A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof

Abstract

The application provides a multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, which comprises the following raw materials in parts by weight: 40-60 parts of a composite polymer resin, 15-25 parts of modified graphene, 5-12 parts of surface-modified composite carbon nanotube / graphitized solid carbon sphere, 2-5 parts of a silane coupling agent, 0.5-1 part of a heat-conducting metal powder, 1-2 parts of zirconium oxide, 1-2 parts of lanthanum oxide, 1-2 parts of boron nitride, 1-3 parts of a modified leveling agent, 1-3 parts of a dispersing agent, 0.5-2 parts of a defoaming agent and 60-80 parts of a solvent. The heat dissipation coating has the properties of good heat dissipation, hydrophobicity and dust repellency, good antibacterial property and energy saving and emission reduction, and has good application value.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of heat dissipation coatings, and particularly relates to a multi-resin-based high-performance heat dissipation coating and a preparation method thereof. BACKGROUND

[0002] The heat dissipation coating technology is a kind of easy, effective, safe and reliable heat dissipation technology which does not change the original structure design and uses the physical heat radiation performance of the coating to take away heat. The heat dissipation coating is a kind of special coating which can improve the heat dissipation efficiency of the object surface and reduce the system temperature. The heat dissipation coating can dissipate heat in the form of radiation, reduce the object surface temperature and achieve the effect of rapid heat dissipation. The heat dissipation coating generally uses a polymer as a base material, and adds metal fillers with good heat conduction performance and non-metal fillers with high thermal conductivity such as aluminum nitride, silicon nitride, aluminum oxide and magnesium oxide, and can be widely applied to the external coating of substrate heat dissipation and pipeline heat dissipation.

[0003] The patent with the application number 202111075482.3 relates to a high-performance nano-carbon heat dissipation composite material which is composed of a carrier and a coating layer. The carrier is a copper foil tape or an aluminum foil tape, and the coating layer is composed of an organic resin, nano-carbon, propyl trimethyl(meth)oxysilane, gamma-methacryloyloxypropyl trimethoxysilane and polyethylene glycol. The present application can improve the heat dissipation performance of the coating. The pretreatment of nano-carbon with gamma-methacryloyloxypropyl trimethoxysilane can improve the compatibility of nano-carbon with the resin material, and further improve the mechanical properties of the composite material as a whole. However, the present application does not involve the research on the hydrophobic and dust-repellent properties and antibacterial properties of the coating.

[0004] Therefore, there is an urgent need for a multi-resin-based high-performance heat dissipation coating and a preparation method thereof, so that the coating can meet the performance of good heat dissipation, hydrophobic and dust-repellent properties, good antibacterial properties and energy saving and emission reduction. SUMMARY

[0005] In view of the existing technical problems, the present application aims to provide a multi-resin-based high-performance heat dissipation coating and a preparation method thereof. The heat dissipation coating provided by the present application has the performance of good heat dissipation, hydrophobic and dust-repellent properties, good antibacterial properties and energy saving and emission reduction.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] In one aspect, the present application provides a multi-resin-based high-performance heat dissipation coating. The coating contains the following raw materials in parts by weight: 40-60 parts of a composite polymer resin, 15-25 parts of modified graphene, 5-12 parts of surface modified composite carbon nanotube / graphitized solid carbon sphere, 2-5 parts of silane coupling agent, 0.5-1 part of heat-conducting metal powder, 1-2 parts of zirconium oxide, 1-2 parts of lanthanum oxide, 1-2 parts of boron nitride, 1-3 parts of modified leveling agent, 1-3 parts of dispersing agent, 0.5-2 parts of defoaming agent and 60-80 parts of solvent.

[0008] The reaction mechanism and action of the present application are as follows:

[0009] 1. The composite polymer resin of the present application is composed of fluorine-containing acrylic ester resin, epoxy resin and silicone resin in a specific mass ratio. The fluorine-containing acrylic ester resin contains fluorine atoms in the molecular structure, so that the resin surface has strong hydrophobicity, the film layer formed has low surface energy, and it is difficult for water molecules and dust to adhere to its surface, which can play a role in preventing pollution and keeping clean; the epoxy resin contains a large number of epoxy groups and aromatic ring structures in the molecular structure, which makes the epoxy resin have high heat resistance and thermal conductivity, can effectively conduct heat, and has good heat dissipation performance; the silicone resin contains silicon-oxygen bonds in the molecular structure, so that its surface has extremely strong hydrophobicity, and the high thermal conductivity of silicon element also gives the silicone resin good heat dissipation performance. The applicant controls the specific mass ratio among the three to improve the heat dissipation, hydrophobicity and dust resistance of the coating.

[0010] 2. There are many functional groups on the surface of graphene oxide, and the modified graphene of the present application is combined with the hydroxyl group on the surface and the chlorine group on the 3,5-dichloro-4-hydroxybenzoic acid, on the one hand, introducing carboxyl and hydroxyl groups on the surface, the carboxyl group can react with the epoxy resin to participate in the curing process of the epoxy resin in the form of chemical reaction, and the hydroxyl group can react with the fluorine-containing acrylic ester resin to participate in the curing process of the fluorine-containing acrylic ester resin in the form of chemical reaction, which can improve the bonding force between the graphene oxide and the film-forming matrix, prevent the migration of graphene after curing, and make the graphene continuously and stably play a role in heat conduction, and the graphene contains multiple reaction sites, which can promote the formation of network cross-linking structure between the composite polymer resin and improve the heat conduction and heat dissipation effect of the graphene; on the other hand, the benzene ring structure is introduced on the surface of graphene, which is rigid and not only anchors the graphene, but also helps to improve the mechanical properties of the coating.

[0011] 3. The modified leveling agent of the present application uses butyl acrylate and 1-hydroxyethyl ethoxy piperazine to modify low-hydrogen silicone oil, on the one hand, the modified leveling agent can better compatibilize with the coating, making the leveling effect better, preventing the occurrence of defects such as shrinkage, orange peel, pinholes, etc. in the paint film, and promoting the formation of a flat, smooth and uniform coating film during the drying and film-forming process. On the other hand, the introduction of ester groups and piperazine groups in the leveling agent increases the hydrophobicity and heat resistance of the coating.

[0012] 4. The surface-modified composite carbon nanotube / graphitized solid carbon sphere of the present application has many active functional groups and loads composite metal sources, which enhances its dispersibility and compatibility in the coating, and improves the heat dissipation and antibacterial properties of the coating.

[0013] In some embodiments, the composite polymer resin is composed of fluorine-containing acrylate resin, epoxy resin and silicone resin, and the mass ratio of the three is 1:(1-2):(2-4).

[0014] In some embodiments, the method for preparing the modified graphene comprises the following steps:

[0015] S1. Mix 3,5-dichloro-4-hydroxybenzoic acid, dimethyl sulfoxide and methanol, heat to 35-45℃ and stir to obtain a mixed solution;

[0016] S2. Ultrasonically disperse the graphene oxide in methanol to form a suspension, then add the mixed solution in step S1, and raise the temperature to 90-100℃, and reflux for 18-24h;

[0017] S3. After the reaction in step S2 is completed, hot-filtrate, rinse for 5-8min under ultrasonic action, filter, and then wash with methanol for 3-4 times, and vacuum dry to obtain the modified graphene.

[0018] In some embodiments, the ratio of the amount of 3,5-dichloro-4-hydroxybenzoic acid, dimethyl sulfoxide and methanol in step S1 is 1g:(8-20)ml:(20-60)ml.

[0019] Specifically, the ratio of the amount of graphene oxide, methanol and mixed solution in step S2 is 0.5g:(80-180)ml:(25-60)ml.

[0020] In some embodiments, the method for preparing the surface-modified composite carbon nanotube / graphitized solid carbon sphere comprises the following steps:

[0021] I. Activate the composite carbon nanotube / graphitized solid carbon sphere with a composite acid to obtain an activated product;

[0022] II. Add the modified solution, the activated product in step I and deionized water into a reaction kettle, ultrasonically disperse, filter, and obtain an intermediate product;

[0023] III. Select fresh hawthorn, filter and separate the filtrate after juicing to remove the filter residue, mix the intermediate product in step II and the filtrate, and then load into a fermentation tank for fermentation, centrifugal separation, washing and drying to obtain a composite material;

[0024] IV. Mix the composite material in step III, a composite metal source and deionized water, transfer to an ultraviolet photocatalytic reactor to simulate solar radiation, centrifugal separation, washing and drying to obtain the surface-modified composite carbon nanotube / graphitized solid carbon sphere.

[0025] In some embodiments, the modifying solution in step two is polyvinylpyrrolidone and tetrabutylammonium bromide, with a mass ratio of (2-3) : 1.

[0026] Preferably, the mass ratio of the modifying solution, the activated product in step one and deionized water is 1 : (0.5-1.2) : (50-120).

[0027] In some embodiments, the mass ratio of the intermediate product and filtrate in step three is 1 : (1.5-2.5); the mass ratio of the composite material, the composite metal source and deionized water in step four is 1 : (0.01-0.08) : (10-30).

[0028] In some embodiments, the method for preparing the composite carbon nanotube / graphitized solid carbon sphere comprises the following steps:

[0029] ①sugar, catalyst and deionized water are added to a reaction kettle, ultrasonic treatment is performed to form a uniform solution;

[0030] ②the ethanol solution of phenolic substance and the aqueous solution of aldehyde substance are sequentially added to the uniform solution in step ①, ultrasonic treatment and magnetic stirring are sequentially performed, a first hydrothermal reaction is performed at 80-120℃ for 12-24h to obtain a carbon sphere intermediate;

[0031] ③the carbon sphere intermediate obtained in step ② and graphene oxide are respectively dispersed in water by ultrasonic treatment, then the two are mixed, a reducing agent is added, a second hydrothermal reaction is performed at 200-230℃ for 5-7h to obtain a graphitized solid carbon sphere;

[0032] ④the graphitized solid carbon sphere obtained in step ③ is placed in a crucible and placed in an isothermal zone of a quartz tube furnace, heated to 700-900℃ under an inert gas protection atmosphere, hydrogen is introduced for 15-40min, ethylene is introduced for 10-60min, cooled to room temperature to obtain a composite carbon nanotube / graphitized solid carbon sphere.

[0033] Further specifically, the sugar in step ① is monosaccharide and / or disaccharide; the catalyst is any one or more of iron acetate, nickel nitrate and cobalt acetate; the mass ratio of the catalyst, sugar and deionized water is 1 : (2-10) : (20-100).

[0034] In some embodiments, the method for preparing the modified leveling agent comprises the following steps:

[0035] Ⅰ. low hydrogen-containing silicone oil, butyl acrylate and toluene are added to a reaction kettle, heated to 60-90℃ under an inert gas protection atmosphere, a catalyst is added and stirred for 3-4h to obtain a reaction solution;

[0036] Ⅱ. When the reaction solution is cooled to 40-50℃, 1-hydroxyethyl ethoxy piperazine is added dropwise, and the reaction is stirred for 2-3h, and then distilled under reduced pressure to obtain the modified leveling agent.

[0037] Specifically, the catalyst is chloroplatinic acid or a chloroplatinic acid complex.

[0038] In some embodiments, the molar ratio of the butyl acrylate and 1-hydroxyethyl ethoxy piperazine is 1:(1.05-1.2).

[0039] In some embodiments, the heat-conducting metal powder is any one or more of silver powder, copper powder, and aluminum powder, and the particle size is 1-20μm.

[0040] In some embodiments, the dispersant is a commonly used high molecular dispersant; specifically, the dispersant is a polyurethane dispersant and / or a polyacrylate dispersant; the silane coupling agent is any one or more of KH-550, KH-560, and KH-570; the defoaming agent is an organic silicon-based defoaming agent; and the solvent is any one or more of ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0041] Another aspect of the present application provides a preparation method of a multi-element resin-based high-performance heat dissipation coating, comprising the following steps:

[0042] (1) mixing a composite polymer resin, modified graphene, surface-modified composite carbon nanotube / graphitized solid carbon sphere, silane coupling agent, heat-conducting metal powder, zirconium oxide, lanthanum oxide, boron nitride, modified leveling agent, dispersant, defoaming agent, and part of the solvent, and stirring to obtain a mixture;

[0043] (2) grinding and dispersing the mixture of step (1) to prepare a heat dissipation slurry;

[0044] (3) adding the defoaming agent and the remaining part of the solvent to the heat dissipation slurry of step (2), and mixing uniformly to prepare the heat dissipation coating.

[0045] Compared with the prior art, the present application has the following advantages:

[0046] 1. The composite polymer resin of the present application is composed of fluorine-containing acrylate resin, epoxy resin, and silicone resin. The fluorine-containing acrylate resin has strong hydrophobicity on the surface, which can play a role in preventing pollution and maintaining cleanliness; the epoxy resin has high heat resistance and heat conductivity, which can effectively conduct heat; the silicone resin has strong hydrophobicity, and the high heat conductivity of silicon element also endows the silicone resin with good heat dissipation performance. The applicant controls the specific mass ratio among the three to improve the heat dissipation, hydrophobicity, and dust resistance of the coating.

[0047] 2. The modified graphene of the present application introduces carboxyl and hydroxyl groups on the surface, which can react with epoxy resin and fluorine-containing acrylic ester resin, thereby improving the interaction between graphene oxide and the film-forming matrix and the heat conduction and heat dissipation effect of graphene; on the other hand, the introduction of benzene ring structure on the surface of graphene can assist in improving the mechanical properties of the coating.

[0048] 3. The modified leveling agent of the present application is more compatible with the coating, thereby achieving better leveling effect; in addition, the introduction of ester groups and piperazine groups in the leveling agent increases the hydrophobicity and heat resistance of the coating.

[0049] 4. The surface-modified composite carbon nanotube / graphitized solid carbon sphere of the present application has many active functional groups on the surface and is loaded with a composite metal source, thereby enhancing the dispersibility and compatibility in the coating and improving the heat dissipation and antibacterial properties of the coating.

[0050] 5. The coating of the present application prolongs the service life of the material, reduces the maintenance cost, and saves electricity consumption through nano heat dissipation during use, thereby achieving energy-saving and environmental protection performance. DETAILED DESCRIPTION

[0051] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples are only used to illustrate the present application, but not to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the spirit or scope of the present application.

[0052] According to the ratio of each raw material and the preparation method specified in the following examples and comparative examples, each heat dissipation coating was prepared.

[0053] In order to facilitate the implementation of the present application by those skilled in the art, the manufacturers of some raw materials in the examples and comparative examples are described as follows:

[0054] Fluorine-containing acrylic ester resin: purchased from Hubei Comdi Chemical Co., Ltd.;

[0055] Silicone resin: purchased from Langfang Wanteng Anti-corrosion Material Co., Ltd.;

[0056] Epoxy resin: purchased from Shanghai Yantitan E-commerce Co., Ltd., model EP137;

[0057] Polyurethane dispersant: purchased from Dongguan Hongrui Chemical Co., Ltd., model 4138;

[0058] Silicone defoaming agent: purchased from Shandong Qimin Chemical Technology Co., Ltd., model BYK-310;

[0059] Polyvinylpyrrolidone: purchased from Jinan Pengduo Business and Trade Co., Ltd., model 30;

[0060] Low hydrogen silicone oil: purchased from Shenzhen Xinyongsheng New Material Co., Ltd.

[0061] Other raw materials are not specially mentioned, which can be purchased from the market.

[0062] Preparation Example 1

[0063] The preparation method of the surface modified composite carbon nanotube / graphitized solid carbon sphere comprises the following steps:

[0064] I. 2g of the composite carbon nanotube / graphitized solid carbon sphere A is added into a mixed solution of 25ml of concentrated nitric acid and 10ml of concentrated sulfuric acid, and stirred at 70°C for 5h, and 15ml of 4mol / l dilute hydrochloric acid and 15ml of 25wt% ammonia water are added to remove impurities, and then washed with deionized water until neutral, and dried at 105°C for 12h to obtain an activated product;

[0065] II. 2g of 1.4g of polyvinylpyrrolidone, 0.6g of tetrabutylammonium bromide, 1.6g of the activated product in step I, and 160g of deionized water are added into a reaction kettle, ultrasonic dispersion is carried out for 20min, and then filtration is carried out to obtain an intermediate product;

[0066] III. Fresh hawthorn is selected, filtered and separated after juicing to remove filter residue, and a filtrate is obtained, 25g of the intermediate product in step II and 50g of the filtrate are mixed and then loaded into a fermentation tank, open tank mouth fermentation is carried out, the fermentation temperature is 26°C, the fermentation time is 13d, centrifugal separation is carried out, washed with deionized water for 3 times, and dried at 60°C for 6h to obtain a composite material;

[0067] IV. 60g of the composite material in step III, 0.9g of silver nitrate, 1.8g of copper chloride dihydrate and 1200ml of deionized water are mixed, transferred into an ultraviolet light catalytic reactor to simulate solar radiation, and then transferred into a horizontal centrifuge to carry out centrifugal treatment at a speed of 5000r / min for 10min, and then separated to obtain a lower layer precipitate, washed with deionized water for 3 times, and dried at 105°C for 12h to obtain the surface modified composite carbon nanotube / graphitized solid carbon sphere.

[0068] The preparation of the composite carbon nanotube / graphitized solid carbon sphere comprises the following steps:

[0069] ① 14g of sucrose, 3.5g of cobalt acetate and 140ml of deionized water are added into a polytetrafluoroethylene reaction kettle, ultrasonic treatment is carried out for 15min to form a uniform solution;

[0070] ② In the homogeneous solution of step ①, 10 ml of an ethanol solution of hydroquinone (containing 1.44 g of hydroquinone), 2.12 g of a formaldehyde aqueous solution (the mass fraction of formaldehyde is 37 wt%), were sequentially added, ultrasonic treatment was performed for 2 h, magnetic stirring was performed for 8 h, hydrothermal reaction was performed at 100℃ for 20 h, solid-liquid separation was performed, the solid powder was air-dried in a fume hood to obtain a carbon sphere intermediate;

[0071] ③ 2 g of the carbon sphere intermediate obtained in step ② and 0.2 g of graphene oxide were respectively dispersed in 80 ml of water by ultrasonic treatment for 3 h, then the two were mixed and uniformly stirred, 10 g of boric acid was added, hydrothermal reaction was performed at 220℃ for 6 h, washing was sequentially performed with 1 mol / L dilute hydrochloric acid, anhydrous ethanol and deionized water, the washing was repeated twice, filtration and drying were performed to obtain graphitized solid carbon spheres;

[0072] ④ The graphitized solid carbon spheres obtained in step ③ were placed in a crucible and placed in the isothermal zone of a quartz tube furnace, heated to 800℃ under an argon protective atmosphere, hydrogen was introduced for 25 min, and ethylene was introduced for 140 min, and then cooled to room temperature to obtain composite carbon nanotubes / graphitized solid carbon spheres.

[0073] Preparation Example 2

[0074] The preparation method of the modified graphene A comprises the following steps:

[0075] S1. 1 mol of 3,5-dichloro-4-hydroxybenzoic acid, 14 mol of dimethyl sulfoxide and 50 mol of methanol were mixed, heated to 40℃ and stirred for 30 min to obtain a mixed solution;

[0076] S2. 1 ml of graphene oxide was ultrasonically dispersed in 80 ml of methanol to form a suspension, and then the mixed solution in step S1 was added, the temperature was raised to 90℃, and reflux reaction was performed for 20 h to obtain a reaction product;

[0077] S3. After the reaction in step S2 was completed, hot suction filtration was performed, rinsing was performed for 6 min under ultrasonic action, filtration was performed, rinsing with methanol was performed 4 times, and vacuum drying was performed at 65℃ for 6 h to obtain the modified graphene A.

[0078] Preparation Example 3

[0079] The preparation method of the modified graphene B is the same as that in Preparation Example 1, except that step S1: 1 mol of 3,5-dichloro-4-hydroxybenzoic acid, 20 mol of dimethyl sulfoxide and 20 mol of methanol were mixed to obtain a mixed solution.

[0080] Preparation Example 4

[0081] The preparation method of the modified leveling agent A comprises the following steps:

[0082] I. 10 g low hydrogen-containing silicone oil, 0.55 mol of butyl acrylate and 100 ml of toluene were added into a reaction kettle, heated to 80℃ under nitrogen atmosphere, 0.2 mmol of chloroplatinic acid was added, stirred for 3 h to obtain a reaction solution;

[0083] II. When the reaction solution was cooled to 45℃, 0.6 mol of 1-hydroxyethyl ethoxy piperazine was added dropwise, stirred for 3 h, and distilled under reduced pressure to obtain modified leveling agent A.

[0084] Preparation Example 5

[0085] The preparation steps of modified leveling agent B are the same as those of Preparation Example 3, except that 2 g of low hydrogen-containing silicone oil, 0.5 mol of butyl acrylate and 0.5 mol of 1-hydroxyethyl ethoxy piperazine are added.

[0086] Example 1

[0087] A kind of multi-resin-based high-performance heat dissipation coating, comprising the following raw materials by weight: fluorine-containing acrylate resin 10 parts, epoxy resin 15 parts, silicone resin 25 parts, modified graphene A 20 parts, surface modified composite carbon nanotube / graphitized solid carbon sphere 8.5 parts, silane coupling agent KH-570 3.5 parts, silver powder 0.8 parts, zirconium oxide 1.5 parts, lanthanum oxide 1.5 parts, boron nitride 1.5 parts, modified leveling agent A 2 parts, polyurethane dispersant 2 parts, silicone defoaming agent 1.2 parts and ethyl acetate 70 parts.

[0088] The preparation method of the multi-resin-based high-performance heat dissipation coating of the present embodiment comprises the following preparation steps:

[0089] (1) Mix fluorine-containing acrylate resin, epoxy resin, silicone resin, modified graphene A, surface modified composite carbon nanotube / graphitized solid carbon sphere, silane coupling agent KH-570, silver powder, zirconium oxide, lanthanum oxide, boron nitride, modified leveling agent A, polyurethane dispersant, silicone defoaming agent and part of ethyl acetate (70 wt% of the total amount) at a stirring speed of 800 r / min to obtain a mixture;

[0090] (2) Grind and disperse the mixture of step (1) to prepare a heat dissipation slurry;

[0091] (3) Add silicone defoaming agent and the remaining part of ethyl acetate (30 wt% of the total amount) to the heat dissipation slurry of step (2) and mix uniformly to prepare the heat dissipation coating.

[0092] Example 2

[0093] A multi-element resin-based high-performance heat dissipation coating, comprising the following raw materials in parts by weight: fluorine-containing acrylic ester resin 10 parts, epoxy resin 10 parts, silicone resin 20 parts, modified graphene A 15 parts, surface-modified composite carbon nanotube / graphitized solid carbon sphere 5 parts, silane coupling agent KH-570 2 parts, silver powder 0.5 parts, zirconium oxide 1 part, lanthanum oxide 1 part, boron nitride 1 part, modified leveling agent A 1 part, polyurethane dispersant 1 part, silicone defoaming agent 0.5 parts, and ethyl acetate 60 parts.

[0094] The preparation method of the multi-element resin-based high-performance heat dissipation coating of the present embodiment is the same as that of Embodiment 1.

[0095] Example 3

[0096] A multi-element resin-based high-performance heat dissipation coating, comprising the following raw materials in parts by weight: fluorine-containing acrylic ester resin 8.5 parts, epoxy resin 17 parts, silicone resin 34 parts, modified graphene A 25 parts, surface-modified composite carbon nanotube / graphitized solid carbon sphere 12 parts, silane coupling agent 5 parts, silver powder 1 part, zirconium oxide 2 parts, lanthanum oxide 2 parts, boron nitride 2 parts, modified leveling agent A 3 parts, polyurethane dispersant 3 parts, silicone defoaming agent 2 parts, and ethyl acetate 80 parts.

[0097] The preparation method of the multi-element resin-based high-performance heat dissipation coating of the present embodiment is the same as that of Embodiment 1.

[0098] Example 4

[0099] A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, the specific implementation manner of which is the same as that of Embodiment 1, except that the fluorine-containing acrylic ester resin is 10 parts, the epoxy resin is 15 parts, and the silicone resin is 25 parts.

[0100] Example 5

[0101] A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, the specific implementation manner of which is the same as that of Embodiment 1, except that an equal amount of modified graphene B is used to replace the modified graphene A.

[0102] Example 6

[0103] A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, the specific implementation manner of which is the same as that of Embodiment 1, except that an equal amount of modified leveling agent B is used to replace the modified leveling agent A.

[0104] Comparative Example 1

[0105] A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, the specific implementation manner of which is the same as that of Embodiment 1, except that an equal amount of graphene oxide is used to replace the modified graphene A.

[0106] Comparative Example 2

[0107] A multi-element resin-based high-performance heat dissipation coating and a preparation method thereof, the specific implementation method is the same as example 1, the difference is that an equal amount of commercially available BYK-310 leveling agent is used to replace the modified leveling agent A.

[0108] Effect evaluation:

[0109] The heat dissipation coatings prepared in examples 1-6 and comparative examples 1-2 are tested and analyzed, and the specific results are shown in table 1.

[0110] Performance test:

[0111] (1) Hydrophobicity test:

[0112] A water droplet of 0.02-0.04 ml is used to test the contact angle of the water droplet on the surface of the coating using a contact angle tester.

[0113] (2) Heat dissipation test:

[0114] The prepared heat dissipation coating is coated on a heat sink with a coating thickness of 30 μm. Under the same standard conditions of the same type of heat source and the same heat source input power (20 W), each heat sink sample is heated, and the temperature of each heat sink sample is detected in real time by an Agilent temperature recorder.

[0115] Table 1

[0116] No. Contact angle / ° Temperature of heat source after reaching thermal equilibrium / °C Example 1 102 62 Example 2 101 66 Example 3 105 60 Example 4 95 72 Example 5 98 74 Example 6 96 72 Comparative Example 1 94 78 Comparative Example 2 93 76

[0117] As can be seen from the results in table 1, the heat dissipation coatings of examples 1-3 have good heat dissipation and hydrophobicity.

[0118] Example 4 changes the mass ratio of fluorine-containing acrylate resin, epoxy resin and silicone resin, so that the synergistic effect between the resins is lost, and the hydrophobicity and heat dissipation of the coating are reduced. Example 5 uses an equal amount of modified graphene B to replace modified graphene A, and comparative example 1 uses an equal amount of graphene oxide to replace modified graphene A, so that the functional groups on the surface of graphene are reduced, affecting the dispersibility of graphene, and thus reducing the thermal conductivity of the coating. Example 6 uses an equal amount of modified leveling agent B to replace modified leveling agent A, and comparative example 2 uses an equal amount of commercially available BYK-310 leveling agent to replace modified leveling agent A, so that the leveling of the coating is poor, and the hydrophobicity and heat resistance of the coating are affected.

[0119] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical scheme of the present application, can make some changes or modifications to the disclosed technical content, which are equivalent to equivalent embodiments. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, without departing from the technical scheme content of the present application, are still within the scope of the technical scheme.

Claims

1. A multi-component resin-based high-performance heat dissipation coating, characterized in that, By weight, it contains the following raw materials: 40-60 parts of composite polymer resin, 15-25 parts of modified graphene, 5-12 parts of surface-modified composite carbon nanotubes / graphitized solid carbon spheres, 2-5 parts of silane coupling agent, 0.5-1 part of thermally conductive metal powder, 1-2 parts of zirconium oxide, 1-2 parts of lanthanum oxide, 1-2 parts of boron nitride, 1-3 parts of modified leveling agent, 1-3 parts of dispersant, 0.5-2 parts of defoamer, and 60-80 parts of solvent; The composite polymer resin is composed of fluorinated acrylate resin, epoxy resin and organosilicon resin, and the mass ratio of the three is 1:(1-2):(2-4). The method for preparing the modified graphene includes the following steps: S1. Mix 3,5-dichloro-4-hydroxybenzoic acid, dimethyl sulfoxide and methanol, heat to 35-45℃ and stir to obtain a mixed solution; S2. Graphene oxide is ultrasonically dispersed in methanol to form a suspension, and then the mixed solution from step S1 is added. The temperature is raised to 90-100℃ and refluxed for 18-24 hours. S3. After the reaction in step S2 is completed, filter while hot, rinse under ultrasonication for 5-8 minutes, filter again, wash with methanol 3-4 times, and vacuum dry to obtain modified graphene. The preparation method of the modified leveling agent includes the following steps: I. Add low-hydrogen silicone oil, butyl acrylate and toluene to a reaction vessel, heat to 60-90℃ under an inert gas protective atmosphere, add catalyst and stir for 3-4 hours to obtain a reaction solution; II. When the reaction solution is cooled to 40-50℃, add 1-hydroxyethylethoxypiperazine dropwise, stir the reaction for 2-3 hours, and then distill under reduced pressure to obtain the modified leveling agent.

2. The multi-component resin-based high-performance heat dissipation coating according to claim 1, characterized in that, The ratio of 3,5-dichloro-4-hydroxybenzoic acid, dimethyl sulfoxide and methanol used in step S1 is 1g: (8-20)ml: (20-60)ml.

3. The multi-component resin-based high-performance heat dissipation coating according to claim 1, characterized in that, The preparation method of the surface-modified composite carbon nanotube / graphitized solid carbon spheres includes the following steps:

1. Activate the composite carbon nanotubes / graphitized solid carbon spheres with a composite acid to obtain the activated product; 2. Add the modified solution, the activation product from step 1, and deionized water to the reaction vessel, disperse by ultrasonication, filter, and obtain the intermediate product; 3. Select fresh hawthorn, juice it, filter it to remove the residue, and obtain the filtrate. Mix the intermediate product from step 2 with the filtrate and put it into a fermentation tank for fermentation. After centrifugation, washing and drying, the composite material is obtained. Fourth, the composite material, composite metal source and deionized water from step three are mixed and transferred to an ultraviolet photocatalytic reactor to simulate solar radiation. After centrifugation, washing and drying, the surface-modified composite carbon nanotubes / graphitized solid carbon spheres are obtained.

4. The multi-component resin-based high-performance heat dissipation coating according to claim 3, characterized in that, The modified solution in step two is polyvinylpyrrolidone and tetrabutylammonium bromide, with a mass ratio of (2-3):

1.

5. The multi-component resin-based high-performance heat dissipation coating according to claim 1, characterized in that, The molar ratio of butyl acrylate to 1-hydroxyethyl ethoxypiperazine is 1:(1.05-1.2).

6. The multi-component resin-based high-performance heat dissipation coating according to claim 1, characterized in that, The thermally conductive metal powder is any one or more of silver powder, copper powder, and aluminum powder, and the particle size is 1-20μm.

7. A method for preparing a multi-component resin-based high-performance heat dissipation coating according to any one of claims 1-6, characterized in that, Includes the following steps: (1) The composite polymer resin, modified graphene, surface-modified composite carbon nanotubes / graphitized solid carbon spheres, silane coupling agent, thermally conductive metal powder, zirconium oxide, lanthanum oxide, boron nitride, modified leveling agent, dispersant, defoamer and part of solvent are mixed and stirred to obtain a mixture. (2) Grind and disperse the mixture from step (1) to obtain a heat dissipation slurry; (3) Add defoamer and the remaining solvent to the heat dissipation slurry in step (2), mix evenly, and obtain the heat dissipation coating.