Multifunctional coating coated with nanochannels and preparation method and application thereof

Abstract

The application provides a multifunctional coating coated with nanometer microchannels, which comprises the following raw materials by weight: 10-25 parts of silicone modified vinyl resin, 10-15 parts of siloxane containing epoxy groups, 40-45 parts of inorganic filler, 4-10 parts of polyester resin, 5-10 parts of oxide modified graphene, 5-10 parts of alcohol organic solvent and 10-20 parts of deionized water. The multifunctional coating provided by the application is a high-performance heat dissipation coating with strong heat conduction performance and rapid and persistent heat dissipation effect, has strong adhesion with the device substrate, is dust-repellent on the surface and can be effectively dusted by using air ducts.

Description

Technical Field

[0001] This invention belongs to the field of heat dissipation coating preparation, and specifically relates to a multifunctional coating with nano-microchannel coating, its preparation method and application. Background Technology

[0002] Electronic components are generally characterized by their small size, long continuous operating time, and enclosed working environment. However, with the increasing intelligence, miniaturization, and integration of electronic devices, the input power of electronic components is constantly increasing, resulting in very high heat flux density. If the large amount of heat generated by electronic components accumulates inside the equipment and cannot be dissipated in a timely and effective manner, it will lead to problems such as local overheating, decreased operating efficiency, reduced equipment stability, and even equipment failure, shortening service life and increasing operating and maintenance costs. Therefore, how to solve the heat dissipation problem has become a current focus of attention.

[0003] There are three common heat transfer mechanisms: heat conduction, heat convection, and heat radiation. Current common heat dissipation technologies mainly focus on reducing the thermal resistance of electronic components and developing effective secondary heat dissipation mechanisms. However, these methods are limited by cost and effectiveness, and their application is not widespread. Among existing technologies, applying coating technology to the heat dissipation of electronic components has shown excellent results. Coating technology refers to thermally conductive coatings, which are often composite polymer materials applied to the surface of electronic components. By enhancing the surface's thermal conduction and radiation capabilities, heat from the heat source is conducted to the heat sink, and then effectively dissipated through the heat sink, improving the surface's heat dissipation efficiency and achieving the purpose of cooling.

[0004] Invention patent CN 114507465A discloses a method for preparing an organosilicon-modified boron nitride heat dissipation coating, which makes boron nitride less prone to becoming smaller particles under external force. At the same time, the active groups on the modified surface improve the dispersion persistence of boron nitride and its affinity with resin, thereby increasing the thermal conductivity. However, the bonding effect between the active groups obtained by the modification of the boron nitride surface and the encapsulating material is limited. Although it can improve the heat dissipation capacity to a certain extent, the sustained heat dissipation capacity may be insufficient. Invention patent CN 117384515A discloses a method for preparing a high heat dissipation insulating protective coating for dry-type transformers. It chemically links two substrates, siloxane and attapulgite clay and graphene oxide, and works synergistically with fluorine-silicon bonds. The resulting protective coating has wear-resistant, high-temperature resistant, insulating and heat dissipation effects. However, due to the certain mismatch between the inorganic filler and the substrate, the mechanical properties of this protective coating still have room for improvement.

[0005] Therefore, there is an urgent need for a multifunctional coating with strong thermal conductivity, fast and long-lasting heat dissipation effect, and more expected functions such as self-cleaning properties, in order to meet the increasing and higher heat dissipation requirements brought about by the rapid development of electronic components. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a multifunctional coating with nano-microchannel coating. This multifunctional coating has strong adhesion to the substrate of electronic components and can quickly and persistently cool down the heat-generating element. In addition, after the electronic components are coated with the multifunctional coating, they not only have heat dissipation properties but also hydrophobic and dust-repellent properties, and dust can be effectively removed using air ducts.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides a multifunctional coating for nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 10-25 parts of organosilicon-modified vinyl resin, 10-15 parts of epoxy group-containing siloxane, 40-45 parts of inorganic filler, 4-10 parts of polyester resin, 5-10 parts of oxide-modified graphene, 5-10 parts of alcohol organic solvent and 10-20 parts of deionized water.

[0009] Preferably, the mass ratio of the organosilicon to the vinyl resin in the organosilicon-modified vinyl resin is (0.1-2):10.

[0010] Preferably, the preparation steps of the organosilicon-modified vinyl resin are as follows:

[0011] Vinyl resin was added to a 500 mL reactor containing refluxed isopropanol and stirred until homogeneous. The mixture was then slowly heated to 80–90 °C for preheating. Hydrogen-terminated polydimethylsiloxane and catalyst were then added dropwise. The reaction was carried out for 10–30 min. After the addition was complete, the mixture was kept at this temperature for 1–10 h to obtain organosilicon-modified vinyl resin.

[0012] Preferably, the mass ratio of the hydrogen-terminated polydimethylsiloxane to the vinyl resin is (0.1-2):10.

[0013] More preferably, the mass ratio of the hydrogen-terminated polydimethylsiloxane to the vinyl resin is 1.1:10.

[0014] Preferably, the catalyst is a cassiterite catalyst.

[0015] More preferably, the amount of catalyst added is 0.01 to 0.1% of the mass of hydrogen-terminated polydimethylsiloxane.

[0016] Preferably, the siloxane containing epoxy groups is KH560.

[0017] The applicant uses organosilicon-modified vinyl resin as the main film-forming material and adds siloxane containing epoxy groups. Through the alkoxy, hydroxy, and epoxy groups contained therein, a dense dendritic or block copolymer coating can be formed on the substrate surface to improve the insulation performance of the coating. Through effective overlap, a thermally conductive chain is formed in the film-forming material. The chemical linking effect of siloxane in the coupling system ensures that the thermal conductivity of the multifunctional coating is improved in both the length and thickness directions. At the same time, uniform thermal conduction is achieved, which is conducive to heat diffusion and avoids the adverse effects of localized heat conduction on the service life of the coating.

[0018] Preferably, each part of the inorganic filler comprises the following parts by weight of raw materials: 8-15 parts of silicon oxide, 10-30 parts of silicon carbide, 10-15 parts of magnesium oxide, 8-15 parts of zirconium oxide and 1-10 parts of silver powder.

[0019] This invention uses a combination of various inorganic fillers such as silicon oxide, silicon carbide, magnesium oxide, zirconium oxide, and silver powder to regulate and utilize the heat resistance and structural hardness of the thermally conductive particles. When these particles overlap the surface of the thermally conductive chain, they form a heat dissipation system with multi-shaped channels. At the same time, the thermal shock resistance of the heat dissipation coating is effectively improved, giving the coating better mechanical properties and structural stability.

[0020] Preferably, the polyester resin is polymethyl methacrylate.

[0021] Preferably, the oxide-modified graphene is zinc oxide-modified graphene.

[0022] Preferably, the preparation steps of the oxide-modified graphene are as follows:

[0023] Graphene and deionized water were added to a reactor, heated to 70–90°C, stirred, and the pH was adjusted to neutral to obtain the first reactant. Zinc oxide solution was then slowly added dropwise to the first reactant, the pH was adjusted to neutral, and the reaction was carried out for 1–3 hours to obtain the second reactant. The second reactant was filtered, dried, and calcined to obtain oxide-modified graphene.

[0024] Preferably, the graphene has a particle size of 10–50 μm;

[0025] More preferably, the mass ratio of graphene to deionized water is 1:(1.5-4).

[0026] Preferably, the concentration of the zinc oxide solution is 1–3 M;

[0027] More preferably, the mass ratio of the zinc oxide solution to the first reactant is (0.5-1.5):1.

[0028] The applicant modified graphene, a material with high thermal conductivity, by adding metal oxides and found that the heat dissipation performance of the multifunctional coating was significantly improved. The possible reason is that zinc oxide is coated on the graphene surface and grows in situ, forming an effective overlap between the two, which increases the heat conduction channels in the coating, enriches the heat conduction network, and achieves efficient heat dissipation. At the same time, due to the strong surface bonding force between the two and the uniform dispersion with other components of the coating system, the heat dissipation effect of the multifunctional coating is rapid and long-lasting.

[0029] Preferably, the alcoholic organic solvent is isopropanol and / or n-butanol.

[0030] Preferably, the multifunctional coating further comprises rare earth powder;

[0031] Preferably, the rare earth powder is yttrium oxide powder with a particle size of 30-50 nm.

[0032] Preferably, the mass ratio of the rare earth powder to the oxide-modified graphene is (0.5-0.8):1.

[0033] The applicant achieved higher thermal emissivity and thermal conductivity in multifunctional coatings by doping with rare earth powder and adjusting the mass ratio of rare earth powder to oxide-modified graphene. The possible reason is that the oxides grown in situ on the surface of the modified graphene provide some support for the structure of the rare earth powder, maintaining and increasing the heat dissipation area of ​​the rare earth powder. This can help improve the thermal conductivity of the coating with a lower amount of rare earth powder added.

[0034] Another aspect of the present invention provides a method for preparing a multifunctional coating coated with nanochannels, comprising the following steps:

[0035] A first mixture is obtained by mixing epoxy-containing siloxane, inorganic filler, polyester resin, oxide-modified graphene, alcohol organic solvent and deionized water; the first mixture is then mixed with organosilicon-modified vinyl resin to obtain a second mixture, which is a multifunctional coating.

[0036] Another aspect of the present invention provides the application of a multifunctional coating with nanochannel coating in the field of electronic components, including applications in the field of batteries.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] (1) The multifunctional coating with nano-microchannel coating provided by the present invention uses organosilicon modified vinyl resin as the main film-forming material and adds siloxane containing epoxy groups. Through the alkoxy, hydroxy, epoxy and other components contained therein, a dense dendritic or block copolymer coating can be formed on the substrate surface, which improves the insulation performance of the coating. At the same time, the chemical linking effect of siloxane in the coupling system ensures that the thermal conductivity of the multifunctional coating is improved in both length and thickness directions, achieving uniform heat conduction and avoiding the adverse effects of local heat conduction on the service life of the coating.

[0039] (2) The multifunctional coating with nano-microchannel coating provided by the present invention regulates and utilizes the heat resistance and structural hardness of inorganic heat-conducting particles, so that they overlap on the surface of the heat-conducting chain in the film-forming material to form a heat dissipation system with multiple shaped channels, thereby improving the heat dissipation coating's resistance to thermal shock and giving the coating better mechanical properties and structural stability.

[0040] (3) The multifunctional coating with nano-microchannel coating provided by the present invention utilizes metal oxide to modify graphene with a particle size range of 10 to 50 μm, forming an effective overlap between the two, increasing the heat conduction channels in the coating, enriching the heat conduction network, and significantly improving the heat dissipation performance of the multifunctional coating. At the same time, due to the strong surface bonding force between the two under the preferred conditions, it is uniformly dispersed with other components of the coating system, achieving a rapid and long-lasting heat dissipation effect.

[0041] (4) The multifunctional coating with nano-microchannel coating provided by the present invention utilizes the structure support of the oxide grown in situ on the surface of the modified graphene by doping rare earth powder and adjusting its mass ratio with oxide modified graphene, thereby maintaining and increasing the heat dissipation area of ​​the rare earth powder and improving the thermal conductivity of the coating with a lower amount of rare earth powder added. Detailed Implementation

[0042] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0043] Unless otherwise specified, all reagents used below are readily available from commercial companies. Vinyl ester resin was purchased from Langfang Tongsheng Anticorrosion Equipment Co., Ltd., hydrogen-terminated polydimethylsiloxane was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., polymethyl methacrylate was purchased from Dongguan Zhengtao Plastics Co., Ltd., and yttrium oxide powder (particle size 30-50nm) was purchased from Shandong Xinbaiyi Metal Materials Co., Ltd.

[0044] Preparation Example 1

[0045] Add 50g of vinyl resin to a 500mL reactor containing refluxed isopropanol, stir until homogeneous, then slowly heat to 85℃ for preheating, then add 5g of hydrogen-terminated polydimethylsiloxane and 0.003g of caster catalyst dropwise, react for 20min, and after the addition is complete, keep warm for 5h to obtain organosilicon modified vinyl resin 1.

[0046] Preparation Example 2

[0047] Add 50g of vinyl resin to a 500mL reactor containing refluxed isopropanol, stir until homogeneous, then slowly heat to 85℃ for preheating, then add 12.5g of hydrogen-capped polydimethylsiloxane and 0.006g of caster catalyst dropwise, react for 20min, and after the addition is complete, keep warm for 5h to obtain organosilicon modified vinyl resin 2.

[0048] Preparation Example 3

[0049] 100g of graphene and 250mL of deionized water were added to a reactor, the temperature was raised to 80℃, the mixture was stirred, and the pH was adjusted to neutral to obtain the first reactant. Then, 100mL of 2mol / L zinc oxide solution was slowly added dropwise to 100mL of the first reactant, the pH was adjusted to neutral, and the reaction was carried out for 2 hours to obtain the second reactant. The second reactant was filtered, dried, and calcined to obtain oxide-modified graphene 1.

[0050] Preparation Example 4

[0051] 100g of graphene and 250mL of deionized water were added to a reactor, the temperature was raised to 80℃, the mixture was stirred, and the pH was adjusted to neutral to obtain the first reactant. Then, 100mL of 4mol / L zinc oxide solution was slowly added dropwise to 100mL of the first reactant, the pH was adjusted to neutral, and the reaction was carried out for 2 hours to obtain the second reactant. The second reactant was filtered, dried, and calcined to obtain oxide-modified graphene 2.

[0052] Example 1

[0053] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 20 parts of silicone-modified vinyl resin 1, 12 parts of KH560, 42 parts of inorganic filler, 7 parts of polymethyl methacrylate, 8 parts of oxide-modified graphene 1, 8 parts of isopropanol, 15 parts of deionized water and 4.8 parts of yttrium oxide powder.

[0054] A method for preparing a multifunctional coating coated with nanochannels includes the following steps:

[0055] KH560, inorganic filler, polymethyl methacrylate, oxide-modified graphene 1, isopropanol, deionized water and rare earth powder are mixed to obtain the first mixture; then the first mixture is mixed with organosilicon-modified vinyl resin 1 to obtain the second mixture, which is the multifunctional coating.

[0056] Each inorganic filler contains the following parts by weight of raw materials: 10 parts silicon oxide, 15 parts silicon carbide, 12 parts magnesium oxide, 12 parts zirconium oxide and 5 parts silver powder.

[0057] Example 2

[0058] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 10 parts of silicone-modified vinyl resin 1, 10 parts of KH560, 40 parts of inorganic filler, 4 parts of polymethyl methacrylate, 5 parts of oxide-modified graphene 1, 5 parts of isopropanol, 10 parts of deionized water and 2.5 parts of yttrium oxide powder.

[0059] The preparation method of the multifunctional coating with nanochannel coating in this embodiment is the same as in Example 1;

[0060] Each portion of inorganic filler contains the following parts by weight of raw materials: 8 parts silicon oxide, 10 parts silicon carbide, 10 parts magnesium oxide, 8 parts zirconium oxide and 1 part silver powder.

[0061] Example 3

[0062] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 25 parts of silicone-modified vinyl resin 1, 15 parts of KH560, 45 parts of inorganic filler, 10 parts of polymethyl methacrylate, 10 parts of oxide-modified graphene, 10 parts of isopropanol, 20 parts of deionized water and 8 parts of yttrium oxide powder.

[0063] The preparation method of the multifunctional coating with nanochannel coating in this embodiment is the same as in Example 1;

[0064] Each inorganic filler contains the following parts by weight of raw materials: 15 parts silicon oxide, 30 parts silicon carbide, 15 parts magnesium oxide, 15 parts zirconium oxide and 10 parts silver powder.

[0065] Example 4

[0066] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 20 parts of silicone-modified vinyl resin 2, 12 parts of KH560, 42 parts of inorganic filler, 7 parts of polymethyl methacrylate, 8 parts of oxide-modified graphene 1, 8 parts of isopropanol, 15 parts of deionized water and 4.8 parts of yttrium oxide powder.

[0067] The preparation method of the multifunctional coating with nano-microchannel coating in this embodiment is the same as that in embodiment 1, except that the organosilicon-modified vinyl resin 2 is replaced by an equal amount of organosilicon-modified vinyl resin 1.

[0068] The inorganic filler is the same as in Example 1.

[0069] Example 5

[0070] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 20 parts of silicone-modified vinyl resin 1, 12 parts of KH560, 42 parts of inorganic filler, 7 parts of polymethyl methacrylate, 8 parts of oxide-modified graphene 2, 8 parts of isopropanol, 15 parts of deionized water and 4.8 parts of yttrium oxide powder.

[0071] The preparation method of the multifunctional coating with nanochannel coating in this embodiment is the same as that in embodiment 1, except that oxide-modified graphene 1 is replaced by oxide-modified graphene 2 in an equal amount.

[0072] The inorganic filler is the same as in Example 1.

[0073] Example 6

[0074] A multifunctional coating with nanochannel coating, the multifunctional coating comprising the following raw materials in parts by weight: 20 parts of silicone-modified vinyl resin 1, 12 parts of KH560, 42 parts of inorganic filler, 7 parts of polymethyl methacrylate, 8 parts of oxide-modified graphene 1, 8 parts of isopropanol, and 15 parts of deionized water.

[0075] The preparation method of the multifunctional coating with nanochannel coating in this embodiment is the same as in Example 1;

[0076] The inorganic filler is the same as in Example 1.

[0077] Comparative Example 1

[0078] A multifunctional coating with nanochannel coating, the specific implementation method is the same as in Example 1, except that the organosilicon-modified vinyl resin 1 is replaced with an equal amount of vinyl resin.

[0079] Comparative Example 2

[0080] A multifunctional coating with nanochannel coating, the specific implementation method is the same as in Example 1, except that graphene is used to replace oxide-modified graphene 1 in an equal amount.

[0081] Performance testing:

[0082] The multifunctional coatings prepared in the above examples and comparative examples were subjected to the following performance tests, and the specific test results are shown in Table 1.

[0083] (1) Heat dissipation performance: The heat conduction analyzer manufactured by Hot Disk was used for testing;

[0084] (2) Hardness: The multi-functional coating was tested with a pencil according to GB / T6739. The pencil hardness grades ranged from 5B to 5H from soft to hard.

[0085] (3) Adhesion: The adhesion of the coating was determined using an F107 cross-cut tester according to the ISO2409-2007 cross-cut test method. Grade 0: The edges of the cut are completely smooth and there is no peeling at the edges of the grid. Grade 1: There is small peeling at the intersection of the cuts and the actual damage in the grid area does not exceed 5%. Grade 2: There is peeling at the edges or intersections of the cuts and the area is 5-15%. Grade 3: There is large peeling at the edges of the cuts and the peeling area is 15-35%.

[0086] (4) Self-cleaning performance: Sprinkle 0.5g of iron oxide powder on the surface of the cured coating sample and tilt it at an angle of 30° with the horizontal plane. Then use a dropper to drip deionized water to rinse the contaminants on the coating surface and conduct a self-cleaning performance test to observe whether there is any contaminant dripping phenomenon.

[0087] Table 1

[0088]

[0089] As shown in Table 1, the multifunctional coatings prepared in Examples 1 to 3 of the present invention have strong adhesion and structural hardness, high thermal conductivity, and are hydrophobic, dust-repellent, and have good cleaning performance.

[0090] Comparing Examples 4, 1, and 1-3, it is evident that improper addition of the hydrogen-capped polydimethylsiloxane modifier leads to an over-enrichment of functional groups in the organosilicon-modified vinyl resin, resulting in a dense thermally conductive network that is detrimental to the system's uniformity. This leads to a decrease in both thermal conductivity and localized hardness. Conversely, the unmodified vinyl resin, when used as a film-forming material, struggles to form effective thermally conductive chains, resulting in insufficient performance. Comparing Examples 5 and 1-3, it is evident that improper addition of the zinc oxide solution leads to an excessive amount of free metal oxides. Appropriate zinc oxide can enhance the auxiliary function of rare earth powder, while excessive amounts hinder the dispersion of rare earth powder in the system, resulting in a decrease in both thermal conductivity and adhesion. Comparing Examples 1-3, 2, and 6, it is evident that the rare earth powder added in this invention, with the assistance of modified graphene, significantly improves the thermal conductivity of the multifunctional coating with a relatively low addition amount. Unmodified graphene, however, struggles to provide structural support for the rare earth powder, leading to a decrease in both thermal conductivity and hardness.

[0091] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A multifunctional coating with nanochannel coating, characterized in that, The multifunctional coating comprises the following raw materials in parts by weight: 10-25 parts of silicone-modified vinyl resin, 10-15 parts of epoxy-containing siloxane, 40-45 parts of inorganic filler, 4-10 parts of polymethyl methacrylate, 5-10 parts of oxide-modified graphene, 5-10 parts of alcohol organic solvent and 10-20 parts of deionized water. The preparation steps of the organosilicon-modified vinyl resin are as follows: Vinyl resin was added to a 500 mL reactor containing refluxed isopropanol and stirred until homogeneous. The temperature was then slowly raised to 80-90°C for preheating. Hydrogen-terminated polydimethylsiloxane and catalyst were then added dropwise. The reaction was carried out for 10-30 min. After the addition was completed, the temperature was maintained for 1-10 h to obtain organosilicon-modified vinyl resin. The preparation steps of the oxide-modified graphene are as follows: Graphene and deionized water were added to a reactor, heated to 70-90°C, stirred, and the pH was adjusted to neutral to obtain the first reactant; zinc chloride solution was then slowly added dropwise to the first reactant, the pH was adjusted to neutral, and the reaction was carried out for 1-3 hours to obtain the second reactant; the second reactant was filtered, dried, and calcined to obtain oxide-modified graphene. The multifunctional coating also contains rare earth powder; The mass ratio of the rare earth powder to the oxide-modified graphene is (0.5–0.8):1; The mass ratio of the hydrogen-terminated polydimethylsiloxane to the vinyl resin is (0.1~2):

10.

2. The multifunctional coating with nanochannel coating according to claim 1, characterized in that, The siloxane containing the epoxy group is KH560.

3. The multifunctional coating with nanochannel coating according to claim 1, characterized in that, Each portion of the inorganic filler comprises the following parts by weight of raw materials: 8-15 parts silicon oxide, 10-30 parts silicon carbide, 10-15 parts magnesium oxide, 8-15 parts zirconium oxide and 1-10 parts silver powder.

4. A method for preparing a multifunctional coating with nanochannel coating as described in any one of claims 1-3, characterized in that, Includes the following steps: A first mixture is obtained by mixing an epoxy-containing siloxane, an inorganic filler, polymethyl methacrylate, an oxide-modified graphene, an alcohol-based organic solvent, deionized water, and rare earth powder; the first mixture is then mixed with an organosilicon-modified vinyl resin to obtain the multifunctional coating.

5. The application of a multifunctional coating with nanochannel coating as described in any one of claims 1-3 in the field of electronic components, including applications in the field of batteries.

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