Photo-thermal polymer / waste carbon composite material as well as spray preparation method and application thereof

Abstract

The invention discloses a photo-thermal polymer / waste carbon composite material as well as a spray preparation method and application thereof, and belongs to the technical field of functional materials. The preparation method comprises the following steps: sequentially adding waste powdered ink, FeCl3. 6H2O, Tween 80 and hydrochloric acid into a mixed solvent of ethanol and deionized water, and ultrasonically stirring to obtain a uniform solution A; mixing and ultrasonically treating dopamine and the like to obtain a solution B; respectively adding the solution A and the solution B into corresponding sprayers, then alternately spraying and mixing the solution A and the solution B for reaction, and finally washing and drying the obtained powder to obtain the modified waste powdered ink with the cross fibrous polymer generated on the surface in situ. The modified waste powdered ink, methyl phenyl silicone resin and MQ resin are dissolved in ethyl acetate, spraying curing is conducted after stirring and ultrasonic treatment, and the photo-thermal polymer / waste carbon composite material is obtained. Recycling of waste powdered ink is achieved through a rapid spraying method, and the prepared composite coating has excellent anti-icing and deicing performance.

Description

Technical Field

[0001] This invention belongs to the field of functional materials technology, specifically relating to a photothermal polymer / waste carbon composite material, its spray preparation method, and its application. Background Technology

[0002] Solar energy, as a green, renewable, and abundant energy source, has been widely applied in various fields such as photothermal conversion, photocatalysis, and photoelectric conversion. Among these, photothermal conversion is one of the important pathways for solar energy utilization. As a direct and efficient energy conversion method, photothermal conversion can efficiently convert incident sunlight into considerable heat energy by introducing well-designed light-absorbing materials, showing significant application prospects in fields such as photothermal de-icing, seawater desalination, wastewater purification, and biomedicine. Photothermal conversion materials include conjugated polymer materials, carbon materials, metallic materials, and semiconductor materials. For example, Chinese patent CN 120795796 A discloses "a flake structure coating based on PDMS / Co@SiO2 composite material and its preparation method and application." This technology solves the problems of low energy efficiency, poor environmental adaptability, and easy failure under extreme conditions of existing anti-icing materials by constructing multi-level micro-nano structures and synergistically combining magnetic response and photothermal effect. In addition, Chinese patent CN 120442088 A discloses "a high-entropy alloy-TiO2 composite carrier photothermal superhydrophobic anti-icing coating and its preparation method." The coating produced by this invention combines the properties of both superhydrophobicity and photothermal properties, achieving compatibility and improving its anti-icing performance, durability, and self-cleaning ability. Although these materials possess excellent photothermal conversion efficiency, they still suffer from heat loss to the surrounding environment during use, limiting light energy utilization. Therefore, developing a simple preparation process and effectively reducing heat loss are crucial breakthroughs that urgently need to be achieved.

[0003] Meanwhile, waste toner from printers, as a typical form of solid waste, faces severe challenges in its disposal. Waste toner particles are extremely fine, easily dispersed, and difficult to degrade naturally. Once leaked, they not only severely pollute the environment but also pose a persistent hazard due to the difficulty in complete cleanup. At certain concentrations in the air, they even pose a risk of dust explosion. Traditional landfill disposal methods cannot avoid long-term environmental risks, while the various additives make chemical recycling technology complex and costly, leading to most waste toner being classified as hazardous waste. It is worth noting that carbon black, the main component of waste toner, endows it with extremely strong light absorption capabilities, and combined with its low cost, it can be used as a photothermal material. However, the surface microstructure of waste toner lacks the multi-scale complexity necessary to construct superhydrophobic surfaces. This, to some extent, limits the further development of its photothermal properties.

[0004] Previously, patent CN 118292276 A, "Rapid Preparation and Application of a Janus-type Photothermal Superhydrophobic Composite Material," employed a spraying method to achieve macroscopic-scale embedded self-assembly of polydopamine-polypyrrole (PDA-PPy) nanofibers on a fabric substrate, breaking through the limits of photothermal performance. However, this method exhibits some selectivity towards the substrate material, limiting its applicability. Furthermore, existing research has focused on preparing PDA-PPy nanofibers via solution methods and combining them with hydrogel matrices to construct piezoresistive sensors. While solution methods have expanded the adaptability of PDA-PPy to different substrates to some extent, they still face challenges such as low composite efficiency and drawbacks including easy aggregation and poor structural controllability. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a photothermal polymer / waste carbon composite material, its spray preparation method, and its application. By in-situ oxidizing copolypyrrole (Py) and dopamine (DA) on the surface of waste toner, the waste toner can be recycled and reused, overcoming the problem of limited light energy utilization. The prepared composite coating can be widely used in anti-icing and de-icing fields, showing good practical application prospects, and the preparation process is simple and low-cost.

[0006] To achieve the above objectives, the present invention employs the following technical solution: A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: S1. Add FeCl3·6H2O, Tween 80 and hydrochloric acid to a mixed solvent composed of ethanol and deionized water, and stir to form a homogeneous mixture. S2. Add waste ink powder to the mixture and disperse it by ultrasonication to obtain solution A; S3. Mix dopamine, pyrrole, ethanol and deionized water, and disperse by ultrasonication to obtain solution B; S4. Add solution A and solution B to their respective sprayers, then spray solution A and solution B alternately to mix and react. After washing and drying, a composite powder is obtained. S5. Dissolve the composite powder, methylphenyl silicone resin and MQ resin in ethyl acetate, mix them evenly, spray them onto the substrate surface and cure them to obtain the waste toner-derived superhydrophobic coating with photothermal response.

[0007] A further improvement of the present invention is that: Preferably, in S1, the mixing ratio of each component by mass is: 1 part FeCl3·6H2O, 0.03~0.06 parts Tween 80, 0.6~0.9 parts hydrochloric acid, 2.0~3.5 parts ethanol, and 2.8~4.2 parts deionized water.

[0008] Preferably, in S2, the ratio of the mixed liquid to waste toner is (15~30) mL: (0.5~1.5) g.

[0009] Preferably, in S3, the mixing ratio of each component by mass is: 0.05~0.2 parts dopamine, 1 part pyrrole, 3~5 parts ethanol, and 4~6 parts deionized water.

[0010] Preferably, in S4, the volume ratio of solution A to solution B spray-mixed is 1:1 to 3:1.

[0011] Preferably, in S5, the mixing ratio of each component by mass is: 1 part composite powder, 4-6 parts methylphenyl silicone resin, 0.5-1.5 parts MQ resin, and 50-60 parts ethyl acetate.

[0012] Preferably, in S5, during spraying, the distance between the nozzle and the substrate is 10~20 cm, the spraying pressure is 0.5~0.8 MPa, the curing temperature is 80~120℃, and the curing time is 1~2 h.

[0013] A photothermal polymer / waste carbon composite material prepared by any of the above preparation methods, wherein the coating is composed of methylphenyl silicone resin and MQ resin, wherein a composite structure composed of waste toner particles coated by a polydopamine-polypyrrole multi-scale fiber network is embedded therein.

[0014] Preferably, the static water contact angle of the coating is ≥163°; and the surface equilibrium temperature of the coating is ≥90°C under irradiation of 1 solar intensity.

[0015] An application of the above-mentioned photothermal polymer / waste carbon composite material is used for anti-icing and de-icing of outdoor power lines, communication lines or building surfaces.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a rapid preparation method for photothermal polymer / waste carbon composite materials and their applications. The method involves in-situ oxidation of copolypyrrole (Py) and dopamine (DA) on the surface of waste toner to induce a copolymerization reaction, successfully constructing a composite structure covered by a multi-scale fiber network. This composite structure is then combined with methylphenyl silicone resin and MQ resin and coated onto a glass substrate, resulting in a multifunctional coating exhibiting both high photothermal conversion efficiency and superhydrophobicity. Compared to the spherical structure formed by the self-polymerization of Py and DA in the liquid phase, this modification method, through alternating spraying, allows the oxidant-loaded waste carbon powder and pre-assembled Py-DA monomers to meet in the form of small droplets generated by atomization and react rapidly, forming a cross-linked fibrous structure. This reduces agglomeration, resulting in a more uniform composite on the waste carbon powder surface and exhibiting higher photothermal conversion efficiency.

[0017] This invention also discloses a photothermal polymer / waste carbon composite material prepared by the above-described method. Due to the inherent properties of waste toner and the multi-scale structure formed on its surface, this coating exhibits excellent photothermal properties. Under 1.0 lux sunlight, the coating surface temperature can reach 91.5°C. Simultaneously, this structure endows the coating with an extremely high static contact angle (163°) and an extremely low roll-off angle (2.5°), demonstrating superior superhydrophobic properties. Furthermore, at -5°C, the freezing time of water droplets on the coating surface is delayed by 16.7 times, and they completely melt within 75 seconds under 1.0 lux sunlight. The coating also exhibits excellent mechanical stability and chemical durability, withstanding a series of stringent tests including sandpaper abrasion, tape peeling, UV aging, and acid / alkali corrosion. This coating has also been applied to horizontal cables, and its anti-icing / de-icing performance has been evaluated in practical applications. The photothermal superhydrophobic coating prepared by this invention not only enables efficient coating of various photothermal superhydrophobic materials, but also effectively utilizes waste toner, achieving resource recycling. This provides significant environmental benefits and broad application prospects for its practical application in the field of anti-icing, and can be applied to LGJ. 300 / 40 type State Grid special conductor. Attached Figure Description

[0018] Figure 1 This is a SEM image of the in-situ grown fibrous polymer on the surface of the toner prepared in Example 1 of this invention. Figure 2 Here is a solar photothermal heating curve of the coating prepared in Example 2 of the present invention; Figure 3 This is a diagram showing the water contact angle of the coating prepared in Example 3 of the present invention to resist the erosion of water-soluble pollutants; Figure 4 These are photographs of the anti-icing process of the coating prepared in Example 4 of this invention at -5°C; Figure 5 This is a photograph of the de-icing process of the coating prepared in Example 5 of the present invention under sunlight; Figure 6 This is a comparison of the melting process of icicles on the surface of the original cable and the coated cable under a certain solar radiation intensity, based on the coating applied to the surface of the LGJ-300 / 40 State Grid special conductor in Embodiment 6 of the present invention. Detailed Implementation

[0019] The present invention will now be described in further detail with reference to the accompanying drawings: To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0020] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0021] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0022] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0023] A photothermal responsive waste ink-derived superhydrophobic coating, its preparation and application, comprising the following steps: Step 1: By mass fraction, add 1 part FeCl3·6H2O, 0.03-0.06 parts Tween 80, and 0.6-0.9 parts hydrochloric acid sequentially to a mixed solvent consisting of 2.0-3.5 parts ethanol and 2.8-4.2 parts deionized water, and stir magnetically to form a homogeneous solution. The stirring speed of the magnetic stirrer is 500-1000 r / min, and the stirring time is 10-20 min.

[0024] Step two: Take a certain amount of the above mixture and add waste ink powder. Disperse the mixture fully by ultrasonic treatment. The resulting suspension is denoted as solution A. The ratio of the mixture to waste ink powder is (15~30) mL : (0.5~1.5) g. The ultrasonic frequency during the ultrasonic process is 40~130 kHz, and the ultrasonic time is 10~20 min. In this process, solution A consists of waste ink powder and the above mixture, which contains FeCl3·6H2O.

[0025] Step 3: Mix 0.05-0.2 parts of dopamine, 1 part of pyrrole, 3-5 parts of ethanol and 4-6 parts of deionized water by mass fraction and disperse by ultrasonication at a frequency of 60-100 kHz for 2-5 min to obtain solution B. Step 4: Add solution A and solution B to the corresponding sprayers respectively, and then spray solution A and solution B alternately into the cavity to mix and react through the spray in the cavity. After washing and drying, a composite powder is obtained. The powder is obtained by washing deionized water 2-4 times with solution A and solution B in a volume ratio of (1~3):1, and then drying at a temperature of 60~100℃ for 8~12h.

[0026] During this process, solutions A and B are sprayed alternately, and as the reaction proceeds and the solvent evaporates, Fe... 3+ The waste toner is effectively loaded onto its surface. Simultaneously, the waste toner adsorbs pre-assembled Py and DA molecules through π-π stacking interactions or hydrogen bonding. When Py and DA come into contact with an oxidant (Fe... 3+ When Py and DA undergo an in-situ oxidative copolymerization reaction on the surface of waste toner, they form a fiber structure with multi-scale characteristics.

[0027] Step 5: By mass fraction, dissolve 1 part of dry powder, 4-6 parts of methylphenyl silicone resin, and 0.5-1.5 parts of MQ resin in 50-60 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray and cure to obtain a photothermally responsive waste toner-derived superhydrophobic coating. During spraying, the distance between the nozzle and the substrate is 10-20 cm, the spraying pressure is 0.5-0.8 MPa, the curing temperature is 80-120℃, and the curing time is 1-2 hours. In this process, the resin is introduced into the entire coating as a binder, which can stabilize the micro-rough structure, thereby greatly enhancing the mechanical stability and durability of the coating.

[0028] A second aspect of this invention discloses a photothermal superhydrophobic coating prepared by the above method. The final coating's main structure consists of methylphenyl silicone resin and MQ resin, with embedded composite structures formed by polydopamine-polypyrrole multi-scale fiber networks coating waste toner particles. This composite structure originates from a composite powder in which the surface of the waste toner particles is formed by an in-situ copolymerization reaction of polydopamine and polypyrrole to create a fiber structure.

[0029] The third aspect of this invention discloses a photothermal superhydrophobic coating for anti-icing and de-icing of outdoor power lines, communication lines or building surfaces.

[0030] The following description, in conjunction with specific embodiments, provides further details.

[0031] Example 1 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.03 parts Tween 80 and 0.6 parts hydrochloric acid to a mixed solvent consisting of 2.0 parts ethanol and 2.8 parts deionized water in sequence, and stir for 10 minutes under magnetic stirring at 600 r / min to obtain a homogeneous solution.

[0032] Step 2: Take 20 ml of the above mixture and add 0.7 g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 60 kHz and ultrasonic time of 10 min. The resulting suspension is denoted as solution A. Step 3: Mix 0.1 parts dopamine, 1 part pyrrole, 3 parts ethanol and 4 parts deionized water, and disperse them under ultrasonic conditions of 60 kHz and 2 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 1:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 60°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 4 parts of methylphenyl silicone resin and 0.5 parts of MQ resin in 50 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 10 cm and a spraying pressure of 0.8 MPa. Then cure it at 120°C for 1 hour to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0033] Figure 1 This is a SEM image of the modified waste ink powder prepared in Example 1 of the present invention. (The image is obtained through...) Figure 1 It can be observed that the waste toner has a relatively smooth overall morphology, with fine nanoscale protrusions and local depressions on its surface. After spray treatment with mixed solution A and mixed solution B, a fibrous structure with multi-scale characteristics is formed. This structure not only effectively improves the surface roughness but also promotes air retention, thereby significantly enhancing the hydrophobic properties of the material and playing a key role in the anti-icing process.

[0034] Example 2 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.03 parts Tween 80 and 0.8 parts hydrochloric acid to a mixed solvent consisting of 2.5 parts ethanol and 3 parts deionized water in sequence, and stir for 10 minutes under magnetic stirring at 700 r / min to obtain a homogeneous solution.

[0035] Step 2: Take 22ml of the above mixture and add 0.6g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 80KHz and ultrasonic time of 10min. The resulting suspension is denoted as solution A. Step 3: Mix 0.1 parts dopamine, 1 part pyrrole, 4 parts ethanol and 5 parts deionized water, and disperse them under ultrasonic conditions of 60 kHz and 2 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 1:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 60°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 5 parts of methylphenyl silicone resin and 1 part of MQ resin in 50 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 10 cm and a spraying pressure of 0.8 MPa. Then cure it at 120°C for 1 hour to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0036] Figure 2 The photothermal temperature rise curve of the coating prepared in Example 2 of this invention under one sun. (By...) Figure 2 It can be seen that under one solar irradiation condition, the highest equilibrium temperature of the coating surface can reach 91.5℃, and remains basically stable with continuous irradiation. This result indicates that the coating has excellent photothermal conversion capability, providing an important condition for achieving efficient photothermal de-icing.

[0037] Example 3 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.06 parts Tween 80 and 0.9 parts hydrochloric acid to a mixed solvent consisting of 2 parts ethanol and 4 parts deionized water in sequence, and stir for 10 minutes under magnetic stirring at 800 r / min to obtain a homogeneous solution.

[0038] Step 2: Take 25ml of the above mixture and add 0.8g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 80KHz and ultrasonic time of 10min. The resulting suspension is denoted as solution A. Step 3: Mix 0.1 parts dopamine, 1 part pyrrole, 5 parts ethanol and 5 parts deionized water, and disperse them under ultrasonic conditions of 60 kHz and 2 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 2:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 60°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 5 parts of methylphenyl silicone resin and 1 part of MQ resin in 55 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 10 cm and a spraying pressure of 0.8 MPa. Then cure the mixture at 120 °C for 1 h to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0039] Figure 3 The image shows the contact angle and anti-fouling properties of the coating prepared in Example 3 of this invention. Figure 3 It can be observed that the water droplets on the prepared coating surface are approximately spherical with a water contact angle as high as 163°. After being immersed in methylene blue solution, the surface is still clean and dry, fully demonstrating excellent superhydrophobic and anti-fouling self-cleaning properties.

[0040] Example 4 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.04 parts Tween 80 and 0.9 parts hydrochloric acid to a mixed solvent consisting of 3.5 parts ethanol and 3.5 parts deionized water in sequence, and stir for 15 minutes under magnetic stirring at 800 r / min to obtain a homogeneous solution.

[0041] Step 2: Take 25ml of the above mixture and add 1.5g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 100KHz and ultrasonic time of 10min. The resulting suspension is denoted as solution A. Step 3: Mix 0.2 parts dopamine, 1 part pyrrole, 4 parts ethanol and 4 parts deionized water, and disperse them under ultrasonic conditions of 80 kHz and 5 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 2:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 60°C for 10 hours. Step 5: Dissolve 1 part of dry powder, 5 parts of methylphenyl silicone resin and 1 part of MQ resin in 55 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 10 cm and a spraying pressure of 0.8 MPa. Then cure the mixture at 120 °C for 1 h to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0042] Figure 4 Photographs of the anti-icing process of the coating and the original glass slide prepared in Example 4 of this invention at -5°C. Figure 4As shown, on a cooling stage at -5°C, the freezing time of a 20-microliter water droplet on the coating surface was extended to 4476 seconds, which is 16.7 times the freezing time of the original glass slide.

[0043] Example 5 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.06 parts Tween 80 and 0.9 parts hydrochloric acid to a mixed solvent consisting of 3.5 parts ethanol and 4.2 parts deionized water in sequence, and stir for 15 minutes under magnetic stirring at 800 r / min to obtain a homogeneous solution.

[0044] Step 2: Take 30ml of the above mixture and add 1.5g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 100KHz and ultrasonic time of 15min. The resulting suspension is denoted as solution A. Step 3: Mix 0.2 parts dopamine, 1 part pyrrole, 5 parts ethanol and 4 parts deionized water, and disperse them under ultrasonic conditions of 80 kHz and 5 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 2:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 60°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 6 parts of methylphenyl silicone resin and 1.5 parts of MQ resin in 60 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 15 cm and a spraying pressure of 0.8 MPa. Then cure it at 120°C for 2 hours to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0045] Figure 5 A photograph of the de-icing process of the coating prepared in Example 5 of the present invention under sunlight. Figure 5 As shown, under one sun exposure, ice droplets frozen on the coating surface can melt rapidly within 75 seconds.

[0046] Example 6 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.06 parts Tween 80 and 0.9 parts hydrochloric acid to a mixed solvent consisting of 3.5 parts ethanol and 4.2 parts deionized water in sequence, and stir for 15 minutes under magnetic stirring at 800 r / min to obtain a homogeneous solution.

[0047] Step 2: Take 30ml of the above mixture and add 1.5g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 100KHz and ultrasonic time of 15min. The resulting suspension is denoted as solution A. Step 3: Mix 0.1 parts dopamine, 1 part pyrrole, 5 parts ethanol and 6 parts deionized water, and disperse them under ultrasonic conditions of 100 kHz and 3 min to obtain solution B. Step four: Add solutions A and B to their respective sprayers, then alternately spray solutions A and B at a volume ratio of 3:1 to mix and react. After the reaction is complete, wash the resulting powder three times with deionized water and then dry it in an oven at 80°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 5 parts of methylphenyl silicone resin and 1 part of MQ resin in 50 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 15 cm and a spraying pressure of 0.8 MPa. Then cure it at 120 °C for 1 h to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0048] Figure 6 The coating prepared for Example 6 of this invention was applied to the surface of a State Grid-specific LGJ-300 / 40 cable. Under a single solar radiation intensity, the melting process of icicles on the surfaces of the original cable and the coated cable was compared. The icicles on the original cable surface began to melt at 1 minute and 2 seconds and were completely melted by 21 minutes and 18 seconds. In contrast, due to the photothermal properties of the coated cable, the icicles began to melt at 56 seconds and completely disappeared by 7 minutes and 12 seconds.

[0049] Example 7 A spray preparation method for a photothermal polymer / waste carbon composite material includes the following steps: Step 1: Add 1 part FeCl3·6H2O, 0.06 parts Tween 80 and 0.9 parts hydrochloric acid to a mixed solvent consisting of 3.5 parts ethanol and 4.2 parts deionized water in sequence, and stir for 15 minutes under magnetic stirring at 800 r / min to obtain a homogeneous solution.

[0050] Step 2: Take 15ml of the above mixture and add 0.5g of waste ink powder. Disperse the mixture thoroughly under the conditions of ultrasonic frequency of 100KHz and ultrasonic time of 15min. The resulting suspension is denoted as solution A. Step 3: Mix 0.05 parts dopamine, 1 part pyrrole, 5 parts ethanol and 6 parts deionized water, and disperse them under ultrasonic conditions of 100 kHz and 3 min to obtain solution B. Step 4: Add solutions A and B to the corresponding sprayers respectively, and then spray solutions A and B alternately at a volume ratio of 3:1 to mix and react. After the reaction is complete, the resulting powder is washed three times with deionized water and then dried in an oven at 90°C for 8 hours. Step 5: Dissolve 1 part of dry powder, 5 parts of methylphenyl silicone resin and 1 part of MQ resin in 50 parts of ethyl acetate. After magnetic stirring and ultrasonic treatment, spray the mixture at a spraying distance of 20 cm and a spraying pressure of 0.5 MPa. Then cure it at 90 °C for 2 h to obtain a photothermal responsive waste toner-derived superhydrophobic coating.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A spray preparation method for a photothermal polymer / waste carbon composite material, characterized in that, Includes the following steps: S1. Add FeCl3·6H2O, Tween 80 and hydrochloric acid to a mixed solvent composed of ethanol and deionized water, and stir to form a homogeneous mixture. S2. Add waste ink powder to the mixture and disperse it by ultrasonication to obtain solution A; S3. Mix dopamine, pyrrole, ethanol and deionized water, and disperse by ultrasonication to obtain solution B; S4. Add solution A and solution B to their respective sprayers, then spray solution A and solution B alternately to mix and react. After washing and drying, a composite powder is obtained. S5. Dissolve the composite powder, methylphenyl silicone resin and MQ resin in ethyl acetate, mix them evenly, spray them onto the substrate surface and cure them to obtain the waste toner-derived superhydrophobic coating with photothermal response.

2. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S1, the mixing ratio of each component by mass is as follows: 1 part FeCl3·6H2O, 0.03~0.06 parts Tween 80, 0.6~0.9 parts hydrochloric acid, 2.0~3.5 parts ethanol, and 2.8~4.2 parts deionized water.

3. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S2, the ratio of the mixed liquid to waste toner is (15~30) mL: (0.5~1.5) g.

4. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S3, the mixing ratio of each component by mass is: 0.05~0.2 parts dopamine, 1 part pyrrole, 3~5 parts ethanol, and 4~6 parts deionized water.

5. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S4, the volume ratio of solution A to solution B spray-mixed is 1:1 to 3:

1.

6. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S5, the mixing ratio of each component by mass is as follows: 1 part composite powder, 4-6 parts methylphenyl silicone resin, 0.5-1.5 parts MQ resin, and 50-60 parts ethyl acetate.

7. The spray preparation method for a photothermal polymer / waste carbon composite material according to claim 1, characterized in that, In S5, during spraying, the distance between the nozzle and the substrate is 10~20 cm, the spraying pressure is 0.5~0.8 MPa, the curing temperature is 80~120℃, and the curing time is 1~2 h.

8. A photothermal polymer / waste carbon composite material prepared by any one of claims 1-7, characterized in that, The coating is composed of methylphenyl silicone resin and MQ resin, wherein a composite structure consisting of waste toner particles encapsulated by a polydopamine-polypyrrole multi-scale fiber network is embedded therein.

9. The photothermal polymer / waste carbon composite material according to claim 8, characterized in that, The coating has a static water contact angle ≥163°; and under irradiation of 1 solar intensity, the coating surface equilibrium temperature ≥90℃.

10. An application of the photothermal polymer / waste carbon composite material according to claim 9, characterized in that, Used for anti-icing and de-icing of outdoor power lines, communication lines, or building surfaces.

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