WO2018028362A1 - Thermally-conductive graphene coating and method for preparing same - Google Patents

Thermally-conductive graphene coating and method for preparing same Download PDF

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WO2018028362A1
WO2018028362A1 PCT/CN2017/092020 CN2017092020W WO2018028362A1 WO 2018028362 A1 WO2018028362 A1 WO 2018028362A1 CN 2017092020 W CN2017092020 W CN 2017092020W WO 2018028362 A1 WO2018028362 A1 WO 2018028362A1
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graphene
diluent
parts
resin
resin mixture
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刘若鹏
隋爱国
李雪
丘忠豪
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深圳光启高等理工研究院
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the field of coating technology, and more particularly to a graphene heat conductive coating and a preparation method thereof.
  • a coating is a material that is applied to the surface of an object to form a solid film of strength and continuity. With the development of technology and the improvement of living standards, the requirements for coating performance are getting higher and higher.
  • Graphene is a two-dimensional crystal that is stripped from a graphite material and consists of only one layer of atomic thickness. It is the newest nanomaterial that is the thinnest, strongest, and most conductive and thermally conductive.
  • the invention promotes the reaction of graphene and isocyanate groups by using a silane coupling agent, increases the binding force of graphene and the coating, and removes bubbles by vacuum stirring, further promotes the combination of graphene and the coating, and ensures the graphite.
  • the invention provides a method for preparing a graphene heat conductive coating, comprising: two-component polyurethane
  • the ester resin, the silane coupling agent and the first diluent are added to the stirring vessel, stirred to obtain a resin mixture; the resin mixture is taken out of the bubble; the graphene and the polyurethane resin are added to the second diluent, ultrasonically, uniformly dispersed, Obtaining a graphene dispersion; and mixing the resin mixture with the graphene dispersion to perform grinding and dispersion to obtain the graphene heat conductive coating.
  • the two-component polyurethane resin comprises a polyurethane main body and a curing agent.
  • the ratio by weight of the polyurethane main body to the curing agent is from 100:50 to 200.
  • the curing agent comprises one or more of an isocyanate resin, a modified polyurethane, sodium carboxymethylcellulose, polyethylene glycol, and polyvinyl alcohol.
  • the ratio by weight of the polyurethane main body, the silane coupling agent and the first diluent is from 100:2 to 10:20 to 100.
  • first diluent and the second diluent are the same, and the first diluent and the second diluent each comprise one of isopropanol, ethanol, and acetone or A variety.
  • first diluent and the second diluent are different, and the first diluent and the second diluent each comprise one of isopropanol, ethanol, and acetone or A variety.
  • the stirring time is 30 to 120 minutes, and the stirring speed is 100 to 3000 rpm.
  • the ratio by weight of the graphene, the urethane resin and the second diluent is from 100:10 to 100:20 to 200.
  • the present invention also provides a graphene heat conductive coating prepared according to the above method.
  • the method for preparing a graphene heat conductive coating provides a stone with enhanced stability Inkene thermal conductive coating.
  • the graphene heat conductive coating is thoroughly mixed with the polyurethane main body by the graphene, so that the graphene reacts with the isocyanate group, the binding force of the graphene and the coating is increased, and the bubble is removed by vacuum stirring to promote the resin mixture and the graphene dispersion. The reaction and combination between the two, to improve the adhesion of the coating to the substrate and the stability of the corrosion resistance.
  • the graphene is uniformly and stably dispersed in the coating by sufficient stirring and grinding by a three-roll mill, which fully exerts the role of graphene in the coating, and greatly improves the stability of the graphene heat conductive coating effect.
  • the invention utilizes the characteristics of graphene itself to ensure the stability of the performance of the graphene heat conductive material while uniformly doping into the coating material, improving the thermal conductivity of the coating, the adhesion to the substrate and the corrosion resistance.
  • 1 is a schematic view of attaching a graphene heat conductive coating to a substrate, wherein 1 is a substrate, 2 is a graphene heat conductive coating layer, and 3 is graphene in a graphene heat conductive coating layer.
  • the curing agent includes one or more of an isocyanate resin, a modified polyurethane, sodium carboxymethylcellulose, polyethylene glycol, and polyvinyl alcohol.
  • the diluent includes one or more of isopropyl alcohol, ethanol, and acetone.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 100 to 3000 rpm for 30 to 120 minutes.
  • diluent comprises one or more of isopropanol, ethanol and acetone.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 2000 rpm for 30 minutes.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 800 rpm for 60 minutes.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 1,500 rpm for 120 minutes.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 100 rpm for 150 minutes.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 3000 rpm for 30 minutes.
  • the resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 2,800 rpm for 90 minutes.
  • Example 2 The same as in Example 1, except that no silane coupling agent was added to the resin mixture and no polyurethane curing agent was added to the graphene dispersion.
  • the present invention increases the binding force of graphene and the coating by adding a silane coupling agent and thoroughly mixing the graphene with the polyurethane main body, thereby increasing the binding force of the graphene and the coating, and removing the bubbles by vacuum stirring.
  • the reaction and bonding between the resin mixture and the graphene dispersion are promoted, and the adhesion of the coating to the substrate and the stability of the corrosion resistance are improved.
  • the graphene heat conductive coating prepared by the method of the present invention has significantly improved adhesion and thermal conductivity and is more stable.
  • the graphene heat conductive material of the invention is large while ensuring superior performance over conventional coatings.
  • the stability and dispersion uniformity of the addition of graphene in the coating are greatly improved, the function of the graphene is fully exerted, and the performance of the coating is enhanced.

Abstract

A method for preparing a thermally-conductive graphene coating and a thermally-conductive coating prepared thereby. The method comprises: adding a two-component polyurethane resin, a silane coupling agent, and a first diluent to a stirring container, and stirring same to obtain a resin mixture; defoaming the resin mixture; adding graphene and a polyurethane resin to a second dilute and performing ultrasonic treatment and uniform dispersion on the mixture to obtain a graphene dispersion; and mixing the resin mixture and the graphene dispersion, and performing grinding and dispersion on the mixture to obtain a thermally-conductive graphene coating.

Description

一种石墨烯导热涂料及其制备方法Graphene heat conductive coating and preparation method thereof 技术领域Technical field
本发明涉及涂料技术领域，更具体地，涉及一种石墨烯导热涂料及其制备方法。The invention relates to the field of coating technology, and more particularly to a graphene heat conductive coating and a preparation method thereof.
背景技术Background technique
涂料是用于涂覆在物体表面，形成具有一定强度、连续的固态薄膜的一种材料。随着科技的发展和生活水平的提高，对涂料性能的要求也越来越高。A coating is a material that is applied to the surface of an object to form a solid film of strength and continuity. With the development of technology and the improvement of living standards, the requirements for coating performance are getting higher and higher.
石墨烯是从石墨材料中剥离出来，由碳原子组成的只有一层原子厚度的二维晶体。是目前发现的最薄、强度最大、导电导热性能最强的一种新型纳米材料。Graphene is a two-dimensional crystal that is stripped from a graphite material and consists of only one layer of atomic thickness. It is the newest nanomaterial that is the thinnest, strongest, and most conductive and thermally conductive.
目前通过将石墨烯应用于传统涂料已经较好地改进了传统涂料的一些不足，例如在涂料中加入石墨烯提高了涂层的耐摩擦性、导热性等。然而在这种导热涂料的制备中，虽然将石墨烯加入涂料，但是由于未将石墨烯和涂料充分混合，因此石墨烯和涂料的结合力差，不能充分发挥石墨烯在涂料中的作用，使得这种石墨烯改性的导热涂料效果不稳定等。因此，本领域仍然存在改进导热涂料的导热性和与基底的附着力的需求。At present, the application of graphene to conventional coatings has improved some of the shortcomings of conventional coatings. For example, the addition of graphene to coatings improves the abrasion resistance and thermal conductivity of the coating. However, in the preparation of such a thermally conductive coating, although graphene is added to the coating, since the graphene and the coating are not sufficiently mixed, the bonding strength of the graphene and the coating is poor, and the role of the graphene in the coating cannot be fully exerted, so that This graphene-modified thermal conductive coating is unstable and the like. Accordingly, there remains a need in the art to improve the thermal conductivity of thermal conductive coatings and adhesion to substrates.
发明内容Summary of the invention
本发明通过使用硅烷偶联剂促进石墨烯与异氰酸酯基团反应，增加了石墨烯和涂料的结合力，并且采用真空搅拌的方法脱出气泡，进一步促进了石墨烯与涂料的结合，保证了该石墨烯导热涂料对基底的附着力以及自身的耐蚀性等，并且大大提高了石墨烯的分散均匀性以及石墨烯导热涂料的稳定性。The invention promotes the reaction of graphene and isocyanate groups by using a silane coupling agent, increases the binding force of graphene and the coating, and removes bubbles by vacuum stirring, further promotes the combination of graphene and the coating, and ensures the graphite. The adhesion of the olefin thermal conductive coating to the substrate and its own corrosion resistance, etc., and greatly improve the dispersion uniformity of the graphene and the stability of the graphene thermal conductive coating.
本发明提供了一种制备石墨烯导热涂料的方法，包括：将双组分聚氨 酯树脂、硅烷偶联剂和第一稀释剂加入到搅拌容器中，搅拌得到树脂混合物；将所述树脂混合物脱出气泡；将石墨烯、聚氨酯树脂加入到第二稀释剂中，超声，均匀分散，得到石墨烯分散液；以及将所述树脂混合物与所述石墨烯分散液混合，进行研磨分散，得到所述石墨烯导热涂料。The invention provides a method for preparing a graphene heat conductive coating, comprising: two-component polyurethane The ester resin, the silane coupling agent and the first diluent are added to the stirring vessel, stirred to obtain a resin mixture; the resin mixture is taken out of the bubble; the graphene and the polyurethane resin are added to the second diluent, ultrasonically, uniformly dispersed, Obtaining a graphene dispersion; and mixing the resin mixture with the graphene dispersion to perform grinding and dispersion to obtain the graphene heat conductive coating.
在上述方法中，其中，所述双组分聚氨酯树脂包括聚氨酯主体和固化剂。In the above method, wherein the two-component polyurethane resin comprises a polyurethane main body and a curing agent.
在上述方法中，其中，所述聚氨酯主体与所述固化剂的重量份数比为100:50～200。In the above method, the ratio by weight of the polyurethane main body to the curing agent is from 100:50 to 200.
在上述方法中，其中，所述固化剂包括异氰酸酯树脂、改性聚氨酯、羧甲基纤维素钠、聚乙二醇、聚乙烯醇中的一种或几种。In the above method, wherein the curing agent comprises one or more of an isocyanate resin, a modified polyurethane, sodium carboxymethylcellulose, polyethylene glycol, and polyvinyl alcohol.
在上述方法中，其中，所述聚氨酯主体、所述硅烷偶联剂和所述第一稀释剂的重量份数比为100:2～10:20～100。In the above method, the ratio by weight of the polyurethane main body, the silane coupling agent and the first diluent is from 100:2 to 10:20 to 100.
在上述方法中，其中，所述第一稀释剂和所述第二稀释剂相同，并且所述第一稀释剂和所述第二稀释剂均包括异丙醇、乙醇和丙酮中的一种或多种。In the above method, wherein the first diluent and the second diluent are the same, and the first diluent and the second diluent each comprise one of isopropanol, ethanol, and acetone or A variety.
在上述方法中，其中，所述第一稀释剂和所述第二稀释剂不同，并且所述第一稀释剂和所述第二稀释剂均包括异丙醇、乙醇和丙酮中的一种或多种。In the above method, wherein the first diluent and the second diluent are different, and the first diluent and the second diluent each comprise one of isopropanol, ethanol, and acetone or A variety.
在上述方法中，其中，所述搅拌的时间为30～120分钟，搅拌速度为100～3000转/分钟。In the above method, the stirring time is 30 to 120 minutes, and the stirring speed is 100 to 3000 rpm.
在上述方法中，其中，采用真空搅拌将所述树脂混合物脱出气泡，并且所述真空搅拌的时间为30～120分钟，搅拌速度为100～3000转/分钟。In the above method, wherein the resin mixture is taken out of the bubble by vacuum stirring, and the vacuum stirring time is 30 to 120 minutes, and the stirring speed is 100 to 3000 rpm.
在上述方法中，其中，石墨烯、所述聚氨酯树脂和所述第二稀释剂的重量份数比为100:10～100:20～200。In the above method, the ratio by weight of the graphene, the urethane resin and the second diluent is from 100:10 to 100:20 to 200.
在上述方法中，其中，所述树脂混合物和所述石墨烯分散液的重量份数比为100:10～100。12.根据权利要求1所述的方法，其特征在于，通过三辊研磨机进行研磨分散，并且研磨时间为0.5～4小时。In the above method, wherein the resin mixture and the graphene dispersion have a weight ratio of 100:10 to 100. 12. The method according to claim 1, wherein the three-roll mill is passed through The polishing dispersion was carried out, and the polishing time was 0.5 to 4 hours.
本发明还提供了一种根据以上方法制备的石墨烯导热涂料。The present invention also provides a graphene heat conductive coating prepared according to the above method.
通过本发明提供的制备石墨烯导热涂料的方法，得到稳定性增强的石 墨烯导热涂料。该石墨烯导热涂料通过石墨烯与聚氨酯主体充分混合，使得石墨烯与异氰酸酯基团反应，增加了石墨烯和涂料的结合力，并且采用真空搅拌法脱出气泡，促进了树脂混合物与石墨烯分散液之间的反应和结合，提高涂层对基底的附着力与耐蚀性的稳定效果。同时通过充分搅拌、三辊研磨机研磨等使得石墨烯均匀稳定地分散在涂料中，充分发挥了石墨烯在涂料中的作用，大大提高了石墨烯导热涂料效果的稳定性。The method for preparing a graphene heat conductive coating provided by the invention provides a stone with enhanced stability Inkene thermal conductive coating. The graphene heat conductive coating is thoroughly mixed with the polyurethane main body by the graphene, so that the graphene reacts with the isocyanate group, the binding force of the graphene and the coating is increased, and the bubble is removed by vacuum stirring to promote the resin mixture and the graphene dispersion. The reaction and combination between the two, to improve the adhesion of the coating to the substrate and the stability of the corrosion resistance. At the same time, the graphene is uniformly and stably dispersed in the coating by sufficient stirring and grinding by a three-roll mill, which fully exerts the role of graphene in the coating, and greatly improves the stability of the graphene heat conductive coating effect.
本发明利用石墨烯自身的特性，通过均匀地掺杂到涂料中，在提高涂料导热率、与基底的附着力与耐蚀性的同时保证了石墨烯导热材料性能的稳定性。The invention utilizes the characteristics of graphene itself to ensure the stability of the performance of the graphene heat conductive material while uniformly doping into the coating material, improving the thermal conductivity of the coating, the adhesion to the substrate and the corrosion resistance.
附图说明DRAWINGS
图1是将石墨烯导热涂料附着在基底上的示意图，其中，1为基底，2为石墨烯导热涂料层，3为石墨烯导热涂料层中的石墨烯。1 is a schematic view of attaching a graphene heat conductive coating to a substrate, wherein 1 is a substrate, 2 is a graphene heat conductive coating layer, and 3 is graphene in a graphene heat conductive coating layer.
具体实施方式detailed description
下面的实施例可以使本领域技术人员更全面地理解本发明，但不以任何方式限制本发明。除非特别限定，以下份数均以重量份数计。The following examples are intended to provide a more complete understanding of the invention, and are not intended to limit the invention in any way. Unless otherwise specified, the following parts are by weight.
将100份的聚氨酯主体、50～200份的固化剂、2～10份的硅烷偶联剂和20～100份的稀释剂加入到搅拌容器中，以100～3000转/分钟的搅拌速度高速搅拌30～120分钟，得到树脂混合物。其中，固化剂包括异氰酸酯树脂、改性聚氨酯、羧甲基纤维素钠、聚乙二醇、聚乙烯醇中的一种或几种。稀释剂包括异丙醇、乙醇和丙酮中的一种或多种。100 parts of the polyurethane main body, 50 to 200 parts of the curing agent, 2 to 10 parts of the silane coupling agent, and 20 to 100 parts of the diluent are added to the stirring vessel, and the mixture is stirred at a high speed of 100 to 3000 rpm. A resin mixture was obtained for 30 to 120 minutes. The curing agent includes one or more of an isocyanate resin, a modified polyurethane, sodium carboxymethylcellulose, polyethylene glycol, and polyvinyl alcohol. The diluent includes one or more of isopropyl alcohol, ethanol, and acetone.
将树脂混合物采用真空搅拌法脱出气泡，以100～3000转/分钟的搅拌速度搅拌30～120分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 100 to 3000 rpm for 30 to 120 minutes.
将100份的石墨烯粉末、10～100份的聚氨酯树脂(作为固化剂使用)加入到20～200份的稀释剂中，超声使之均匀分散，得到石墨烯分散液。其中，稀释剂包括异丙醇、乙醇和丙酮中的一种或多种。100 parts of graphene powder and 10 to 100 parts of a urethane resin (used as a curing agent) are added to 20 to 200 parts of a diluent, and uniformly dispersed by ultrasonication to obtain a graphene dispersion. Wherein the diluent comprises one or more of isopropanol, ethanol and acetone.
将100份的树脂混合物和10～100份的石墨烯分散液混合，通过三辊研磨机研磨0.5～4小时，得到如图1所示石墨烯导热涂料层中的石墨烯导热 涂料。上述份数均以重量计。100 parts of the resin mixture and 10 to 100 parts of the graphene dispersion are mixed and ground by a three-roll mill for 0.5 to 4 hours to obtain graphene heat conduction in the graphene heat conductive coating layer as shown in FIG. coating. The above parts are all by weight.
实施例一Embodiment 1
将100份的聚氨酯主体、50份的异氰酸酯树脂、2份的硅烷偶联剂和30份的水加入到搅拌容器中，以200转/分钟的搅拌速度高速搅拌30分钟，得到树脂混合物。100 parts of the polyurethane main body, 50 parts of the isocyanate resin, 2 parts of the silane coupling agent, and 30 parts of water were placed in a stirring vessel, and stirred at a high speed of 200 rpm for 30 minutes to obtain a resin mixture.
将树脂混合物采用真空搅拌法脱出气泡，以2000转/分钟的搅拌速度搅拌30分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 2000 rpm for 30 minutes.
将100份的石墨烯粉末、50份的聚氨酯树脂加入到100份的水中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder and 50 parts of urethane resin were added to 100 parts of water, and ultrasonically dispersed to uniformly obtain a graphene dispersion.
将100份的树脂混合物和10份的石墨烯分散液混合，通过三辊研磨机研磨2小时，得到石墨烯导热涂料。100 parts of the resin mixture and 10 parts of the graphene dispersion were mixed and ground by a three-roll mill for 2 hours to obtain a graphene heat conductive paint.
实施例二 Embodiment 2
将100份的聚氨酯主体、90份的羧甲基纤维素钠、10份的硅烷偶联剂和20份的乙醇加入到搅拌容器中，以100转/分钟的搅拌速度高速搅拌120分钟，得到树脂混合物。100 parts of a polyurethane main body, 90 parts of sodium carboxymethylcellulose, 10 parts of a silane coupling agent, and 20 parts of ethanol were placed in a stirring vessel, and stirred at a high speed of 100 rpm for 120 minutes to obtain a resin. mixture.
将树脂混合物采用真空搅拌法脱出气泡，以800转/分钟的搅拌速度搅拌60分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 800 rpm for 60 minutes.
将100份的石墨烯粉末、10份的聚氨酯树脂加入到200份的乙醇中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder and 10 parts of urethane resin were added to 200 parts of ethanol, and uniformly dispersed by ultrasonication to obtain a graphene dispersion.
将100份的树脂混合物和50份的石墨烯分散液混合，通过三辊研磨机研磨0.5小时，得到石墨烯导热涂料。100 parts of the resin mixture and 50 parts of the graphene dispersion were mixed and ground by a three-roll mill for 0.5 hour to obtain a graphene heat conductive paint.
实施例三Embodiment 3
将100份的聚氨酯主体、200份的改性聚氨酯、10份的硅烷偶联剂和100份的异丙醇加入到搅拌容器中，以3000转/分钟的搅拌速度高速搅拌40分钟，得到树脂混合物。100 parts of the polyurethane main body, 200 parts of the modified polyurethane, 10 parts of the silane coupling agent, and 100 parts of isopropyl alcohol were placed in a stirring vessel, and stirred at a high speed of 3000 rpm for 40 minutes to obtain a resin mixture. .
将树脂混合物采用真空搅拌法脱出气泡，以1500转/分钟的搅拌速度搅拌120分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 1,500 rpm for 120 minutes.
将100份的石墨烯粉末、100份的聚氨酯树脂加入到200份的异丙醇 中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder, 100 parts of polyurethane resin added to 200 parts of isopropanol In the ultrasonic, it is uniformly dispersed to obtain a graphene dispersion.
将100份的树脂混合物和80份的石墨烯分散液混合，通过三辊研磨机研磨4小时，得到石墨烯导热涂料。100 parts of the resin mixture and 80 parts of the graphene dispersion were mixed and ground by a three-roll mill for 4 hours to obtain a graphene heat conductive paint.
实施例四Embodiment 4
将100份的聚氨酯主体、150份的聚乙烯醇、6份的硅烷偶联剂和60份的丙酮加入到搅拌容器中，以2000转/分钟的搅拌速度高速搅拌70分钟，得到树脂混合物。100 parts of a polyurethane main body, 150 parts of polyvinyl alcohol, 6 parts of a silane coupling agent, and 60 parts of acetone were placed in a stirring vessel, and stirred at a high speed of 2000 rpm for 70 minutes to obtain a resin mixture.
将树脂混合物采用真空搅拌法脱出气泡，以100转/分钟的搅拌速度搅拌150分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 100 rpm for 150 minutes.
将100份的石墨烯粉末、80份的聚氨酯树脂加入到20份的丙酮中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder and 80 parts of urethane resin were added to 20 parts of acetone, and uniformly dispersed by ultrasonication to obtain a graphene dispersion.
将100份的树脂混合物和100份的石墨烯分散液混合，通过三辊研磨机研磨3小时，得到石墨烯导热涂料。100 parts of the resin mixture and 100 parts of the graphene dispersion were mixed and ground by a three-roll mill for 3 hours to obtain a graphene heat conductive paint.
实施例五Embodiment 5
将100份的聚氨酯主体、100份的聚乙二醇、7份的硅烷偶联剂和80份的乙醇加入到搅拌容器中，以1800转/分钟的搅拌速度高速搅拌50分钟，得到树脂混合物。100 parts of a polyurethane main body, 100 parts of polyethylene glycol, 7 parts of a silane coupling agent, and 80 parts of ethanol were placed in a stirring vessel, and stirred at a high speed of 1800 rpm for 50 minutes to obtain a resin mixture.
将树脂混合物采用真空搅拌法脱出气泡，以3000转/分钟的搅拌速度搅拌30分钟。The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 3000 rpm for 30 minutes.
将100份的石墨烯粉末、60份的聚氨酯树脂加入到80份的乙醇中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder and 60 parts of urethane resin were added to 80 parts of ethanol, and uniformly dispersed by ultrasonication to obtain a graphene dispersion.
将100份的树脂混合物和90份的石墨烯分散液混合，通过三辊研磨机研磨3.5小时，得到石墨烯导热涂料。100 parts of the resin mixture and 90 parts of the graphene dispersion were mixed and ground by a three-roll mill for 3.5 hours to obtain a graphene heat conductive paint.
实施例六Embodiment 6
将100份的聚氨酯主体、200份的异氰酸酯树脂、10份的硅烷偶联剂和100份的水加入到搅拌容器中，以3000转/分钟的搅拌速度高速搅拌50分钟，得到树脂混合物。100 parts of a polyurethane main body, 200 parts of an isocyanate resin, 10 parts of a silane coupling agent, and 100 parts of water were placed in a stirring vessel, and stirred at a high speed of 3000 rpm for 50 minutes to obtain a resin mixture.
将树脂混合物采用真空搅拌法脱出气泡，以2800转/分钟的搅拌速度搅拌90分钟。 The resin mixture was bubbled out by vacuum stirring, and stirred at a stirring speed of 2,800 rpm for 90 minutes.
将100份的石墨烯粉末、40份的聚氨酯树脂加入到150份的乙醇中，超声使之均匀分散，得到石墨烯分散液。100 parts of graphene powder and 40 parts of urethane resin were added to 150 parts of ethanol, and uniformly dispersed by ultrasonication to obtain a graphene dispersion.
将100份的树脂混合物和100份的石墨烯分散液混合，通过三辊研磨机研磨2.5小时，得到石墨烯导热涂料。100 parts of the resin mixture and 100 parts of the graphene dispersion were mixed and ground by a three-roll mill for 2.5 hours to obtain a graphene heat conductive paint.
对比例一Comparative example one
与实施例一相同，除了在树脂混合物中未加入硅烷偶联剂以及在石墨烯分散液中未加入聚氨酯固化剂。The same as in Example 1, except that no silane coupling agent was added to the resin mixture and no polyurethane curing agent was added to the graphene dispersion.
对比例二Comparative example two
与实施例二相同，除了未包括对树脂混合物脱出气泡的步骤。The same as in the second embodiment except that the step of removing bubbles from the resin mixture is not included.
通过本领域常用的方法测量以上实施例得到的石墨烯导热涂料对基底的附着力和导热率，结果如表1所示：The adhesion and thermal conductivity of the graphene heat conductive coating obtained in the above examples to the substrate were measured by methods commonly used in the art, and the results are shown in Table 1:
表1Table 1
  附着力/MPaAdhesion / MPa 导热率(W/mk)Thermal conductivity (W/mk)
实施例一Embodiment 1 3.83.8 185185
实施例二 Embodiment 2 4.24.2 191191
实施例三Embodiment 3 3.93.9 187187
实施例四Embodiment 4 4.14.1 195195
实施例五Embodiment 5 4.04.0 183183
实施例六Embodiment 6 4.44.4 193193
对比例一Comparative example one 2.52.5 131131
对比例二Comparative example two 3.03.0 145145
由表1可知，本发明通过添加硅烷偶联剂并且使石墨烯与聚氨酯主体充分混合，使得石墨烯与异氰酸酯基团反应，增加了石墨烯和涂料的结合力，并且采用真空搅拌法脱出气泡，促进了树脂混合物与石墨烯分散液之间的反应和结合，提高了涂层对基底的附着力与耐蚀性的稳定效果。通过本发明的方法制备的石墨烯导热涂料的附着力和导热率显著提高，并且更具稳定性。It can be seen from Table 1 that the present invention increases the binding force of graphene and the coating by adding a silane coupling agent and thoroughly mixing the graphene with the polyurethane main body, thereby increasing the binding force of the graphene and the coating, and removing the bubbles by vacuum stirring. The reaction and bonding between the resin mixture and the graphene dispersion are promoted, and the adhesion of the coating to the substrate and the stability of the corrosion resistance are improved. The graphene heat conductive coating prepared by the method of the present invention has significantly improved adhesion and thermal conductivity and is more stable.
本发明的石墨烯导热材料在保证超越传统涂料的优越性能的同时，大 大提高了涂料中加入石墨烯的稳定性和分散均匀性，充分发挥了石墨烯的作用，增强了涂料的性能。The graphene heat conductive material of the invention is large while ensuring superior performance over conventional coatings. The stability and dispersion uniformity of the addition of graphene in the coating are greatly improved, the function of the graphene is fully exerted, and the performance of the coating is enhanced.
本领域技术人员应理解，以上实施例仅是示例性实施例，在不背离本发明的精神和范围的情况下，可以进行多种变化、替换以及改变。 Those skilled in the art will appreciate that the above-described embodiments are merely exemplary embodiments, and various changes, substitutions and changes may be made without departing from the spirit and scope of the invention.

Claims (13)

  1. 一种制备石墨烯导热涂料的方法，其特征在于，包括：A method for preparing a graphene heat conductive coating, comprising:
    将双组分聚氨酯树脂、硅烷偶联剂和第一稀释剂加入到搅拌容器中，搅拌得到树脂混合物；Adding a two-component polyurethane resin, a silane coupling agent and a first diluent to a stirring vessel, and stirring to obtain a resin mixture;
    将所述树脂混合物脱出气泡；Removing the resin mixture from the bubbles;
    将石墨烯、聚氨酯树脂加入到第二稀释剂中，超声，均匀分散，得到石墨烯分散液；以及Adding graphene and polyurethane resin to the second diluent, ultrasonically and uniformly dispersing to obtain a graphene dispersion;
    将所述树脂混合物与所述石墨烯分散液混合，进行研磨分散，得到所述石墨烯导热涂料。The resin mixture is mixed with the graphene dispersion, and ground and dispersed to obtain the graphene heat conductive coating.
  2. 根据权利要求1所述的方法，其特征在于，所述双组分聚氨酯树脂包括聚氨酯主体和固化剂。The method of claim 1 wherein said two-component polyurethane resin comprises a polyurethane body and a curing agent.
  3. 根据权利要求2所述的方法，其特征在于，所述聚氨酯主体与所述固化剂的重量份数比为100:50～200。The method according to claim 2, wherein the ratio by weight of the polyurethane main body to the curing agent is from 100:50 to 200.
  4. 根据权利要求2所述的方法，其特征在于，所述固化剂包括异氰酸酯树脂、改性聚氨酯、羧甲基纤维素钠、聚乙二醇、聚乙烯醇中的一种或几种。The method according to claim 2, wherein the curing agent comprises one or more of an isocyanate resin, a modified polyurethane, sodium carboxymethylcellulose, polyethylene glycol, and polyvinyl alcohol.
  5. 根据权利要求2所述的方法，其特征在于，所述聚氨酯主体、所述硅烷偶联剂和所述第一稀释剂的重量份数比为100:2～10:20～100。The method according to claim 2, wherein the polyurethane main body, the silane coupling agent and the first diluent have a weight ratio of from 100:2 to 10:20 to 100.
  6. 根据权利要求1所述的方法，其特征在于，所述第一稀释剂和所述第二稀释剂相同，并且所述第一稀释剂和所述第二稀释剂均包括异丙醇、乙醇和丙酮中的一种或多种。The method of claim 1 wherein said first diluent and said second diluent are the same, and said first diluent and said second diluent both comprise isopropanol, ethanol, and One or more of acetone.
  7. 根据权利要求1所述的方法，其特征在于，所述第一稀释剂和所述第二稀释剂不同，并且所述第一稀释剂和所述第二稀释剂均包括异丙醇、乙醇和丙酮中的一种或多种。The method of claim 1 wherein said first diluent and said second diluent are different, and said first diluent and said second diluent both comprise isopropanol, ethanol, and One or more of acetone.
  8. 根据权利要求1所述的方法，其特征在于，所述搅拌的时间为30～120分钟，搅拌速度为100～3000转/分钟。The method according to claim 1, wherein the stirring time is 30 to 120 minutes, and the stirring speed is 100 to 3000 rpm.
  9. 根据权利要求1所述的方法，其特征在于，采用真空搅拌将所述树脂混合物脱出气泡，并且所述真空搅拌的时间为30～120分钟，搅拌速度为 100～3000转/分钟。The method according to claim 1, wherein the resin mixture is taken out of the bubble by vacuum stirring, and the vacuum stirring time is 30 to 120 minutes, and the stirring speed is 100 to 3000 rpm.
  10. 根据权利要求1所述的方法，其特征在于，石墨烯、所述聚氨酯树脂和所述第二稀释剂的重量份数比为100:10～100:20～200。The method according to claim 1, wherein the ratio by weight of the graphene, the polyurethane resin and the second diluent is from 100:10 to 100:20 to 200.
  11. 根据权利要求1所述的方法，其特征在于，所述树脂混合物和所述石墨烯分散液的重量份数比为100:10～100。The method according to claim 1, wherein the resin mixture and the graphene dispersion have a weight ratio of from 100:10 to 100.
  12. 根据权利要求1所述的方法，其特征在于，通过三辊研磨机进行研磨分散，并且研磨时间为0.5～4小时。The method according to claim 1, wherein the grinding and dispersing is performed by a three-roll mill, and the grinding time is 0.5 to 4 hours.
  13. 一种根据权利要求1-12中任一项所述的方法制备的石墨烯导热涂料。 A graphene thermally conductive coating prepared by the method of any of claims 1-12.
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