle powder.

[0096] (2) 76.8 mg of aminopropyl-terminated polydimethylsiloxane and 33.2 mg of trimesalicylaldehyde were added to 20 mL of tetrahydrofuran to prepare solution A by stirring and reacting.

[0097] (3) 21 mg of the aged modified lignin nanobottle, 150 μL of hexadecyltrimethylsilane, and 100 μL of methyltrimethylsilane were added to 3 mL of ethanol to prepare solution B by stirring and mixing.

[0098] (4) 2 mL of solution A and 2 mL of solution B were mixed to prepare a superhydrophobic coating by stirring, at a stirring speed of 400 rpm for 1 h.

[0099] (5) The superhydrophobic coating was poured into a spray gun at a spraying amount of 1 mL / cm 2 , sprayed on the surface of an aluminum alloy substrate at 0.1 MPa and a spray pen sample distance of 15 cm, and finally dried at 80°C to obtain a lignin nanobottle-based photothermal superhydrophobic deicing coating.

[0100] Example 6

[0101] A method for preparing a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0102] (1) 75 mL of a 1 mg / mL lignin nanobottle solution was placed in a 100 mL high-pressure reaction kettle and aged and modified at 180°C for 12 h. The aged and modified lignin nanobottle solution was freeze-dried to obtain an aged and modified lignin nanobottle powder.

[0103] (2) 76.8 mg of aminopropyl-terminated polydimethylsiloxane and 33.2 mg of trimesalicylaldehyde were added to 20 mL of tetrahydrofuran to prepare solution A by stirring and reacting.

[0104] (3) 9 mg of the aged and modified lignin nanobottle, 150 μL of hexadecyltrimethylsilane, and 100 μL of methyltrimethylsilane were added to 3 mL of ethanol to prepare solution B by stirring and mixing.

[0105] (4) 2 mL of solution A and 2 mL of solution B were mixed to prepare a superhydrophobic coating by stirring, at a stirring speed of 400 rpm for 1 h.

[0106] (5) The superhydrophobic coating was poured into a spray gun at a spraying amount of 0.5 mL / cm 2 , sprayed on the surface of an aluminum alloy substrate at 0.1 MPa and a spray pen sample distance of 15 cm, and finally dried at 105°C to obtain a lignin nanobottle-based photothermal superhydrophobic deicing coating.

[0107] Example 7

[0108] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0109] (1) 75 mL of 1 mg / mL lignin nanobottle solution was placed in a 100 mL high-pressure reactor and modified at 180°C for 12 h. After freeze-drying the modified lignin nanobottle solution, a modified lignin nanobottle powder was obtained.

[0110] (2) 33.2 mg of aminopropyl-terminated polydimethylsiloxane and 78.4 mg of trimesaldehyde were added to 20 mL of tetrahydrofuran and stirred to prepare solution A.

[0111] (3) 9 mg of modified lignin nanobottle, 50 μL of hexadecyltrimethylsiloxane, and 50 μL of methyltrimethylsiloxane were added to 3 mL of ethanol and stirred to prepare solution B.

[0112] (4) 1 mL of solution A and 2 mL of solution B were mixed and stirred to prepare a superhydrophobic coating, with a stirring speed of 400 rpm and a stirring time of 1 h.

[0113] (5) The superhydrophobic coating was poured into a spray gun at a spraying amount of 1 mL / cm 2 , and sprayed on the surface of an aluminum alloy substrate at 0.1 MPa and a spray pen sample distance of 15 cm. Finally, the solvent was evaporated at 105°C to obtain a deicing coating.

[0114] Comparative Example 1

[0115] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0116] Compared with Example 4, the difference is that step (1) is deleted in this comparative example, and lignin nanobottle is used instead of modified lignin nanobottle in step (4), and the remaining steps are the same as those of Example 4.

[0117] Comparative Example 2

[0118] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0119] Compared with Example 4, the difference is that step (2) is modified to: 110 mg of aminopropyl-terminated polydimethylsiloxane is added to 20 mL of tetrahydrofuran and stirred to prepare solution A, and the remaining steps are the same as those of Example 4.

[0120] Comparative Example 3

[0121] A preparation method of a lignin nanobottle-based photothermal superhydrophobic deicing coating, comprising the following steps:

[0122] Compared with Example 4, the difference is that step (2) of this comparative example is modified as follows: 110 mg of pyromellitic aldehyde is added to 20 mL of tetrahydrofuran and stirred to prepare solution A. The remaining steps are the same as those in Example 4.

[0123] Comparative Example 4

[0124] Classic method for preparing lignin superhydrophobic coatings:

[0125] (1) Weigh 2g of sulfate lignin using an electronic balance and disperse it in 60mL of deionized water. Stir at 300r / min at room temperature for 5min to obtain solution A. Pour solution A into a 250mL three-necked flask and continue stirring at 0.5m... 3 Nitrogen gas was introduced at a flow rate of / h, and 3.5g of imidazole was weighed and added to solution A and stirred for 1h. Acetone was measured using a graduated cylinder and poured into a beaker, and 2mL of perfluorooctyltriethoxysilane (FOTS) was measured using a graduated cylinder and poured into 36mL of acetone solution. The beaker was sealed with sealing film and stirred at 300r / min for 1h to obtain solution B. Solution B was added dropwise to solution A using an acid burette. After heating to 50℃ and stirring for 24h, 300mL of deionized water was added to precipitate lignin. After standing for 30min, solution A was poured into a centrifuge tube and centrifuged for 10min. The supernatant was poured off, and the precipitate was placed in a vacuum drying oven and dried under vacuum at 85℃ for 12h to obtain silane-modified lignin.

[0126] (2) Using an electronic balance, weigh 100 mg of silane-modified lignin and 100 mg of nano-silica and mix them in 10 mL of acetone to obtain solution C. Use a pipette to transfer 0.16 mL of polydimethylsiloxane and 0.05 mL of epoxy resin into solution C, and stir at 500 r / min at room temperature for 15 min. Use a pipette to measure 0.016 mL of polydimethylsiloxane curing agent and 0.05 mL of diethylenetriamine into solution C, and stir for 15 min to obtain a superhydrophobic coating.

[0127] (3) According to 0.0016 g / cm 2 The superhydrophobic coating was poured into the spray gun, the nozzle diameter was adjusted to 0.5 mm, the distance between the spray gun and the sample was 15 cm, and after spraying on the sample surface, it was placed in a vacuum drying oven and cured at 85°C for 10 h to obtain the superhydrophobic coating.

[0128] Comparative Example 5

[0129] An aluminum alloy substrate with no surface treatment.

[0130] Experimental Example 1:

[0131] (1) Hydrophobicity

[0132] The surface hydrophobicity of Examples 1-7 and Comparative Examples 1-5 was tested using an OCA50 contact angle meter. A 3 μL water droplet was placed on the sample surface, and the water contact angle was measured. The results are shown in Table 1.

[0133] Table 1. Contact angle and sliding angle of the embodiments and comparative examples.

[0134]

[0135]

[0136] Note: "-" indicates that this data was not measured. The slip angle usually describes the wettability of superhydrophobic materials; for non-superhydrophobic materials, the slip angle is usually too large to be meaningful for measurement.

[0137] As shown in Table 1, the coatings improved the hydrophobic angle of Comparative Example 5 to varying degrees. The contact angles of Examples 1-7 and Comparative Examples 2, 3, and 4 were all >150°, meeting the requirement for a superhydrophobic coating (water contact angle >150°); the sliding angles were all <10°, meeting the requirement for a superhydrophobic coating (sliding angle <10°), with Examples 3, 4, 5, and 7 and Comparative Example 4 having sliding angles <2°. In contrast, Comparative Example 1 did not achieve superhydrophobic properties, indicating that the hydrothermal curing modification provided by this invention significantly improves the hydrophobicity of the lignin nanobottle, facilitating the preparation of a lignin superhydrophobic coating. Furthermore, the traditional lignin coating (Comparative Example 4) also met the requirement for a contact angle (water contact angle >150°).

[0138] (2) Weather resistance test

[0139] I: Abrasion Test: A 2cm × 2cm coated sample prepared under optimal reaction conditions in Example 4 was placed face-to-face on a 23cm × 28cm sheet of 1000-grit sandpaper. A 100g weight was attached to the back of the sample using double-sided tape to apply pressure to the coating. The abrasion test was conducted at 0.08ms. -1 The sample was moved laterally a distance of 20 cm at a certain speed. The contact angle and sliding angle of the sample were measured after every 10 wear cycles.

[0140] Depend on Figure 1 It can be seen that the coating prepared under the optimal reaction conditions of Example 4 exhibits significant stability under severe mechanical wear. After repeated wear, the surface retains its superhydrophobicity, and the contact angle and slip angle do not change significantly. This demonstrates that the coating has excellent wear resistance.

[0141] II: Acid-base test: The coating samples prepared from the examples and comparative examples with size of 2cm x 2cm were placed in 0.1M HC1 (pH = 1) or 0.1M NaOH (pH = 13) aqueous solution for 120min, and the contact angle and sliding angle of the samples were recorded every 30min.

[0142] Table 2: Alkali resistance (contact angle (°)) of the coating obtained from the examples and comparative examples

[0143]

[0144]

[0145] Table 3: Alkali resistance (contact angle (°)) of the coating obtained from the examples and comparative examples

[0146] NaOH / min 0 120 Example 3 165.0 161.7 Example 4 169.1 166 Example 5 167.8 163.5 Example 7 165.8 160.7 Comparative Example 1 132.3 123.5 Comparative Example 2 153.2 78.8 Comparative Example 3 152.5 80.1 Comparative Example 4 158 128 Comparative Example 5 75.8 76.9

[0147] As can be seen from Table 2, Table 3, the coating prepared from the examples exhibits significant stability under harsh chemical corrosion, and the contact angle does not change greatly and still meets the requirements of super-hydrophobic coating. After being immersed in 0.1M HC1 (pH = 1) or 0.1M NaOH (pH = 13) aqueous solution for 120min, the contact angle does not change greatly and still meets the requirements of super-hydrophobic coating. The contact angle of Comparative Example 1 changes greatly, which shows that the maturation treatment used in the present application effectively improves the stability of the lignin nanobottle. Comparative Example 2 and Comparative Example 3 lack the stable structure produced by the reaction of trimesalyl chloride and aminopropyl-terminated polydimethylsiloxane, so after being immersed in the solution, the surface coating structure is re-dissolved in the solution, which destroys the super-hydrophobic structure and loses the super-hydrophobic property. In addition, the traditional lignin-based super-hydrophobic coating (Comparative Example 4) also loses the super-hydrophobic property under harsh environment.

[0148] (3) Self-healing test

[0149] The sample coating surface prepared from Example 4 and Comparative Example 4 under the optimal reaction conditions was severely damaged by plasma etching. Then the plasma-etched coating was placed at room temperature for 2h for self-healing, and the contact angle and sliding angle were monitored.

[0150] Table 4: Self-healing of the sample coating prepared from Example 4 and Comparative Example 4

[0151]

[0152] Note: "-" means that the data is not measured. The sliding angle generally describes the wettability of super-hydrophobic materials, and the sliding angle of non-super-hydrophobic materials is usually too large to have no measurement significance.

[0153] As can be seen from Table 4, the coating made from Example 4 under the optimal reaction conditions has excellent self-healing properties due to the dynamic imine bond in the coating. The contact angle and sliding angle after self-healing at room temperature can still achieve excellent super-hydrophobic properties. In contrast, Comparative Example 4 does not achieve the recovery of super-hydrophobic properties because no dynamic imine bond is formed in the coating.

[0154] (4) De-icing test

[0155] Photo-thermal passive de-icing test: Under the condition of -20℃, the process of water droplet freezing on the coating surface of the sample of Example 4 under the optimal conditions was recorded under 1 sun irradiation, i.e. the process of water droplet from transparent to opaque.

[0156] Photo-thermal active de-icing test: On the contrary, under the condition of -20℃, the process of ice droplet melting on the coating surface of the sample of Example 4 under the optimal conditions was recorded under 1 sun irradiation, i.e. the process of ice droplet from opaque to transparent water droplet.

[0157] Table 5 Photo-thermal passive de-icing test and photo-thermal active de-icing test results

[0158] Example / Comparative Example Freezing time / s Ice cube slide time / s Example 4 1683 12 Comparative Example 1 156 - Comparative Example 4 185 39 Comparative Example 5 50 -

[0159] As can be seen from Table 5, Figure 2 and Figure 3 the coating made from Example 4 under the optimal conditions exhibits excellent de-icing ability. Example 4 can prolong the freezing time to 1683s compared with Comparative Example 1, Comparative Example 4 and Comparative Example 5, and the passive de-icing effect is significantly improved. In terms of active de-icing effect, Example 4 can make the ice block slide off to achieve the purpose of de-icing in 12s, while Comparative Example 1 and Comparative Example 5 cannot achieve the purpose of de-icing because they do not achieve super-hydrophobic properties, resulting in strong adhesion between the water after thawing and the surface and thus cannot slide. Because the photo-thermal performance of lignin in Comparative Example 4 is poor, it takes 39s to make the ice block slide off. Comparative Example 2 and Comparative Example 3 have too poor coating stability, and it is not practical to study the de-icing performance thereof.

[0160] The preferred embodiments of the present application have been described above with reference to the drawings, but the present application is not limited to the above examples, and various modifications and changes can be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition, characterized in that, By mass, it includes: 1-20 parts of aged and modified lignin nanobottle, 1-10 parts of aminopropyl-terminated polydimethylsiloxane, 1-10 parts of pyromellitic methylaldehyde, 10-100 parts of hexadecyltrimethylsiloxane, 10-70 parts of methyltrimethoxysiloxane, and 3000-3500 parts of solvent. The lignin nanobottle solution was aged at 80-200℃ for 2-20 hours and then dried to obtain the aged and modified lignin nanobottle.

2. The lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition as described in claim 1, characterized in that, The solvent includes at least one of tetrahydrofuran, ethanol, and acetone.

3. The lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition as described in claim 1, characterized in that, By mass, it includes: 5-15 parts of aged and modified lignin nanobottle, 2-8 parts of aminopropyl-terminated polydimethylsiloxane, 2-8 parts of pyromellitic methylaldehyde, 30-100 parts of hexadecyltrimethylsiloxane, 30-70 parts of methyltrimethoxysiloxane, and 3300-3400 parts of solvent.

4. The lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition as described in claim 1, characterized in that, By mass, it includes: 10-15 parts of aged and modified lignin nanobottle, 5-8 parts of aminopropyl-terminated polydimethylsiloxane, 2-5 parts of pyromellitic methylaldehyde, 80-100 parts of hexadecyltrimethylsiloxane, 50-70 parts of methyltrimethoxysiloxane, and 3300-3400 parts of solvent. The solvent is a mixture of tetrahydrofuran and ethanol in a volume ratio of 0.9-1.1:0.9-1.

1.

5. A method for preparing the lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition according to any one of claims 1-4, characterized in that, include: The aminopropyl-terminated polydimethylsiloxane and trimesin were added to a solvent and stirred to obtain the first slurry. A second slurry was obtained by adding aged and modified lignin nanobottles, hexadecyltrimethylsiloxane and methyltrimethoxysiloxane to a solvent; The first slurry and the second slurry are mixed to obtain a lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition. The method for preparing the aged and modified lignin nanobottle is as follows: the lignin nanobottle solution is aged at 80-200℃ for 2-20 h and then dried.

6. The preparation method according to claim 5, characterized in that, The drying process is freeze-drying.

7. The preparation method according to claim 5, characterized in that, The solvent for the first slurry includes any one of tetrahydrofuran, ethanol, and acetone; The solvent for the second slurry includes any one of tetrahydrofuran, ethanol, and acetone.

8. The preparation method according to claim 7, characterized in that, The solvent for the first slurry is tetrahydrofuran.

9. The preparation method according to claim 7, characterized in that, The solvent for the second slurry is ethanol.

10. The preparation method according to claim 5, characterized in that, The first and second slurries are mixed in equal volumes.

11. A lignin nano-bottle-based photothermal superhydrophobic de-icing coating, characterized in that, The lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition according to any one of claims 1-4 or the lignin nano-bottle-based photothermal superhydrophobic de-icing coating composition prepared by any one of the preparation methods according to claims 5-10 is sprayed onto the surface of an aluminum alloy substrate and cured to obtain the final product.

12. The application of the lignin nano-bottle-based photothermal superhydrophobic de-icing coating of claim 11 in de-icing.

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