A nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating, preparation method and application

Abstract

The present invention relates to the field of powder coatings, and particularly to a nano high thermal conductivity aluminum substitute for copper heat dissipation tube powder coating, its preparation method and application, which solves the problem that the existing aluminum substitute for copper heat dissipation tube powder coating has insufficient corrosion resistance and seriously affects the thermal conductivity of the aluminum substitute for copper heat dissipation tube; the powder coating uses graphene oxide modified polyester resin as the main raw material, endowing it with excellent adhesion performance, corrosion resistance and thermal conductivity, which can ensure that a firm coating is formed on the surface of the aluminum substitute for copper heat dissipation tube, and can effectively resist the erosion of environmental factors, protect the heat dissipation tube from damage, and at the same time can effectively conduct the heat of the heat dissipation tube out, improving the heat dissipation efficiency. Adding modified thermal conductive fillers to it can further enhance the thermal conductivity of the coating, thereby improving the heat dissipation performance of the aluminum substitute for copper heat dissipation tube; moreover, the preparation method has a simple process, is easy to industrialize, and has good market application prospects.

Description

Technical Field

[0001] The present invention relates to the field of powder coatings, and particularly to a nano high thermal conductivity aluminum replacing copper heat dissipation tube powder coating and its preparation method and application. Background Art

[0002] In fields such as electronic devices and power systems, heat dissipation tubes play a crucial role. They can timely dissipate the heat generated by the devices to ensure the normal operation of the devices. Traditional heat dissipation tubes mostly use copper materials because copper has good thermal conductivity. However, the cost of copper is relatively high, and the resources are relatively scarce, which to a certain extent limits its wide application.

[0003] The technology of aluminum replacing copper has become an important trend due to the advantages of aluminum's light weight, low cost, and resource sustainability. However, the thermal conductivity of aluminum is relatively poor compared to copper (the thermal conductivity of aluminum is about 237 W / (m·K), and the thermal conductivity of copper is about 401 W / (m·K)), and its surface is prone to oxidation and has insufficient corrosion resistance. Currently, most aluminum tubes are not coated for anti-corrosion treatment, resulting in easy corrosion and failure. Although conventional coatings can provide certain protection, they will reduce the thermal conductivity of the aluminum tube and thus significantly reduce the heat dissipation efficiency. Therefore, it is of great practical significance to develop a nano high thermal conductivity aluminum replacing copper heat dissipation tube powder coating with both high thermal conductivity and corrosion resistance, as well as its preparation method and application. Summary of the Invention

[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide a nano high thermal conductivity aluminum replacing copper heat dissipation tube powder coating and its preparation method and application, which solves the problems of insufficient corrosion resistance of the existing aluminum replacing copper heat dissipation tube powder coating and seriously affecting the thermal conductivity of the aluminum replacing copper heat dissipation tube.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A nano high thermal conductivity aluminum replacing copper heat dissipation tube powder coating, comprising the following components in parts by weight:

[0007] 100 - 200 parts of graphene oxide modified polyester resin, 10 - 30 parts of triglycidyl isocyanurate, 5 - 30 parts of modified thermal conductive filler, 10 - 30 parts of modified pearlescent pigment, 6 - 9 parts of leveling agent, 3 - 5 parts of benzoin, and 1 - 3 parts of anti-hydrolysis agent;

[0008] Among them, the graphene oxide modified polyester resin is prepared by the following steps:

[0009] Step a1: Add concentrated sulfuric acid, graphite powder, and sodium nitrate into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 - 30 min under the conditions of a temperature of 0 - 3°C and a stirring rate of 200 - 300 r / min. Then add potassium permanganate and continue to stir and react for 1 - 2 h under the condition of heating to 8 - 10°C. Then continue to stir and react for 1 - 2 h under the condition of heating to 40 - 45°C. Then add deionized water and continue to stir and react for 1 - 2 h under the condition of heating to 95 - 100°C. Then add hydrogen peroxide and continue to stir and react for 20 - 30 min. After the reaction is completed, cool the reaction product to room temperature. Then perform ultrasonic treatment for 30 - 50 min under the condition of an ultrasonic power of 300 - 350 W. Then centrifuge, wash the precipitate with distilled water 3 - 5 times. Then place it in a vacuum drying oven and dry it for 3 - 5 h under the condition of a temperature of 60 - 65°C to obtain graphene oxide powder;

[0010] Step a2: Add graphene oxide powder and absolute ethanol into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Perform ultrasonic treatment for 20 - 40 min under the condition of an ultrasonic power of 300 - 350 W. Then adjust the pH to 3 - 4 with a hydrochloric acid solution. Then stir and react for 10 - 15 min under the conditions of a temperature of 20 - 25°C and a stirring rate of 200 - 300 r / min. Then heat to 60 - 65°C and gradually add silane coupling agent KH-560 dropwise while stirring, controlling the dropping rate to be 1 - 2 drops / s. After the dropping is completed, continue to stir and react for 8 - 10 h. After the reaction is completed, cool the reaction product to room temperature. Then centrifuge, wash the precipitate with distilled water 3 - 5 times. Then place it in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 60 - 65°C to obtain modified graphene oxide powder;

[0011] Step a3: Add hexafluoroisopropanol, 2,2 - bis(bromomethyl)-1,3 - propanediol, triethylamine, and chloroform into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Pass in nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 20 - 25°C and a stirring rate of 200 - 300 r / min. Then continue to stir and react for 6 - 8 h under the condition of heating to 100 - 110°C. After the reaction is completed, cool the reaction product to room temperature. Then rotate and evaporate to remove the solvent. Then wash it with absolute ethanol 3 - 5 times. Then place it in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 60 - 65°C to obtain polyfluorodiol;

[0012] Step a4: Add the polyol containing polyfluorodiol, polybasic acid, catalyst, and water-carrying agent into a three-necked flask equipped with a stirrer, thermometer, and gas pipe. Introduce nitrogen for protection. Stir and react at a temperature of 130 - 140 °C and a stirring rate of 200 - 300 r / min for 20 - 30 min. Then, raise the temperature to 170 - 180 °C and continue stirring and reacting for 2 - 3 h. Then, raise the temperature to 220 - 240 °C and continue stirring and reacting for 3 - 5 h. Then, lower the temperature to 170 - 180 °C, add modified graphene oxide powder and acid decomposer, and continue stirring and reacting for 20 - 30 min. Then, raise the temperature to 210 - 220 °C and continue stirring and reacting for 2 - 3 h. After the reaction ends, cool the reaction product to room temperature, and then place it in a vacuum drying oven and dry it at a temperature of 60 - 65 °C for 4 - 5 h to obtain graphene oxide modified polyester resin.

[0013] As a further solution of the present invention: The dosage ratio of the concentrated sulfuric acid, graphite powder, sodium nitrate, potassium permanganate, deionized water, and hydrogen peroxide in step a1 is 25 - 30 mL: 1 g: 0.5 - 0.6 g: 3 - 3.5 g: 80 - 90 mL: 15 - 20 mL.

[0014] As a further solution of the present invention: The mass fraction of the concentrated sulfuric acid in step a1 is 98%, and the mass fraction of the hydrogen peroxide is 30%.

[0015] As a further solution of the present invention: The dosage ratio of the graphene oxide powder, absolute ethanol, and silane coupling agent KH-560 in step a2 is 1 g: 50 - 60 mL: 0.3 - 1.5 g.

[0016] As a further solution of the present invention: The mass fraction of the hydrochloric acid solution in step a2 is 10 - 15%.

[0017] As a further solution of the present invention: The dosage ratio of the hexafluoroisopropanol, dibromoneopentyl glycol, triethylamine, and chloroform in step a3 is 20 mmol: 10 mmol: 25 - 30 mmol: 60 - 70 mL.

[0018] As a further solution of the present invention: The dosage ratio of the polyol containing polyfluorodiol, polybasic acid, catalyst, modified graphene oxide powder, acid decomposer, and water-carrying agent in step a4 is 50 - 60 g: 55 - 65 g: 0.1 - 0.2 g: 0.8 - 2.2 g: 15 - 19 g: 30 - 35 mL.

[0019] As a further solution of the present invention: the polyol containing polyfluorodiol in step a4 is a mixture of neopentyl glycol, polyfluorodiol, trimethylolethane, and 1,4-cyclohexanedimethanol in a dosage ratio of 30 - 40 g : 1 - 9 g : 1 - 5 g : 1.5 - 2.5 g.

[0020] As a further solution of the present invention: the polybasic acid in step a4 is a mixture of terephthalic acid and adipic acid in a dosage ratio of 35 - 45 g : 1 - 5 g.

[0021] As a further solution of the present invention: the catalyst in step a4 is monobutyltin oxide.

[0022] As a further solution of the present invention: the acid decomposing agent in step a4 is isophthalic acid.

[0023] As a further solution of the present invention: the water-carrying agent in step a4 is xylene.

[0024] As a further solution of the present invention: a preparation method of a nano high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating includes the following steps:

[0025] Step 1: Weigh 100 - 200 parts of graphene oxide modified polyester resin, 10 - 30 parts of triglycidyl isocyanurate, 5 - 30 parts of modified thermal conductive filler, 10 - 30 parts of modified pearlescent pigment, 6 - 9 parts of leveling agent, 3 - 5 parts of benzoin, and 1 - 3 parts of anti-hydrolysis agent by weight, and set aside;

[0026] Step 2: Add the graphene oxide modified polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and anti-hydrolysis agent into a mixer and mix evenly. Then, extrude through an extruder, cool, crush, and sieve to obtain the nano high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating.

[0027] As a further solution of the present invention: the modified thermal conductive filler is prepared by the following steps:

[0028] Add the thermal conductive filler, silane coupling agent KH-550, and ethanol solution into a three-necked flask equipped with a stirrer and a thermometer. Stir and react at a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min for 10 - 15 min. Then, raise the temperature to 75 - 80 °C and continue to stir and react for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with distilled water 3 - 5 times, and then place it in a vacuum drying oven and dry at a temperature of 60 - 65 °C for 2 - 3 h to obtain the modified thermal conductive filler.

[0029] As a further solution of the present invention: the dosage ratio of the heat-conducting filler, silane coupling agent KH-550 and ethanol solution is 5 g: 0.5-1.3 g: 50-60 mL.

[0030] As a further solution of the present invention: the heat-conducting filler is a mixture of carbon nanotubes and boron nitride in a mass ratio of 1-2: 10; the model of the carbon nanotubes is Macklin G991390G; the model of the boron nitride is Aladdin B106033; the volume fraction of the ethanol solution is 85-90%.

[0031] As a further solution of the present invention: the modified pearlescent pigment is prepared by the following steps:

[0032] Add the pearlescent pigment, titanate coupling agent NDZ-311W, deionized water and isopropanol into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and stir and react at a temperature of 25-30 °C and a stirring rate of 200-300 r / min for 10-15 min, then heat up to the reflux condition and continue to stir and react for 3-4 h. After the reaction is completed, filter the reaction product while it is hot, then cool it to room temperature, then centrifuge, wash the precipitate with anhydrous ethanol 3-5 times, and then place it in a vacuum drying oven and dry it at a temperature of 60-65 °C for 5-6 h to obtain the modified pearlescent pigment.

[0033] As a further solution of the present invention: the dosage ratio of the pearlescent pigment, titanate coupling agent NDZ-311W, deionized water and isopropanol is 5 g: 0.2-1.2 g: 10-12 mL: 90-100 mL.

[0034] As a further solution of the present invention: the pearlescent pigment is the mica titanium pearlescent pigment of Guangzhou Xuanlang Fine Chemical Co., Ltd., its model is SL8302, the color is gold, and the particle size is 10-60 μm.

[0035] As a further solution of the present invention: the leveling agent is leveling agent GLP588; the hydrolysis-resistant agent is hydrolysis-resistant agent CHINOX P-500.

[0036] As a further solution of the present invention: the application of the nano high heat-conducting aluminum-substituted copper heat dissipation tube powder coating prepared by the preparation method as described in the aluminum-substituted copper heat dissipation tube painting treatment.

[0037] The beneficial effects of the present invention:

[0038] A nano high thermal conductivity aluminum instead of copper heat dissipation tube powder coating, its preparation method and application of the present invention. By adding graphene oxide modified polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin and hydrolysis inhibitor into a mixer and mixing evenly, then melt extruding through an extruder, and then cooling, crushing, pulverizing and sieving to obtain the nano high thermal conductivity aluminum instead of copper heat dissipation tube powder coating; this powder coating uses graphene oxide modified polyester resin as the main raw material, endowing it with excellent adhesion performance, corrosion resistance and thermal conductivity, which can ensure that the powder coating forms a firm coating on the surface of the aluminum instead of copper heat dissipation tube, and can effectively resist the erosion of environmental factors such as ultraviolet rays, oxygen and moisture, protect the heat dissipation tube from damage, and at the same time can effectively conduct the heat of the heat dissipation tube out, improving the heat dissipation efficiency. Then adding a modified thermal conductive filler to it can further enhance the thermal conductivity of the coating, thereby improving the heat dissipation performance of the aluminum instead of copper heat dissipation tube; moreover, the preparation method has a simple process, is easy to industrialize, and has good market application prospects.

[0039] In the process of preparing the nano high thermal conductivity aluminum instead of copper heat dissipation tube powder coating, a graphene oxide modified polyester resin was first prepared. First, graphene oxide powder was prepared from graphite powder, and then the graphene oxide powder was modified with silane coupling agent KH-560, grafted onto the particle surface of the graphene oxide powder to improve its dispersion and avoid its agglomeration. At the same time, a large number of epoxy groups were introduced to obtain modified graphene oxide powder. Then, hexafluoroisopropanol and 2,2-bis(bromomethyl)-1,3-propanediol were reacted, and the hydroxyl group on hexafluoroisopropanol and the bromine atom on 2,2-bis(bromomethyl)-1,3-propanediol reacted to introduce a large number of fluorine atoms to obtain polyfluorodiol. Then, polyols and polyacids containing polyfluorodiol were polymerized to form polyester, and at the same time, the epoxy group on the modified graphene oxide powder and the hydroxyl group on the polyfluorodiol participated in the polymerization reaction to obtain graphene oxide modified polyester resin; the molecular structure of this graphene oxide modified polyester resin contains a large number of fluorine atoms and grafted graphene oxide. The two-dimensional sheet structure of graphene oxide plays a physical barrier role in the polyester resin. After being evenly dispersed inside the polyester resin, it can form a multi-layer barrier layer, significantly improving the corrosion resistance of the polyester resin. At the same time, graphene oxide also has excellent thermal conductivity, which can build an efficient heat conduction network inside the polyester resin to achieve rapid heat transfer. A large number of fluorine atoms can make the surface of the polyester resin have a lower surface energy, making its surface not easily adhered and adsorbed by corrosive substances, further improving the corrosion resistance of the polyester resin.

[0040] In the process of preparing the nano-high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating, a modified thermal conductive filler was also prepared. The thermal conductive filler is a mixture of carbon nanotubes and boron nitride, which can fully fill the thermal conductive network constructed by graphene oxide, realize the enrichment and extension of the thermal conductive network, further improve the thermal conductivity of the powder coating, and after modification, can improve the dispersion of the thermal conductive filler in the powder coating, and utilize the chemical reaction of the functional groups introduced on the surface of the thermal conductive filler, so as to realize the interfacial bonding force of the interaction between the thermal conductive filler and the resin, give full play to the thermal conductivity of the thermal conductive filler, and at the same time enhance the overall performance of the coating.

[0041] In the process of preparing the nano-high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating, a modified pearlescent pigment was also prepared. The modified pearlescent pigment can be evenly dispersed in the powder coating, realize the color uniformity of the powder coating, improve the aesthetics of the powder coating, and expand its market application prospects. Specific embodiments

[0042] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0043] Example 1:

[0044] This embodiment is a preparation method of a nano-high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating, including the following steps:

[0045] Step S1: Add 25 mL of concentrated sulfuric acid with a mass fraction of 98%, 1 g of graphite powder, and 0.5 g of sodium nitrate into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 20 min at a temperature of 0 °C and a stirring rate of 200 r / min, then add 3 g of potassium permanganate and continue to stir and react for 1 h at a temperature of 8 °C, then continue to stir and react for 1 h at a temperature of 40 °C, then add 80 mL of deionized water and continue to stir and react for 1 h at a temperature of 95 °C, then add 15 mL of hydrogen peroxide with a mass fraction of 30% and continue to stir and react for 20 min. After the reaction is completed, cool the reaction product to room temperature, then perform ultrasonic treatment for 30 min under the condition of an ultrasonic power of 300 W, then centrifuge, wash the precipitate with distilled water 3 times, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 60 °C to obtain graphene oxide powder;

[0046] Step S2: Add 1 g of graphene oxide powder and 50 mL of absolute ethanol into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel. Under the condition of an ultrasonic power of 300 W, perform ultrasonic treatment for 20 min. Then, adjust the pH to 3 with a 10% hydrochloric acid solution. After that, carry out a stirring reaction at a temperature of 20 °C and a stirring rate of 200 r / min for 10 min. Then, while stirring, gradually add 0.3 g of silane coupling agent KH-560 dropwise at a temperature of 60 °C, controlling the dropping rate at 1 drop / s. After the dropping is completed, continue the stirring reaction for 8 h. After the reaction ends, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water 3 times, and then place it in a vacuum drying oven and dry it at a temperature of 60 °C for 2 h to obtain modified graphene oxide powder;

[0047] Step S3: Add 20 mmol of hexafluoroisopropanol, 10 mmol of dibromoneopentyl glycol, 25 mmol of triethylamine and 60 mL of chloroform into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe. Pass in nitrogen for protection. Carry out a stirring reaction at a temperature of 20 °C and a stirring rate of 200 r / min for 20 min. Then, continue the stirring reaction at a temperature of 100 °C for 6 h. After the reaction ends, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent, then wash it with absolute ethanol 3 times, and then place it in a vacuum drying oven and dry it at a temperature of 60 °C for 2 h to obtain polyfluorodiol;

[0048] Step S4: Add 50 g of polyol containing polyfluorodiol, 55 g of polybasic acid, 0.1 g of monobutyltin oxide catalyst and 30 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe. Pass in nitrogen for protection. Carry out a stirring reaction at a temperature of 130 °C and a stirring rate of 200 r / min for 20 min. Then, continue the stirring reaction at a temperature of 170 °C for 2 h. Then, continue the stirring reaction at a temperature of 220 °C for 3 h. Then, cool down to 170 °C and add 0.8 g of modified graphene oxide powder and 15 g of isophthalic acid acidolysis agent and continue the stirring reaction for 20 min. Then, continue the stirring reaction at a temperature of 210 °C for 2 h. After the reaction ends, cool the reaction product to room temperature, and then place it in a vacuum drying oven and dry it at a temperature of 60 °C for 4 h to obtain graphene oxide modified polyester resin; the polyol containing polyfluorodiol is composed of neopentyl glycol, polyfluorodiol, trimethylolethane and 1,4-cyclohexanedimethanol in a dosage ratio of 30 g:1 g:1 g:1.5 g; the polybasic acid is composed of terephthalic acid and adipic acid in a dosage ratio of 35 g:1 g;

[0049] Step S5: Add 5 g of thermal conductive filler, which is a mixture of carbon nanotubes of model Macklin G991390 and boron nitride of model Aladdin B106033 in a mass ratio of 1:10, 0.5 g of silane coupling agent KH-550, and 50 mL of ethanol solution with a volume fraction of 85% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 10 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, continue to stir and react for 4 h under the condition of heating to 75°C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate 3 times with distilled water, and then place it in a vacuum drying oven and dry for 2 h under the condition of a temperature of 60°C to obtain the modified thermal conductive filler;

[0050] Step S6: Add 5 g of mica titanium pearlescent pigment of model SL8302, 0.2 g of titanate coupling agent NDZ-311W, 10 mL of deionized water, and 90 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react for 10 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, continue to stir and react for 3 h under the condition of heating to reflux. After the reaction is completed, filter the reaction product while it is hot, then cool it to room temperature, then centrifuge, wash the precipitate 3 times with anhydrous ethanol, and then place it in a vacuum drying oven and dry for 5 h under the condition of a temperature of 60°C to obtain the modified pearlescent pigment;

[0051] Step S7: Weigh 100 parts of graphene oxide modified polyester resin, 10 parts of isocyanuric acid tris(epoxypropyl) ester, 5 parts of modified thermal conductive filler, 10 parts of modified pearlescent pigment, 6 parts of leveling agent, 3 parts of benzoin, and 1 part of anti-hydrolysis agent, and set aside; the leveling agent is leveling agent GLP588; the anti-hydrolysis agent is anti-hydrolysis agent CHINOX P-500;

[0052] Step S8: Add graphene oxide modified polyester resin, isocyanuric acid tris(epoxypropyl) ester, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and anti-hydrolysis agent into a mixer and mix evenly. Then, melt and extrude through an extruder, and then cool, crush, and pulverize and screen to obtain the nano high thermal conductivity aluminum bronze substitute heat dissipation tube powder coating.

[0053] Example 2:

[0054] This example is a preparation method of a nano high thermal conductivity aluminum bronze substitute heat dissipation tube powder coating, including the following steps:

[0055] Step S1: Add 28 mL of concentrated sulfuric acid with a mass fraction of 98%, 1 g of graphite powder, and 0.55 g of sodium nitrate into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 25 min at a temperature of 1 °C and a stirring rate of 250 r / min. Then add 3.2 g of potassium permanganate and continue to stir and react for 1.5 h while heating to 9 °C. Then continue to stir and react for 1.5 h while heating to 42 °C. Then add 85 mL of deionized water and continue to stir and react for 1.5 h while heating to 98 °C. Then add 18 mL of hydrogen peroxide with a mass fraction of 30% and continue to stir and react for 25 min. After the reaction is completed, cool the reaction product to room temperature. Then perform ultrasonic treatment for 40 min under the condition of an ultrasonic power of 330 W. Then centrifuge, wash the precipitate 4 times with distilled water, and then place it in a vacuum drying oven and dry it for 4 h at a temperature of 62 °C to obtain graphene oxide powder;

[0056] Step S2: Add 1 g of graphene oxide powder and 55 mL of absolute ethanol into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Perform ultrasonic treatment for 30 min under the condition of an ultrasonic power of 330 W. Then adjust the pH to 3.5 with a hydrochloric acid solution with a mass fraction of 12%. Then stir and react for 12 min at a temperature of 22 °C and a stirring rate of 250 r / min. Then while heating to 62 °C, gradually add 0.9 g of silane coupling agent KH-560 drop by drop while stirring, control the dropping rate to be 1 drop / s. After the dropping is completed, continue to stir and react for 9 h. After the reaction is completed, cool the reaction product to room temperature. Then centrifuge, wash the precipitate 4 times with distilled water, and then place it in a vacuum drying oven and dry it for 2.5 h at a temperature of 62 °C to obtain modified graphene oxide powder;

[0057] Step S3: Add 20 mmol of hexafluoroisopropanol, 10 mmol of dibromoneopentyl glycol, 28 mmol of triethylamine, and 65 mL of chloroform into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Pass in nitrogen for protection and stir and react for 25 min at a temperature of 22 °C and a stirring rate of 250 r / min. Then continue to stir and react for 7 h while heating to 105 °C. After the reaction is completed, cool the reaction product to room temperature. Then rotate and evaporate to remove the solvent. Then wash 4 times with absolute ethanol. Then place it in a vacuum drying oven and dry it for 2.5 h at a temperature of 62 °C to obtain polyfluorodiol;

[0058] Step S4: Add 55 g of polyol containing polyfluorodiol, 60 g of polybasic acid, 0.15 g of monobutyltin oxide catalyst, and 32 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react at a temperature of 135 °C and a stirring rate of 250 r / min for 25 min. Then, continue to stir and react at a temperature of 175 °C for 2.5 h. Then, continue to stir and react at a temperature of 230 °C for 4 h. Then, cool to 175 °C and add 1.5 g of modified graphene oxide powder and 17 g of isophthalic acid acidolysis agent, and continue to stir and react for 25 min. Then, continue to stir and react at a temperature of 215 °C for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, and then place it in a vacuum drying oven and dry it at a temperature of 62 °C for 4.5 h to obtain graphene oxide-modified polyester resin; the polyol containing polyfluorodiol is composed of neopentyl glycol, polyfluorodiol, trimethylolethane, and 1,4-cyclohexanedimethanol mixed in a dosage ratio of 35 g:5 g:3 g:2 g; the polybasic acid is composed of terephthalic acid and adipic acid mixed in a dosage ratio of 40 g:3 g;

[0059] Step S5: Add 5 g of thermal conductive filler, which is a mixture of carbon nanotubes of model Macklin G991390G and boron nitride of model Aladdin B106033 in a mass ratio of 1.5:10, 0.9 g of silane coupling agent KH-550, and 55 mL of ethanol solution with a volume fraction of 88% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react at a temperature of 28 °C and a stirring rate of 250 r / min for 12 min. Then, continue to stir and react at a temperature of 78 °C for 4.5 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate 4 times with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 62 °C for 2.5 h to obtain modified thermal conductive filler;

[0060] Step S6: Add 5 g of mica titanium pearlescent pigment of model SL8302, 0.7 g of titanate coupling agent NDZ-311W, 11 mL of deionized water, and 95 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react at a temperature of 28 °C and a stirring rate of 250 r / min for 12 min. Then, continue to stir and react under reflux conditions for 3.5 h. After the reaction is completed, filter the reaction product while it is hot, and then cool to room temperature. Then, centrifuge. Wash the precipitate 4 times with absolute ethanol, and then place it in a vacuum drying oven and dry it at a temperature of 62 °C for 5.5 h to obtain modified pearlescent pigment;

[0061] Step S7: Weigh 150 parts of graphene oxide modified polyester resin, 20 parts of triglycidyl isocyanurate, 17 parts of modified thermal conductive filler, 20 parts of modified pearlescent pigment, 8 parts of leveling agent, 4 parts of benzoin, and 2 parts of hydrolysis inhibitor, and set aside; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P-500;

[0062] Step S8: Add the graphene oxide modified polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and hydrolysis inhibitor into a mixer and mix evenly. Then, extrude and melt through an extruder, and then cool, crush, pulverize, and screen to obtain the nano high thermal conductive aluminum alloyed copper heat dissipation tube powder coating.

[0063] Example 3:

[0064] This example is a preparation method of a nano high thermal conductive aluminum alloyed copper heat dissipation tube powder coating, including the following steps:

[0065] Step S1: Add 30 mL of concentrated sulfuric acid with a mass fraction of 98%, 1 g of graphite powder, and 0.6 g of sodium nitrate into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min at a temperature of 3 °C and a stirring rate of 300 r / min. Then, add 3.5 g of potassium permanganate and continue to stir and react for 2 h while heating up to 10 °C. Then, continue to stir and react for 2 h while heating up to 45 °C. Then, add 90 mL of deionized water and continue to stir and react for 2 h while heating up to 100 °C. Then, add 20 mL of hydrogen peroxide solution with a mass fraction of 30% and continue to stir and react for 30 min. After the reaction is completed, cool the reaction product to room temperature. Then, perform ultrasonic treatment for 50 min under an ultrasonic power of 350 W. Then, centrifuge, wash the precipitate with distilled water 5 times, and then place it in a vacuum drying oven and dry for 5 h at a temperature of 65 °C to obtain graphene oxide powder;

[0066] Step S2: Add 1 g of graphene oxide powder and 60 mL of absolute ethanol into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Perform ultrasonic treatment for 40 min under an ultrasonic power of 350 W. Then, adjust the pH to 4 with a hydrochloric acid solution with a mass fraction of 15%. Then, stir and react for 15 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 1.5 g of silane coupling agent KH-560 while heating up to 65 °C, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 10 h. After the reaction is completed, cool the reaction product to room temperature. Then, centrifuge, wash the precipitate with distilled water 5 times, and then place it in a vacuum drying oven and dry for 3 h at a temperature of 65 °C to obtain modified graphene oxide powder;

[0067] Step S3: Add 20 mmol of hexafluoroisopropanol, 10 mmol of dibromoneopentyl glycol, 30 mmol of triethylamine, and 70 mL of chloroform into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 300 r / min. Then, raise the temperature to 110°C and continue to stir and react for 8 h. After the reaction is completed, cool the reaction product to room temperature. Then, remove the solvent by rotary evaporation. Then, wash it 5 times with absolute ethanol. Then, place it in a vacuum drying oven and dry it for 3 h under the condition of a temperature of 65°C to obtain polyfluorodiol;

[0068] Step S4: Add 60 g of polyol containing polyfluorodiol, 65 g of polybasic acid, 0.2 g of monobutyltin oxide catalyst, and 35 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 140°C and a stirring rate of 300 r / min. Then, raise the temperature to 180°C and continue to stir and react for 3 h. Then, raise the temperature to 240°C and continue to stir and react for 5 h. Then, lower the temperature to 180°C and add 2.2 g of modified graphene oxide powder and 19 g of isophthalic acid acidolysis agent and continue to stir and react for 30 min. Then, raise the temperature to 220°C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature. Then, place it in a vacuum drying oven and dry it for 5 h under the condition of a temperature of 65°C to obtain graphene oxide-modified polyester resin; the polyol containing polyfluorodiol is composed of neopentyl glycol, polyfluorodiol, trimethylolethane, and 1,4-cyclohexanedimethanol mixed in a dosage ratio of 40 g: 9 g: 5 g: 2.5 g; the polybasic acid is composed of terephthalic acid and adipic acid mixed in a dosage ratio of 45 g: 5 g;

[0069] Step S5: Add 5 g of thermal conductive filler obtained by mixing carbon nanotubes of model Macklin G991390G and boron nitride of model Aladdin B106033 in a mass ratio of 2:10, 1.3 g of silane coupling agent KH-550, and 60 mL of ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min. Then, raise the temperature to 80°C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature. Then, centrifuge it, wash the precipitate 5 times with distilled water. Then, place it in a vacuum drying oven and dry it for 3 h under the condition of a temperature of 65°C to obtain modified thermal conductive filler;

[0070] Step S6: Add 5 g of mica-titanium pearlescent pigment with model number SL8302, 1.2 g of titanate coupling agent NDZ-311W, 12 mL of deionized water, and 100 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min. Then, raise the temperature to the reflux condition and continue stirring and reacting for 4 h. After the reaction ends, filter the reaction product while it is hot, then cool it to room temperature, and then centrifuge it. Wash the precipitate 5 times with absolute ethanol, and then place it in a vacuum drying oven and dry it for 6 h under the condition of a temperature of 65°C to obtain the modified pearlescent pigment;

[0071] Step S7: Weigh 200 parts of graphene oxide modified polyester resin, 30 parts of isocyanuric acid triglycidyl ester, 30 parts of modified thermal conductive filler, 30 parts of modified pearlescent pigment, 9 parts of leveling agent, 5 parts of benzoin, and 3 parts of hydrolysis inhibitor, and set aside; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P-500;

[0072] Step S8: Add graphene oxide modified polyester resin, isocyanuric acid triglycidyl ester, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and hydrolysis inhibitor into a mixer and mix them evenly. Then, melt and extrude them through an extruder, and then cool, crush, and pulverize and screen them to obtain the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating.

[0073] Comparative Example 1:

[0074] This comparative example is a preparation method of a nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating, including the following steps:

[0075] Step S1: Add 60 g of polyol, 65 g of polybasic acid, 0.2 g of monobutyltin oxide catalyst, and 35 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Pass in nitrogen for protection, and stir and react for 30 min under the conditions of a temperature of 140°C and a stirring rate of 300 r / min. Then, raise the temperature to 180°C and continue stirring and reacting for 3 h. Then, raise the temperature to 240°C and continue stirring and reacting for 5 h. Then, lower the temperature to 180°C and add 19 g of isophthalic acid acidolysis agent and continue stirring and reacting for 30 min. Then, raise the temperature to 220°C and continue stirring and reacting for 3 h. After the reaction ends, cool the reaction product to room temperature, and then place it in a vacuum drying oven and dry it for 5 h under the condition of a temperature of 65°C to obtain the polyester resin; the polyol is composed of neopentyl glycol, trimethylolethane, and 1,4-cyclohexanedimethanol mixed in a dosage ratio of 40 g:5 g:2.5 g; the polybasic acid is composed of terephthalic acid and adipic acid mixed in a dosage ratio of 45 g:5 g;

[0076] Step S2: Weigh 200 parts of polyester resin, 30 parts of triglycidyl isocyanurate, 30 parts of heat-conducting filler, 30 parts of pearlescent pigment, 9 parts of leveling agent, 5 parts of benzoin and 3 parts of hydrolysis inhibitor, and set aside; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P-500; the heat-conducting filler is a mixture of carbon nanotubes of model Macklin G991390G and boron nitride of model Aladdin B106033 in a mass ratio of 2:10; the pearlescent pigment is mica titanium pearlescent pigment of model SL8302;

[0077] Step S3: Add the polyester resin, triglycidyl isocyanurate, heat-conducting filler, pearlescent pigment, leveling agent, benzoin and hydrolysis inhibitor into a mixer and mix evenly, then melt and extrude through an extruder, and then cool, crush, pulverize and screen to obtain a nano high heat-conducting aluminum bronze replacement heat dissipation tube powder coating.

[0078] Comparative Example 2:

[0079] This comparative example is a preparation method of a nano high heat-conducting aluminum bronze replacement heat dissipation tube powder coating, which includes the following steps:

[0080] Step S1: Add 60 g of polyol, 65 g of polybasic acid, 0.2 g of monobutyltin oxide catalyst and 35 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen for protection, and stir and react at a temperature of 140 °C and a stirring rate of 300 r / min for 30 min, then raise the temperature to 180 °C and continue to stir and react for 3 h, then raise the temperature to 240 °C and continue to stir and react for 5 h, then lower the temperature to 180 °C and add 19 g of isophthalic acid hydrolysis agent and continue to stir and react for 30 min, then raise the temperature to 220 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then place it in a vacuum drying oven and dry it at a temperature of 65 °C for 5 h to obtain polyester resin; the polyol is composed of neopentyl glycol, trimethylolethane and 1,4-cyclohexanedimethanol mixed in a dosage ratio of 40 g:5 g:2.5 g; the polybasic acid is composed of terephthalic acid and adipic acid mixed in a dosage ratio of 45 g:5 g;

[0081] Step S2: Add 5 g of thermal conductive filler, which is a mixture of carbon nanotubes of model McLane G991390 and boron nitride of model Aladdin B106033 in a mass ratio of 2:10, 1.3 g of silane coupling agent KH-550, and 60 mL of ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 80 °C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it for 3 h under the condition of a temperature of 65 °C to obtain the modified thermal conductive filler;

[0082] Step S3: Add 5 g of mica titanium pearlescent pigment of model SL8302, 1.2 g of titanate coupling agent NDZ-311W, 12 mL of deionized water, and 100 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to reflux and continue to stir and react for 4 h. After the reaction is completed, filter the reaction product while it is hot, then cool it to room temperature, then centrifuge. Wash the precipitate 5 times with absolute ethanol, and then place it in a vacuum drying oven and dry it for 6 h under the condition of a temperature of 65 °C to obtain the modified pearlescent pigment;

[0083] Step S4: Weigh 200 parts of polyester resin, 30 parts of triglycidyl isocyanurate, 30 parts of modified thermal conductive filler, 30 parts of modified pearlescent pigment, 9 parts of leveling agent, 5 parts of benzoin, and 3 parts of anti-hydrolysis agent by weight for standby; the leveling agent is leveling agent GLP588; the anti-hydrolysis agent is anti-hydrolysis agent CHINOX P-500;

[0084] Step S5: Add the polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and anti-hydrolysis agent into a mixer and mix them evenly. Then, melt and extrude them through an extruder, and then cool, crush, and screen them to obtain the nano high thermal conductivity aluminum bronze substitute heat dissipation tube powder coating.

[0085] Comparative Example 3:

[0086] This comparative example is a preparation method of a nano high thermal conductivity aluminum bronze substitute heat dissipation tube powder coating, which includes the following steps:

[0087] Step S1: Add 20 mmol of hexafluoroisopropanol, 10 mmol of dibromoneopentyl glycol, 30 mmol of triethylamine, and 70 mL of chloroform into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 8 h under the condition of raising the temperature to 110 °C. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash it 5 times with absolute ethanol, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 65 °C to obtain polyfluorodiol;

[0088] Step S2: Add 60 g of polyol containing polyfluorodiol, 65 g of polybasic acid, 0.2 g of monobutyltin oxide catalyst, and 35 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 140 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 3 h under the condition of raising the temperature to 180 °C. Then, continue to stir and react for 5 h under the condition of raising the temperature to 240 °C. Then, cool down to 180 °C and add 19 g of isophthalic acid acidolysis agent and continue to stir and react for 30 min. Then, continue to stir and react for 3 h under the condition of raising the temperature to 220 °C. After the reaction is completed, cool the reaction product to room temperature, then place it in a vacuum drying oven and dry it for 5 h at a temperature of 65 °C to obtain modified polyester resin; The polyol containing polyfluorodiol is composed of neopentyl glycol, polyfluorodiol, trimethylolethane, and 1,4-cyclohexanedimethanol mixed according to a dosage ratio of 40 g: 9 g: 5 g: 2.5 g; The polybasic acid is composed of terephthalic acid and adipic acid mixed according to a dosage ratio of 45 g: 5 g;

[0089] Step S3: Add 5 g of thermally conductive filler obtained by mixing carbon nanotubes of model Macklin G991390 and boron nitride of model Aladdin B106033 according to a mass ratio of 2:10, 1.3 g of silane coupling agent KH-550, and 60 mL of ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 5 h under the condition of raising the temperature to 80 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 65 °C to obtain modified thermally conductive filler;

[0090] Step S4: Add 5 g of mica titania pearlescent pigment with model number SL8302, 1.2 g of titanate coupling agent NDZ-311W, 12 mL of deionized water, and 100 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to the reflux condition and continue to stir and react for 4 h. After the reaction is completed, filter the reaction product while it is hot, then cool it to room temperature, and then centrifuge. Wash the precipitate 5 times with absolute ethanol, and then place it in a vacuum drying oven and dry it at a temperature of 65 °C for 6 h to obtain the modified pearlescent pigment;

[0091] Step S5: Weigh 200 parts of modified polyester resin, 30 parts of triglycidyl isocyanurate, 30 parts of modified thermal conductive filler, 30 parts of modified pearlescent pigment, 9 parts of leveling agent, 5 parts of benzoin, and 3 parts of hydrolysis inhibitor according to weight parts for standby; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P-500;

[0092] Step S6: Add the modified polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and hydrolysis inhibitor into a mixer and mix them evenly. Then, melt and extrude them through an extruder, and then cool, crush, and pulverize and sieve them to obtain the nano high thermal conductive aluminum bronze replacement heat dissipation tube powder coating.

[0093] Comparative Example 4:

[0094] This comparative example is a preparation method of a nano high thermal conductive aluminum bronze replacement heat dissipation tube powder coating, including the following steps:

[0095] Step S1: Add 30 mL of concentrated sulfuric acid with a mass fraction of 98%, 1 g of graphite powder, and 0.6 g of sodium nitrate into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 3 °C and a stirring rate of 300 r / min. Then, add 3.5 g of potassium permanganate and raise the temperature to 10 °C and continue to stir and react for 2 h. Then, raise the temperature to 45 °C and continue to stir and react for 2 h. Then, add 90 mL of deionized water and raise the temperature to 100 °C and continue to stir and react for 2 h. Then, add 20 mL of hydrogen peroxide with a mass fraction of 30% and continue to stir and react for 30 min. After the reaction is completed, cool the reaction product to room temperature, then perform ultrasonic treatment for 50 min under the condition of an ultrasonic power of 350 W, then centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 65 °C for 5 h to obtain graphene oxide powder;

[0096] Step S2: Add 1 g of graphene oxide powder and 60 mL of absolute ethanol into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Ultrasonically treat for 40 min under the condition of an ultrasonic power of 350 W. Then adjust the pH to 4 with a 15% hydrochloric acid solution by mass. After that, stir and react for 15 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then raise the temperature to 65 °C and gradually add 1.5 g of silane coupling agent KH-560 drop by drop while stirring, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 10 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry for 3 h at a temperature of 65 °C to obtain modified graphene oxide powder;

[0097] Step S3: Add 60 g of polyol, 65 g of polyacid, 0.2 g of monobutyltin oxide catalyst, and 35 mL of xylene water-carrying agent into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection and stir and react for 30 min at a temperature of 140 °C and a stirring rate of 300 r / min. Then raise the temperature to 180 °C and continue to stir and react for 3 h. Then raise the temperature to 240 °C and continue to stir and react for 5 h. Then lower the temperature to 180 °C and add 2.2 g of modified graphene oxide powder and 19 g of isophthalic acid hydrolysis agent and continue to stir and react for 30 min. Then raise the temperature to 220 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then place it in a vacuum drying oven and dry for 5 h at a temperature of 65 °C to obtain graphene oxide-modified polyester resin; The polyol is composed of neopentyl glycol, trimethylolethane, and 1,4-cyclohexanedimethanol mixed in a dosage ratio of 40 g:5 g:2.5 g; The polyacid is composed of terephthalic acid and adipic acid mixed in a dosage ratio of 45 g:5 g;

[0098] Step S4: Add 5 g of thermally conductive filler, which is a mixture of carbon nanotubes of model Macklin G991390G and boron nitride of model Aladdin B106033 in a mass ratio of 2:10, 1.3 g of silane coupling agent KH-550, and 60 mL of ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then raise the temperature to 80 °C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate 5 times with distilled water, and then place it in a vacuum drying oven and dry for 3 h at a temperature of 65 °C to obtain modified thermally conductive filler;

[0099] Step S5: Add 5 g of mica-titanium pearlescent pigment with model number SL8302, 1.2 g of titanate coupling agent NDZ-311W, 12 mL of deionized water, and 100 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. Stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min. Then, raise the temperature to reflux and continue stirring and reacting for 4 h. After the reaction is completed, filter the reaction product while it is hot, then cool it to room temperature, and then centrifuge. Wash the precipitate 5 times with absolute ethanol, and then place it in a vacuum drying oven and dry it at a temperature of 65°C for 6 h to obtain the modified pearlescent pigment;

[0100] Step S6: Weigh 200 parts of graphene oxide modified polyester resin, 30 parts of isocyanuric acid triglycidyl ester, 30 parts of modified thermal conductive filler, 30 parts of modified pearlescent pigment, 9 parts of leveling agent, 5 parts of benzoin, and 3 parts of hydrolysis inhibitor according to weight, and set aside; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P-500;

[0101] Step S7: Add graphene oxide modified polyester resin, isocyanuric acid triglycidyl ester, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and hydrolysis inhibitor into a mixer and mix evenly. Then, melt and extrude through an extruder, and then cool, crush, and pulverize and sieve to obtain the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating.

[0102] Spray the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coatings of Examples 1-3 and Comparative Examples 1-4 on the degreased and derusted aluminum plate through an electrostatic spray gun, bake at a temperature of 200°C for 10 min to obtain a coating with a thickness of 80 ± 2 μm, and then conduct performance tests. The test results are shown in the following table:

[0103]

[0104] Referring to the data in the above table, according to the data of Examples 1-3, it can be known that the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating of the present application has excellent thermal conductivity and water and corrosion resistance.

[0105] Among them, according to the comparison between Example 3 and Comparative Example 1, it can be known that the use of polyol containing polyfluorodiol, modified graphene oxide powder, and the modification of thermal conductive filler and pearlescent pigment can significantly improve the thermal conductivity and water and corrosion resistance of the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating;

[0106] Among them, according to the comparison between Comparative Example 1 and Comparative Example 2, it can be known that the modification of thermal conductive filler and pearlescent pigment can significantly improve the thermal conductivity of the nano high thermal conductive aluminum bronze substitute heat dissipation tube powder coating;

[0107] Among them, according to the comparison between Comparative Example 2 and Comparative Example 3, it can be known that the use of polyol containing polyfluorodiol can significantly improve the water resistance and anti-corrosion performance of the nano-high thermal conductivity aluminum substituted copper heat dissipation tube powder coating;

[0108] Among them, according to the comparison between Comparative Example 2 and Comparative Example 4, it can be known that the use of modified graphene oxide powder can significantly improve the thermal conductivity, water resistance and anti-corrosion performance of the nano-high thermal conductivity aluminum substituted copper heat dissipation tube powder coating.

[0109] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0110] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the invention or exceed the scope defined by this application, they should all belong to the protection scope of the present invention.

Claims

1. A nano high thermal conductivity aluminum - substituted copper heat - dissipation tube powder coating, characterized in that, Comprising the following components in parts by weight: 100 - 200 parts of graphene oxide modified polyester resin, 10 - 30 parts of triglycidyl isocyanurate, 5 - 30 parts of modified thermal conductive filler, 10 - 30 parts of modified pearlescent pigment, 6 - 9 parts of leveling agent, 3 - 5 parts of benzoin, and 1 - 3 parts of hydrolysis inhibitor; Among them, the graphene oxide modified polyester resin is prepared by the following steps: Step a1: Stir and react concentrated sulfuric acid, graphite powder, and sodium nitrate, then successively add potassium permanganate, deionized water, and hydrogen peroxide and continue to stir and react. After the reaction ends, cool the reaction product, then perform ultrasonic treatment, then centrifuge, wash and dry the precipitate to obtain graphene oxide powder; Step a2: Perform ultrasonic treatment on the graphene oxide powder and absolute ethanol, then adjust the pH with hydrochloric acid solution, then stir and react, then add silane coupling agent KH - 560 and continue to stir and react. After the reaction ends, cool the reaction product, then centrifuge, wash and dry the precipitate to obtain modified graphene oxide powder; Step a3: Stir and react hexafluoroisopropanol, 2,2 - dibromoneopentyl glycol, triethylamine, and chloroform. After the reaction ends, cool the reaction product, then perform rotary evaporation, then wash and dry to obtain polyfluorodiol; Step a4: Stir and react the polyol containing polyfluorodiol, polybasic acid, catalyst, and water - carrying agent, then add modified graphene oxide powder and acid decomposing agent and continue to stir and react. After the reaction ends, cool the reaction product, then dry to obtain graphene oxide modified polyester resin.

2. The nano high thermal conductivity aluminum-substituted copper heat dissipation tube powder coating according to claim 1, characterized in that, The dosage ratio of the concentrated sulfuric acid, graphite powder, sodium nitrate, potassium permanganate, deionized water, and hydrogen peroxide in step a1 is 25 - 30 mL:1 g:0.5 - 0.6 g:3 - 3.5 g:80 - 90 mL:15 - 20 mL; the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 30%.

3. The nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating according to claim 1, characterized in that The dosage ratio of the graphene oxide powder, absolute ethanol, and silane coupling agent KH - 560 in step a2 is 1 g:50 - 60 mL:0.3 - 1.5 g; the mass fraction of the hydrochloric acid solution is 10 - 15%.

4. The nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating according to claim 1, characterized in that, The dosage ratio of the hexafluoroisopropanol, 2,2 - dibromoneopentyl glycol, triethylamine, and chloroform in step a3 is 20 mmol:10 mmol:25 - 30 mmol:60 - 70 mL.

5. A nano high thermal conductivity aluminum instead of copper heat dissipation tube powder coating according to claim 1, characterized in that The dosage ratio of the polyol containing polyfluorodiol, polybasic acid, catalyst, modified graphene oxide powder, acid decomposing agent, and water - carrying agent in step a4 is 50 - 60 g:55 - 65 g:0.1 - 0.2 g:0.8 - 2.2 g:15 - 19 g:30 - 35 mL; The polyol containing polyfluorodiol is a mixture of neopentyl glycol, polyfluorodiol, trimethylolethane, and 1,4 - cyclohexanedimethanol with a dosage ratio of 30 - 40 g:1 - 9 g:1 - 5 g:1.5 - 2.5 g; The polybasic acid is a mixture of terephthalic acid and adipic acid with a dosage ratio of 35 - 45 g:1 - 5 g; The catalyst is monobutyltin oxide; The acid decomposing agent is isophthalic acid; The water - carrying agent is xylene.

6. A preparation method of a nano high thermal conductivity aluminum - substituted copper heat - dissipation tube powder coating, characterized in that, Including the following steps: Step 1: Weigh 100 - 200 parts of graphene oxide modified polyester resin, 10 - 30 parts of triglycidyl isocyanurate, 5 - 30 parts of modified thermal conductive filler, 10 - 30 parts of modified pearlescent pigment, 6 - 9 parts of leveling agent, 3 - 5 parts of benzoin, and 1 - 3 parts of hydrolysis inhibitor for standby; the leveling agent is leveling agent GLP588; the hydrolysis inhibitor is hydrolysis inhibitor CHINOX P - 500; Step 2: Add graphene oxide modified polyester resin, triglycidyl isocyanurate, modified thermal conductive filler, modified pearlescent pigment, leveling agent, benzoin, and hydrolysis inhibitor into a mixer and mix evenly. Then, extrude through an extruder by melting, and then cool, crush, and screen through a sieve to obtain a nano - high - thermal - conductivity aluminum - substituted copper heat - dissipation tube powder coating.

7. The preparation method of a nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating according to claim 6, characterized in that, The modified thermal conductive filler is prepared by the following steps: Stir and react the thermal conductive filler, silane coupling agent KH - 550, and ethanol solution. After the reaction ends, cool the reaction product, then centrifuge, wash and dry the precipitate to obtain the modified thermal conductive filler; The modified pearlescent pigment is prepared by the following steps: Stir and react the pearlescent pigment, titanate coupling agent NDZ - 311W, deionized water, and isopropanol. After the reaction ends, filter the reaction product while it is hot, then cool, and then centrifuge. Wash and dry the precipitate to obtain the modified pearlescent pigment.

8. The preparation method of a nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating according to claim 7, characterized in that, The dosage ratio of the thermal conductive filler, silane coupling agent KH - 550, and ethanol solution is 5g: 0.5 - 1.3g: 50 - 60mL; the thermal conductive filler is a mixture of carbon nanotubes and boron nitride with a mass ratio of 1 - 2: 10; the volume fraction of the ethanol solution is 85 - 90%.

9. The preparation method of a nano high thermal conductivity aluminum substituted copper heat dissipation tube powder coating according to claim 7, characterized in that, The dosage ratio of the pearlescent pigment, titanate coupling agent NDZ - 311W, deionized water, and isopropanol is 5g: 0.2 - 1.2g: 10 - 12mL: 90 - 100mL.

10. Application of a nano - high - thermal - conductivity aluminum - substituted copper heat - dissipation tube powder coating prepared by the preparation method according to any one of claims 6 - 9 in the coating treatment of an aluminum - substituted copper heat - dissipation tube.

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