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WO2022056974A1 - Insulating polyvinyl alcohol composite heat-conducting film and preparation method therefor - Google Patents

Insulating polyvinyl alcohol composite heat-conducting film and preparation method therefor Download PDF

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Publication number
WO2022056974A1
WO2022056974A1 PCT/CN2020/120791 CN2020120791W WO2022056974A1 WO 2022056974 A1 WO2022056974 A1 WO 2022056974A1 CN 2020120791 W CN2020120791 W CN 2020120791W WO 2022056974 A1 WO2022056974 A1 WO 2022056974A1
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polyvinyl alcohol
graphene oxide
graphene
preparation
thermally conductive
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French (fr)
Chinese (zh)
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陈国华
罗芳华
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Huaqiao University
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Huaqiao University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Definitions

  • the invention relates to the technical field of thermally conductive materials, in particular to an insulating polyvinyl alcohol composite thermally conductive film and a preparation method thereof.
  • the object of the present invention is to provide a kind of insulating polyvinyl alcohol composite heat-conducting film and preparation method thereof, and the insulating polyvinyl alcohol composite heat-conducting film provided by the present invention has good thermal conductivity, insulation performance and flexibility simultaneously.
  • the invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer;
  • the thickness of the polyvinyl alcohol-graphene layer is 6-100 ⁇ m; the thickness of the polyvinyl alcohol layer is independently 0.1-3 ⁇ m.
  • the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 1-10 wt %.
  • the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 4-8 wt %.
  • the invention provides a preparation method of an insulating polyvinyl alcohol composite thermally conductive film, comprising the following steps:
  • polyvinyl alcohol, film-forming aid and water are mixed to obtain polyvinyl alcohol solution
  • the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand and heat-dried to obtain an insulating polyvinyl alcohol composite thermally conductive film; the temperature of the heat-drying is 60-100° C., The time is 8 to 16h;
  • the steps (1) to (2) are not limited in time sequence.
  • the degree of polymerization of polyvinyl alcohol in the step (1) is 1500-2400.
  • the film-forming adjuvant in the step (1) is one or more of glycerol, sodium alginate, propylene glycol and dopamine.
  • the mass ratio of the polyvinyl alcohol, the film-forming aid and the water is 5-9:0.5-2:100.
  • the mass concentration of the graphene oxide aqueous dispersion liquid is 0.1-2 wt %; the sheet thickness of the graphene oxide is 0.8-1.3 nm.
  • the reducing agent in the step (3) is one or more of ascorbic acid, hydrazine hydrate and hydrogen iodide.
  • the mass ratio of polyvinyl alcohol to graphene oxide is 100:1 to 10; the mass ratio of the reducing agent to graphene oxide is 1 to 13:1.
  • the step (3) includes the following steps:
  • the polyvinyl alcohol/graphene oxide mixed solution and the reducing agent are magnetically stirred and mixed to obtain the polyvinyl alcohol/graphene oxide/reducing agent mixed solution.
  • the power of the ultrasonic mixing is 100W, and the time is 1-5min;
  • the rotating speed of the magnetic stirring and mixing is 200-500 rpm, and the time is 0.5-2h.
  • the temperature for standing in the step (4) is 25-40° C., and the time is 1-2 h.
  • the invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer; the polyvinyl alcohol-graphene layer
  • the thickness of the polyvinyl alcohol layer is 6-100 ⁇ m; the thickness of the polyvinyl alcohol layer is independently 0.1-3 ⁇ m.
  • the composite heat-conducting film provided by the invention has a "sandwich" structure, both sides of the composite heat-conducting film are polyvinyl alcohol layers, and the surface does not contain graphene, so that the composite heat-conducting film has good insulating properties; the middle layer is polyvinyl alcohol-graphite Graphene layer, wherein graphene can form a thermal conduction network inside the composite thermally conductive film, so that the composite thermally conductive film has excellent thermal conductivity; the present invention uses polyvinyl alcohol as the main raw material of the composite thermally conductive film, which can make the composite thermally conductive film have good flexibility.
  • the results of the examples show that the volume resistivity of the insulating polyvinyl alcohol composite thermally conductive film provided by the present invention is >10 9 ⁇ cm, the thermal conductivity can reach 4.00Wm -1 K -1 , and has good flexibility.
  • the invention provides a preparation method of an insulating polyvinyl alcohol composite thermally conductive film.
  • the present invention mixes the polyvinyl alcohol solution, graphene oxide aqueous dispersion and a reducing agent, and a polyvinyl alcohol/graphene oxide/reducing agent mixed solution , and then the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand, and heated to dry to obtain an insulating polyvinyl alcohol composite heat-conducting film.
  • scraping film forming is performed first, and then the graphene oxide is in-situ reduced to reduced graphene oxide in the process of standing.
  • the water solvent in the film layer will evaporate continuously after the film is wiped. Hydrogen bonds between vinyl alcohols and reduced graphene oxide will agglomerate, and at the same time a small amount of polyvinyl alcohol in the film tends to be distributed on both sides of the composite film, so that the film has polyvinyl alcohol/polyvinyl alcohol-graphene/ Sandwich structure of polyvinyl alcohol.
  • the invention can make the obtained composite film have a three-layer structure with stable and clear interface.
  • the present invention solves the problem of directly using graphene as a filler and is difficult to disperse by first forming and then reducing graphene oxide to graphene in situ, and is conducive to the preparation of a uniform composite thermally conductive film.
  • the preparation method provided by the invention does not use organic solvents, is environmentally friendly and pollution-free; the invention has simple operation, low cost, and is easy to realize industrialized mass production.
  • Fig. 1 is the AFM figure of graphene oxide in embodiment 1;
  • Fig. 2 is the sheet thickness of graphene oxide in embodiment 1;
  • Fig. 3 is the TEM image of the insulating polyvinyl alcohol composite thermally conductive film obtained in Example 1;
  • Fig. 5 is the tensile strength diagram of the films obtained in Examples 1-5 and Comparative Example 1;
  • FIG. 7 is a graph showing the flexibility of the film obtained in Example 3.
  • the invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer.
  • the thickness of the polyvinyl alcohol/graphene layer is preferably 6-100 ⁇ m, more preferably 10-80 ⁇ m, further preferably 20-60 ⁇ m; the thickness of the polyvinyl alcohol layer is preferably 0.1-3 ⁇ m independently , more preferably 0.2 to 2 ⁇ m, still more preferably 0.5 to 2 ⁇ m.
  • the thickness of the insulating polyvinyl alcohol composite thermally conductive film is preferably 6.2 to 106 ⁇ m, more preferably 10 to 80 ⁇ m, and further preferably 20 to 50 ⁇ m.
  • the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is preferably 1-10 wt %, more preferably 4-8 wt %.
  • the present invention uses polyvinyl alcohol as the main raw material of the composite heat-conducting film, which can make the film have good flexibility; both sides of the composite heat-conducting film are polyvinyl alcohol layers, and the surface does not contain graphene, so that the composite heat-conducting film has good insulation performance ;
  • the middle layer is a polyvinyl alcohol-graphene layer, wherein graphene can form a thermal conductive network inside the composite film, so that the composite thermal conductive film has excellent thermal conductivity.
  • the degree of polymerization of the polyvinyl alcohol is preferably 1500-2400, more preferably 1700-2000; the sheet thickness of the graphene oxide is 0.8-1.3 nm, more preferably 1-1.2 nm.
  • the present invention provides a method for preparing the above-mentioned insulating polyvinyl alcohol composite thermally conductive film, comprising the following steps:
  • polyvinyl alcohol, film-forming aid and water are mixed to obtain polyvinyl alcohol solution
  • the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand and heat-dried to obtain an insulating polyvinyl alcohol composite thermally conductive film; the temperature of the heat-drying is 60-100° C., The time is 8 to 16h;
  • the steps (1) to (2) are not limited in time sequence.
  • polyvinyl alcohol, film-forming aid and water are mixed to obtain a polyvinyl alcohol solution.
  • the degree of polymerization of the polyvinyl alcohol is preferably 1500-2400, more preferably 1700-2000; the polyvinyl alcohol is preferably polyvinyl alcohol particles.
  • the film-forming adjuvant is preferably one or more of glycerol, sodium alginate, propylene glycol and dopamine.
  • the mass ratio of the polyvinyl alcohol, the film-forming aid and the water is preferably 5-9:0.5-2:100, more preferably 6-8:1-1.5:100.
  • the present invention has no special requirements on the mixing method, and a mixing method well-known to those skilled in the art can be used, such as stirring and mixing.
  • the present invention has no special requirements on the mixing time, and it is sufficient to ensure that the polyvinyl alcohol solution is a uniform and transparent solution.
  • the mixing is magnetic stirring, and the temperature of the magnetic stirring is 90° C. and the time is 2 hours.
  • Polyvinyl alcohol is an environmentally friendly water-soluble polymer with good film-forming properties.
  • the formed film is transparent, strong and soft. Compared with other resin materials, its tensile strength, tearing Physical properties such as strength and wear resistance are higher.
  • the present invention uses polyvinyl alcohol as the matrix of the composite heat-conducting film, which can make the composite heat-conducting film have good flexibility.
  • the present invention provides a graphene oxide aqueous dispersion.
  • the mass concentration of the graphene oxide aqueous dispersion is preferably 0.1-2wt%, more preferably 0.5-1.5wt%; the graphene oxide sheet thickness is 0.8-1.3nm, more preferably 1 ⁇ 1.2nm.
  • the present invention has no special instructions on the source of the graphene oxide aqueous dispersion, and the conventional commercially available graphene oxide aqueous dispersion in this field can be used or prepared by itself.
  • the preparation method of the graphene oxide aqueous dispersion is preferably: mixing graphene oxide with water to obtain the graphene oxide aqueous dispersion.
  • the mixing is ultrasonic 2min under 100W.
  • the present invention uses graphene oxide as the raw material of the composite thermally conductive film, wherein the cost of graphene oxide is much lower than that of graphene, and it contains many oxygen-containing functional groups such as hydroxyl and carboxyl groups, which can be well dispersed in the water-soluble polymer matrix, and can reduce Interfacial thermal resistance effect caused by poor compatibility between thermally conductive fillers and polymer matrix and weak interfacial bonding.
  • the present invention mixes the polyvinyl alcohol solution, the graphene oxide aqueous dispersion and the reducing agent to obtain a polyvinyl alcohol/graphene oxide/reducing agent mixed solution.
  • the reducing agent is preferably one or more of ascorbic acid, hydrazine hydrate and hydrogen iodide.
  • the mass ratio of the polyvinyl alcohol to graphene oxide is preferably 100:1-10, more preferably 100:4-8; the mass ratio of the reducing agent to graphene oxide is preferably 1-13 : 1, more preferably 4 to 9:1.
  • the mixing preferably comprises the following steps:
  • the polyvinyl alcohol/graphene oxide mixed solution and the reducing agent are magnetically stirred and mixed to obtain the polyvinyl alcohol/graphene oxide/reducing agent mixed solution.
  • the power of the ultrasonic mixing is preferably 100W, and the time is preferably 1-5 minutes, more preferably 2-4 minutes; the rotating speed of the magnetic stirring and mixing is preferably 200-500 rpm, and the time is preferably 0.5- 2h.
  • the graphene oxide and the PVA can be uniformly mixed by such a mixing manner, and the operation is convenient.
  • the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, allowed to stand and heated and dried to obtain insulating polyvinyl alcohol.
  • Composite thermally conductive film In the present invention, the carrier substrate of the film is preferably stainless steel when the film is scraped; in the present invention, an automatic film coating machine is preferably used for the scraping, and the scraping rate is preferably 75-100 mm/s.
  • the fillers (referring to graphene oxide) can be arranged in an orderly manner in the polyvinyl alcohol matrix, which can effectively reduce phonon scattering, build a thermal conduction network, and improve the thermal conduction of the composite material. performance.
  • the standing time is preferably 25-40° C., more preferably 30-35° C., and the time is preferably 1-2 h, more preferably 1.5 h.
  • the heating and drying are preferably carried out in a constant temperature oven; in the present invention, the temperature of the heating and drying is preferably 60-100°C, more preferably 70-90°C; the time is preferably 8-16h, more preferably 10 ⁇ 14h.
  • the invention can make the obtained composite film have a three-layer structure with stable and clear interface.
  • the water solvent in the wet film layer will evaporate continuously after scraping the film.
  • the covalent bond in the reduced graphene oxide sheet layer is stronger than
  • the hydrogen bond between graphene oxide and polyvinyl alcohol is reduced, and the reduced graphene oxide will agglomerate, and a small amount of polyvinyl alcohol in the film layer tends to be distributed on both sides of the composite film, so that the film layer has polyvinyl alcohol/polyvinyl alcohol.
  • the insulating polyvinyl alcohol composite thermally conductive film provided by the present invention and its preparation method will be described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.
  • step (3) 100 mL of the polyvinyl alcohol solution obtained in step (1) and 13 mL of the graphene oxide dispersion obtained in step (2) were mixed and ultrasonically dispersed for 2 min under high-frequency ultrasound to obtain uniformly dispersed polyvinyl alcohol/graphene oxide mixture;
  • the AFM diagram of the graphene oxide used in the present invention is shown in FIG. 1
  • the sheet thickness of the graphene oxide is shown in FIG. 2 .
  • FIG. 3 A transmission electron microscope (TEM) test is carried out on the cross section of the obtained insulating polyvinyl alcohol composite thermally conductive film, and the obtained results are shown in Figure 3.
  • the insulating polyvinyl alcohol composite thermally conductive film provided by the present invention has a "sandwich" shape.
  • the structure has a polyvinyl alcohol-graphene layer located in the middle and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer, wherein the thickness of the polyvinyl alcohol-graphene layer is about 6-100 ⁇ m, and the polyethylene The thickness of the layer is about 0.1 to 3 ⁇ m.
  • Example 2 The difference between Example 2 and Example 1 is that in step (3), the volume of the graphene oxide dispersion liquid is 40 mL, and finally an insulating polyvinyl alcohol composite thermal conductive film with a graphene content of 3 wt % is obtained.
  • the obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .
  • Example 3 The difference between Example 3 and Example 1 is that in step (3), the volume of the graphene oxide dispersion liquid is 67 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 5 wt % is obtained.
  • the obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .
  • Example 4 The difference between Example 4 and Example 1 is that the volume of the graphene oxide dispersion in step (3) is 97 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 7 wt % is obtained.
  • the obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .
  • Example 5 The difference between Example 5 and Example 1 is that the volume of the graphene oxide dispersion in step (3) is 142 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 10 wt % is obtained.
  • the obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .
  • the thermal conductivity, tensile strength and electrical insulation properties of the films obtained in Examples 1 to 5 and Comparative Example 1 were tested respectively, and the results obtained are listed in Table 1.
  • the thermal conductivity diagram of the film is shown in Figure 4, the tensile strength diagram is shown in Figure 5, and the volume resistivity diagram is shown in Figure 6.
  • Example 1 0.930 50.3 4.51 ⁇ 10 9
  • Example 2 3.13 54.1 3.66 ⁇ 10 9
  • Example 3 4.00 55.7 3.26 ⁇ 10 9
  • Example 4 3.91 60.0 2.47 ⁇ 10 9
  • Example 5 3.44 71.8 1.53 ⁇ 10 9 Comparative Example 1 0.410 6.79 --
  • the insulating polyvinyl alcohol composite thermally conductive film prepared by the present invention has good electrical insulation properties, and its volume resistivity is all >10 9 ⁇ , and when the graphene content is 5wt%, the composite film thermally The conductivity reaches the maximum value of 4.00Wm -1 K -1 , which is 971% higher than that of pure polyvinyl alcohol film 0.4125Wm -1 K -1 , which greatly expands the application of polymer materials in the field of thermal management. Scope of application.
  • the insulating polyvinyl alcohol composite thermally conductive film obtained in Example 3 was rolled and folded into a boat shape, as shown in FIG. 7 . It can be seen from FIG. 7 that no cracks are found on the surface of the film during the process of rolling and folding, indicating that the film prepared by the present invention has good flexibility and has great application potential in flexible electronic devices.

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Abstract

An insulating polyvinyl alcohol composite heat-conducting film and a preparation method therefor. The composite heat-conducting film comprises a polyvinyl alcohol-graphene layer and polyvinyl alcohol layers located on both sides of the polyvinyl alcohol-graphene layer. The thickness of the polyvinyl alcohol-graphene layer is 6-100 μm, and the thicknesses of the polyvinyl alcohol layers are independently 0.1-3 μm. The composite heat-conducting film has a "sandwich" structure, both sides of the composite heat-conducting film are polyvinyl alcohol layers, the surface does not contain graphene, and the middle layer is a polyvinyl alcohol-graphene layer, so that the composite heat-conducting film has excellent heat-conducting properties and good flexibility.

Description

[根据细则37.2由ISA制定的发明名称]　绝缘聚乙烯醇复合导热薄膜及其制备方法[Name of invention formulated by ISA according to Rule 37.2] Insulating polyvinyl alcohol composite thermally conductive film and its preparation method

本申请要求于2020年9月18日提交中国专利局、申请号为202010984458.0、发明名称为“一种绝缘聚乙烯醇复合导热薄膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on September 18, 2020 with the application number 202010984458.0 and the invention titled "An insulating polyvinyl alcohol composite thermally conductive film and its preparation method", the entire contents of which are approved by Reference is incorporated in this application.

技术领域technical field

本发明涉及导热材料技术领域，特别涉及一种绝缘聚乙烯醇复合导热薄膜及其制备方法。The invention relates to the technical field of thermally conductive materials, in particular to an insulating polyvinyl alcohol composite thermally conductive film and a preparation method thereof.

背景技术Background technique

在电子产品不断朝着向小型化、轻薄化发展的过程中，其散热问题也逐渐凸显出来。研究表明电子产品的可靠性与工作温度呈指数关系，工作温度的微小差异(10～15℃)将导致电子设备的使用寿命降低50％。聚合物由于具有重量轻、柔韧、成本低、易加工成型等优点，在现代电子产品的热管理方面具有广阔的应用前景。然而，聚合物极低的本征热导率(<0.5Wm -1K -1)限制了其在热电材料方面的应用。众多研究热衷于通过向聚合物基体中添加大量无机填料如BN、Al 2O 3、AlN等来提升热导率，但通常热导率值提升至1～5W/(Mk)，填料的含量需要高于30wt％，这将严重损失聚合物良好的柔韧性，甚至使其加工成型变得困难。因此，在低填料载荷下使用具有较高热导率的填料来提升聚合物复合材料的导热性能是至关重要的。 In the process of developing towards miniaturization and thinning of electronic products, the heat dissipation problem has gradually become prominent. Studies have shown that the reliability of electronic products is exponentially related to operating temperature, and a small difference in operating temperature (10-15°C) will reduce the service life of electronic equipment by 50%. Polymers have broad application prospects in the thermal management of modern electronic products due to their advantages of light weight, flexibility, low cost, and easy processing. However, the extremely low intrinsic thermal conductivity (<0.5Wm -1 K -1 ) of polymers limits their application in thermoelectric materials. Many studies are keen to increase the thermal conductivity by adding a large amount of inorganic fillers such as BN, Al 2 O 3 , AlN, etc. Above 30wt%, this will seriously lose the good flexibility of the polymer, and even make it difficult to process and shape. Therefore, it is crucial to use fillers with higher thermal conductivity at low filler loadings to improve the thermal conductivity of polymer composites.

自2004年被发现以来，石墨烯因具有独特的性质引起了广泛的关注，如大的比表面积(约为2630m 2g -1)和超高的热导率(约为5300Wm -1K -1)，使得石墨烯成为制备聚合物基导热复合材料的理想选择。然而，石墨烯因具有高的电导率(10 6S/cm)，当石墨烯掺杂到聚合物基体中构建复合材料时，将会显著提升复合材料的电导率，严重限制了其在电子器件热管理领域的应用。因此，如何在不牺牲复合材料优良的电绝缘性能和柔韧性的前提下提高材料的热导率仍然是一个很大的挑战。 Since its discovery in 2004, graphene has attracted widespread attention due to its unique properties, such as a large specific surface area (about 2630m 2 g -1 ) and ultra-high thermal conductivity (about 5300Wm -1 K -1 ) ), making graphene an ideal choice for the preparation of polymer-based thermally conductive composites. However, due to the high electrical conductivity (10 6 S/cm) of graphene, when graphene is doped into the polymer matrix to construct the composite material, the electrical conductivity of the composite material will be significantly improved, which severely limits its application in electronic devices. Applications in the field of thermal management. Therefore, how to improve the thermal conductivity of the composites without sacrificing the excellent electrical insulating properties and flexibility of the composites remains a great challenge.

发明内容SUMMARY OF THE INVENTION

有鉴于此，本发明的目的在于提供一种绝缘聚乙烯醇复合导热薄膜及其制备方法，本发明提供的绝缘聚乙烯醇复合导热薄膜同时具有良好的导 热性能、绝缘性能和柔性。In view of this, the object of the present invention is to provide a kind of insulating polyvinyl alcohol composite heat-conducting film and preparation method thereof, and the insulating polyvinyl alcohol composite heat-conducting film provided by the present invention has good thermal conductivity, insulation performance and flexibility simultaneously.

为了实现上述发明的目的，本发明提供以下技术方案：In order to realize the purpose of the above invention, the present invention provides the following technical solutions:

本发明提供了一种绝缘聚乙烯醇复合导热薄膜，包括聚乙烯醇-石墨烯层和位于所述聚乙烯醇-石墨烯层两侧的聚乙烯醇层；The invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer;

所述聚乙烯醇-石墨烯层的厚度为6～100μm；所述聚乙烯醇层的厚度独立为0.1～3μm。The thickness of the polyvinyl alcohol-graphene layer is 6-100 μm; the thickness of the polyvinyl alcohol layer is independently 0.1-3 μm.

优选的，所述绝缘聚乙烯醇复合导热薄膜中石墨烯的含量为1～10wt％。Preferably, the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 1-10 wt %.

优选的，所述绝缘聚乙烯醇复合导热薄膜中石墨烯的含量为4～8wt％。Preferably, the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 4-8 wt %.

本发明提供了一种绝缘聚乙烯醇复合导热薄膜的制备方法，包括以下步骤：The invention provides a preparation method of an insulating polyvinyl alcohol composite thermally conductive film, comprising the following steps:

(1)将聚乙烯醇、成膜助剂和水混合，得到聚乙烯醇溶液；(1) polyvinyl alcohol, film-forming aid and water are mixed to obtain polyvinyl alcohol solution;

(2)提供氧化石墨烯水分散液；(2) providing graphene oxide aqueous dispersion;

(3)将所述聚乙烯醇溶液、氧化石墨烯水分散液和还原剂混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液；(3) mixing described polyvinyl alcohol solution, graphene oxide aqueous dispersion and reducing agent, obtains polyvinyl alcohol/graphene oxide/reducing agent mixed solution;

(4)将所述聚乙烯醇/氧化石墨烯/还原剂混合液依次进行刮膜、静置和加热干燥，得到绝缘聚乙烯醇复合导热薄膜；所述加热干燥的温度为60～100℃，时间为8～16h；(4) The polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand and heat-dried to obtain an insulating polyvinyl alcohol composite thermally conductive film; the temperature of the heat-drying is 60-100° C., The time is 8 to 16h;

所述步骤(1)～(2)没有时间顺序的限制。The steps (1) to (2) are not limited in time sequence.

优选的，所述步骤(1)中聚乙烯醇的聚合度为1500～2400。Preferably, the degree of polymerization of polyvinyl alcohol in the step (1) is 1500-2400.

优选的，所述步骤(1)中的成膜助剂为甘油、海藻酸钠、丙二醇和多巴胺中的一种或几种。Preferably, the film-forming adjuvant in the step (1) is one or more of glycerol, sodium alginate, propylene glycol and dopamine.

优选的，所述聚乙烯醇、成膜助剂和水的质量比为5～9:0.5～2:100。Preferably, the mass ratio of the polyvinyl alcohol, the film-forming aid and the water is 5-9:0.5-2:100.

优选的，所述步骤(2)中氧化石墨烯水分散液的质量浓度为0.1～2wt％；所述氧化石墨烯的片层厚度为0.8～1.3nm。Preferably, in the step (2), the mass concentration of the graphene oxide aqueous dispersion liquid is 0.1-2 wt %; the sheet thickness of the graphene oxide is 0.8-1.3 nm.

优选的，所述步骤(3)中的还原剂为抗坏血酸、水合肼和碘化氢中的一种或几种。Preferably, the reducing agent in the step (3) is one or more of ascorbic acid, hydrazine hydrate and hydrogen iodide.

优选的，所述聚乙烯醇/氧化石墨烯/还原剂混合液中，聚乙烯醇与氧化石墨烯的质量比为100：1～10；所述还原剂与氧化石墨烯的质量比为1～13:1。Preferably, in the polyvinyl alcohol/graphene oxide/reducing agent mixed solution, the mass ratio of polyvinyl alcohol to graphene oxide is 100:1 to 10; the mass ratio of the reducing agent to graphene oxide is 1 to 13:1.

优选的，所述步骤(3)包括以下步骤：Preferably, the step (3) includes the following steps:

(31)将聚乙烯醇溶液和氧化石墨烯水分散液进行超声混合，得到聚乙烯醇/氧化石墨烯混合液；(31) ultrasonic mixing is carried out with polyvinyl alcohol solution and graphene oxide aqueous dispersion to obtain polyvinyl alcohol/graphene oxide mixed solution;

(32)将所述聚乙烯醇/氧化石墨烯混合液与还原剂进行磁力搅拌混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液。(32) The polyvinyl alcohol/graphene oxide mixed solution and the reducing agent are magnetically stirred and mixed to obtain the polyvinyl alcohol/graphene oxide/reducing agent mixed solution.

优选的，所述超声混合的功率为100W，时间为1～5min；Preferably, the power of the ultrasonic mixing is 100W, and the time is 1-5min;

所述磁力搅拌混合的转速为200～500转/分钟，时间为0.5～2h。The rotating speed of the magnetic stirring and mixing is 200-500 rpm, and the time is 0.5-2h.

优选的，所述步骤(4)中静置的温度为25～40℃，时间为1～2h。Preferably, the temperature for standing in the step (4) is 25-40° C., and the time is 1-2 h.

本发明提供了一种绝缘聚乙烯醇复合导热薄膜，包括聚乙烯醇-石墨烯层和位于所述聚乙烯醇-石墨烯层两侧的聚乙烯醇层；所述聚乙烯醇-石墨烯层的厚度为6～100μm；所述聚乙烯醇层的厚度独立为0.1～3μm。本发明提供的复合导热薄膜具有“三明治”结构，复合导热薄膜的两侧均为聚乙烯醇层，表面不含有石墨烯，使得复合导热薄膜具有良好的绝缘性能；中间层为聚乙烯醇-石墨烯层，其中石墨烯能够在复合导热薄膜内部形成导热网络，使得复合导热薄膜具有优异的导热性能；本发明使用聚乙烯醇作为复合导热薄膜的主要原料，能够使复合导热薄膜具有良好的柔性。实施例结果表明，本发明提供的绝缘聚乙烯醇复合导热薄膜的体积电阻率>10 9Ω·cm，热导率可达4.00Wm -1K -1，且具有良好的柔性。 The invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer; the polyvinyl alcohol-graphene layer The thickness of the polyvinyl alcohol layer is 6-100 μm; the thickness of the polyvinyl alcohol layer is independently 0.1-3 μm. The composite heat-conducting film provided by the invention has a "sandwich" structure, both sides of the composite heat-conducting film are polyvinyl alcohol layers, and the surface does not contain graphene, so that the composite heat-conducting film has good insulating properties; the middle layer is polyvinyl alcohol-graphite Graphene layer, wherein graphene can form a thermal conduction network inside the composite thermally conductive film, so that the composite thermally conductive film has excellent thermal conductivity; the present invention uses polyvinyl alcohol as the main raw material of the composite thermally conductive film, which can make the composite thermally conductive film have good flexibility. The results of the examples show that the volume resistivity of the insulating polyvinyl alcohol composite thermally conductive film provided by the present invention is >10 9 Ω·cm, the thermal conductivity can reach 4.00Wm -1 K -1 , and has good flexibility.

本发明提供了一种绝缘聚乙烯醇复合导热薄膜的制备方法，本发明将所述聚乙烯醇溶液、氧化石墨烯水分散液和还原剂混合，聚乙烯醇/氧化石墨烯/还原剂混合液，再将所述聚乙烯醇/氧化石墨烯/还原剂混合液依次进行刮膜、静置和加热干燥，得到绝缘聚乙烯醇复合导热薄膜。本发明先进行刮膜成型，再在静置的过程中将氧化石墨烯被原位还原为还原氧化石墨烯。在静置和加热干燥的过程中，刮膜后膜层中的水溶剂会不断蒸发，在溶剂蒸发的过程中，由于还原氧化石墨烯片层中的共价键强于还原氧化石墨烯与聚乙烯醇之间氢键，还原氧化石墨烯会发生团聚，同时膜层中的少量聚乙烯醇趋向于分布于复合薄膜的两侧，从而使膜层具有聚乙烯醇/聚乙烯醇-石墨烯/聚乙烯醇的三明治结构。本发明通过对加热干燥的温度和时间进行控制，能够使所得的复合薄膜具有稳定、界面清晰的三层结构。本发明通过先成型再将氧化石墨烯原位还原为石墨烯的方法，解决了直接 用石墨烯作为填料难分散的问题，有利于制备均匀的复合导热薄膜。同时，本发明提供的制备方法不使用有机溶剂，环保无污染；本发明操作简单、成本低廉，易于实现工业化大批量生产。The invention provides a preparation method of an insulating polyvinyl alcohol composite thermally conductive film. The present invention mixes the polyvinyl alcohol solution, graphene oxide aqueous dispersion and a reducing agent, and a polyvinyl alcohol/graphene oxide/reducing agent mixed solution , and then the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand, and heated to dry to obtain an insulating polyvinyl alcohol composite heat-conducting film. In the present invention, scraping film forming is performed first, and then the graphene oxide is in-situ reduced to reduced graphene oxide in the process of standing. During the process of standing and heating and drying, the water solvent in the film layer will evaporate continuously after the film is wiped. Hydrogen bonds between vinyl alcohols and reduced graphene oxide will agglomerate, and at the same time a small amount of polyvinyl alcohol in the film tends to be distributed on both sides of the composite film, so that the film has polyvinyl alcohol/polyvinyl alcohol-graphene/ Sandwich structure of polyvinyl alcohol. By controlling the temperature and time of heating and drying, the invention can make the obtained composite film have a three-layer structure with stable and clear interface. The present invention solves the problem of directly using graphene as a filler and is difficult to disperse by first forming and then reducing graphene oxide to graphene in situ, and is conducive to the preparation of a uniform composite thermally conductive film. At the same time, the preparation method provided by the invention does not use organic solvents, is environmentally friendly and pollution-free; the invention has simple operation, low cost, and is easy to realize industrialized mass production.

附图说明Description of drawings

图1为实施例1中氧化石墨烯的AFM图；Fig. 1 is the AFM figure of graphene oxide in embodiment 1;

图2为实施例1中氧化石墨烯的片层厚度；Fig. 2 is the sheet thickness of graphene oxide in embodiment 1;

图3为实施例1所得绝缘聚乙烯醇复合导热薄膜的TEM图；Fig. 3 is the TEM image of the insulating polyvinyl alcohol composite thermally conductive film obtained in Example 1;

图4为实施例1～5和对比例1所得薄膜的热导率图；4 is a thermal conductivity diagram of the films obtained in Examples 1 to 5 and Comparative Example 1;

图5为实施例1～5和对比例1所得薄膜的抗拉强度图；Fig. 5 is the tensile strength diagram of the films obtained in Examples 1-5 and Comparative Example 1;

图6为实施例1～5所得薄膜的体积电阻率图；6 is a volume resistivity diagram of the thin films obtained in Examples 1 to 5;

图7为实施例3所得薄膜的柔韧性展示图。FIG. 7 is a graph showing the flexibility of the film obtained in Example 3. FIG.

具体实施方式detailed description

本发明提供了一种绝缘聚乙烯醇复合导热薄膜，包括聚乙烯醇-石墨烯层和位于所述聚乙烯醇-石墨烯层两侧的聚乙烯醇层。The invention provides an insulating polyvinyl alcohol composite heat-conducting film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer.

在本发明中，所述聚乙烯醇/石墨烯层的厚度优选为6～100μm，更优选为10～80μm，进一步优选为20～60μm；所述聚乙烯醇层的厚度独立优选为0.1～3μm，更优选为0.2～2μm，进一步优选为0.5～2μm。在本发明中，所述绝缘聚乙烯醇复合导热薄膜的厚度优选为6.2～106μm，更优选为10～80μm，进一步优选为20～50μm。In the present invention, the thickness of the polyvinyl alcohol/graphene layer is preferably 6-100 μm, more preferably 10-80 μm, further preferably 20-60 μm; the thickness of the polyvinyl alcohol layer is preferably 0.1-3 μm independently , more preferably 0.2 to 2 μm, still more preferably 0.5 to 2 μm. In the present invention, the thickness of the insulating polyvinyl alcohol composite thermally conductive film is preferably 6.2 to 106 μm, more preferably 10 to 80 μm, and further preferably 20 to 50 μm.

在本发明中，所述绝缘聚乙烯醇复合导热薄膜中石墨烯的含量优选为1～10wt％，更优选为4～8wt％。In the present invention, the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is preferably 1-10 wt %, more preferably 4-8 wt %.

本发明使用聚乙烯醇作为复合导热薄膜的主要原料，能够使薄膜具有良好的柔性；复合导热薄膜的两侧均为聚乙烯醇层，表面不含有石墨烯，使得复合导热薄膜具有良好的绝缘性能；中间层为聚乙烯醇-石墨烯层，其中石墨烯能够在复合薄膜内部形成导热网络，使得复合导热薄膜具有优异的导热性能。The present invention uses polyvinyl alcohol as the main raw material of the composite heat-conducting film, which can make the film have good flexibility; both sides of the composite heat-conducting film are polyvinyl alcohol layers, and the surface does not contain graphene, so that the composite heat-conducting film has good insulation performance ; The middle layer is a polyvinyl alcohol-graphene layer, wherein graphene can form a thermal conductive network inside the composite film, so that the composite thermal conductive film has excellent thermal conductivity.

在本发明中，所述聚乙烯醇的聚合度优选为1500～2400，更优选为1700～2000；所述氧化石墨烯的片层厚度为0.8～1.3nm，更优选为1～1.2nm。In the present invention, the degree of polymerization of the polyvinyl alcohol is preferably 1500-2400, more preferably 1700-2000; the sheet thickness of the graphene oxide is 0.8-1.3 nm, more preferably 1-1.2 nm.

本发明提供了上述绝缘聚乙烯醇复合导热薄膜的制备方法，包括以下步骤：The present invention provides a method for preparing the above-mentioned insulating polyvinyl alcohol composite thermally conductive film, comprising the following steps:

(1)将聚乙烯醇、成膜助剂和水混合，得到聚乙烯醇溶液；(1) polyvinyl alcohol, film-forming aid and water are mixed to obtain polyvinyl alcohol solution;

(2)提供氧化石墨烯水分散液；(2) providing graphene oxide aqueous dispersion;

(3)将所述聚乙烯醇溶液、氧化石墨烯水分散液和还原剂混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液；(3) mixing described polyvinyl alcohol solution, graphene oxide aqueous dispersion and reducing agent, obtains polyvinyl alcohol/graphene oxide/reducing agent mixed solution;

(4)将所述聚乙烯醇/氧化石墨烯/还原剂混合液依次进行刮膜、静置和加热干燥，得到绝缘聚乙烯醇复合导热薄膜；所述加热干燥的温度为60～100℃，时间为8～16h；(4) The polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand and heat-dried to obtain an insulating polyvinyl alcohol composite thermally conductive film; the temperature of the heat-drying is 60-100° C., The time is 8 to 16h;

所述步骤(1)～(2)没有时间顺序的限制。The steps (1) to (2) are not limited in time sequence.

如无特殊说明，本发明所用原料均为市售。Unless otherwise specified, the raw materials used in the present invention are all commercially available.

本发明将聚乙烯醇、成膜助剂和水混合，得到聚乙烯醇溶液。在本发明中，所述聚乙烯醇的聚合度优选为1500～2400，更优选为1700～2000；所述聚乙烯醇优选为聚乙烯醇颗粒。在本发明中，所述成膜助剂优选为甘油、海藻酸钠、丙二醇和多巴胺中的一种或几种。在本发明中，所述聚乙烯醇、成膜助剂和水的质量比优选为5～9:0.5～2:100，更优选为6～8:1～1.5:100。本发明对所述混合的方式没有特殊的要求，使用本领域技术人员熟知的混合方式即可，具体的如搅拌混合。本发明对所述混合的时间没有特殊的要求，保证所述聚乙烯醇溶液为均一透明溶液即可。作为本发明的一个具体实施例，所述混合为磁力搅拌，所述磁力搅拌的温度为90℃，时间为2h。聚乙烯醇是一种环境友好的水溶性聚合物，具有良好的成膜性，所形成的膜具有透明、强韧、柔软的特点，并且相对于其他树脂类材料，其抗张强度、撕裂强度、耐磨强度等物理性能更高。本发明使用聚乙烯醇作为复合导热薄膜的基体，能够使复合导热薄膜具有良好的柔性。In the present invention, polyvinyl alcohol, film-forming aid and water are mixed to obtain a polyvinyl alcohol solution. In the present invention, the degree of polymerization of the polyvinyl alcohol is preferably 1500-2400, more preferably 1700-2000; the polyvinyl alcohol is preferably polyvinyl alcohol particles. In the present invention, the film-forming adjuvant is preferably one or more of glycerol, sodium alginate, propylene glycol and dopamine. In the present invention, the mass ratio of the polyvinyl alcohol, the film-forming aid and the water is preferably 5-9:0.5-2:100, more preferably 6-8:1-1.5:100. The present invention has no special requirements on the mixing method, and a mixing method well-known to those skilled in the art can be used, such as stirring and mixing. The present invention has no special requirements on the mixing time, and it is sufficient to ensure that the polyvinyl alcohol solution is a uniform and transparent solution. As a specific embodiment of the present invention, the mixing is magnetic stirring, and the temperature of the magnetic stirring is 90° C. and the time is 2 hours. Polyvinyl alcohol is an environmentally friendly water-soluble polymer with good film-forming properties. The formed film is transparent, strong and soft. Compared with other resin materials, its tensile strength, tearing Physical properties such as strength and wear resistance are higher. The present invention uses polyvinyl alcohol as the matrix of the composite heat-conducting film, which can make the composite heat-conducting film have good flexibility.

本发明提供氧化石墨烯水分散液。在本发明中，所述氧化石墨烯水分散液的质量浓度优选为0.1～2wt％，更优选为0.5～1.5wt％；所述氧化石墨烯的片层厚度为0.8～1.3nm，更优选为1～1.2nm。本发明对所述氧化石墨烯水分散液的来源没有特殊的说明，使用本领域常规市售的氧化石墨烯水分散液或自行制备均可。当自行制备所述氧化石墨烯水分散液时，所述氧化石墨烯水分散液的制备方法优选为：将氧化石墨烯与水混合，得到氧化石墨烯水分散液。作为本发明的一个具体实施例，所述混合为100W下超 声2min。The present invention provides a graphene oxide aqueous dispersion. In the present invention, the mass concentration of the graphene oxide aqueous dispersion is preferably 0.1-2wt%, more preferably 0.5-1.5wt%; the graphene oxide sheet thickness is 0.8-1.3nm, more preferably 1～1.2nm. The present invention has no special instructions on the source of the graphene oxide aqueous dispersion, and the conventional commercially available graphene oxide aqueous dispersion in this field can be used or prepared by itself. When preparing the graphene oxide aqueous dispersion by oneself, the preparation method of the graphene oxide aqueous dispersion is preferably: mixing graphene oxide with water to obtain the graphene oxide aqueous dispersion. As a specific embodiment of the present invention, the mixing is ultrasonic 2min under 100W.

本发明使用氧化石墨烯作为复合导热薄膜的原料，其中氧化石墨烯成本远低于石墨烯，且含有羟基、羧基等众多含氧官能团，可以很好地分散在水溶性聚合物基体中，能减少因导热填料与聚合物基体相容性差、界面结合较弱而引起的界面热阻效应。The present invention uses graphene oxide as the raw material of the composite thermally conductive film, wherein the cost of graphene oxide is much lower than that of graphene, and it contains many oxygen-containing functional groups such as hydroxyl and carboxyl groups, which can be well dispersed in the water-soluble polymer matrix, and can reduce Interfacial thermal resistance effect caused by poor compatibility between thermally conductive fillers and polymer matrix and weak interfacial bonding.

得到聚乙烯醇溶液和氧化石墨烯水分散液后，本发明将所述聚乙烯醇溶液、氧化石墨烯水分散液和还原剂混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液。在本发明中，所述还原剂优选为抗坏血酸、水合肼和碘化氢中的一种或几种。在本发明中，所述聚乙烯醇与氧化石墨烯的质量比优选为100：1～10，更优选为100:4～8；所述还原剂与氧化石墨烯的质量比优选为1～13:1，更优选为4～9:1。After the polyvinyl alcohol solution and the graphene oxide aqueous dispersion are obtained, the present invention mixes the polyvinyl alcohol solution, the graphene oxide aqueous dispersion and the reducing agent to obtain a polyvinyl alcohol/graphene oxide/reducing agent mixed solution. In the present invention, the reducing agent is preferably one or more of ascorbic acid, hydrazine hydrate and hydrogen iodide. In the present invention, the mass ratio of the polyvinyl alcohol to graphene oxide is preferably 100:1-10, more preferably 100:4-8; the mass ratio of the reducing agent to graphene oxide is preferably 1-13 : 1, more preferably 4 to 9:1.

在本发明中，所述混合优选包括以下步骤：In the present invention, the mixing preferably comprises the following steps:

(31)将聚乙烯醇溶液和氧化石墨烯水分散液进行超声混合，得到聚乙烯醇/氧化石墨烯混合液；(31) ultrasonic mixing is carried out with polyvinyl alcohol solution and graphene oxide aqueous dispersion to obtain polyvinyl alcohol/graphene oxide mixed solution;

(32)将所述聚乙烯醇/氧化石墨烯混合液与还原剂进行磁力搅拌混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液。(32) The polyvinyl alcohol/graphene oxide mixed solution and the reducing agent are magnetically stirred and mixed to obtain the polyvinyl alcohol/graphene oxide/reducing agent mixed solution.

在本发明中，所述超声混合的功率优选为100W，时间优选为1～5min，更优选为2～4min；所述磁力搅拌混合的转速优选为200～500转/分钟，时间优选为0.5～2h。本发明通过此种混合方式，能够使氧化石墨烯与PVA达到均匀混合，且操作方便。In the present invention, the power of the ultrasonic mixing is preferably 100W, and the time is preferably 1-5 minutes, more preferably 2-4 minutes; the rotating speed of the magnetic stirring and mixing is preferably 200-500 rpm, and the time is preferably 0.5- 2h. In the present invention, the graphene oxide and the PVA can be uniformly mixed by such a mixing manner, and the operation is convenient.

得到所述聚乙烯醇/氧化石墨烯/还原剂混合液后，本发明将所述聚乙烯醇/氧化石墨烯/还原剂混合液依次进行刮膜、静置和加热干燥，得到绝缘聚乙烯醇复合导热薄膜。在本发明中，所述刮膜时薄膜的承载基体优选为不锈钢；本发明优选使用自动涂膜机进行所述刮膜，所述刮膜的速率优选为75～100mm/s。本发明通过使用自动刮膜机进行所述刮膜，可以使填料(指氧化石墨烯)在聚乙烯醇基体中有序排列，能够有效地减少声子散射，构建导热网络，提升复合材料的导热性能。After the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is obtained, in the present invention, the polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, allowed to stand and heated and dried to obtain insulating polyvinyl alcohol. Composite thermally conductive film. In the present invention, the carrier substrate of the film is preferably stainless steel when the film is scraped; in the present invention, an automatic film coating machine is preferably used for the scraping, and the scraping rate is preferably 75-100 mm/s. In the present invention, by using an automatic film scraping machine to perform the scraping, the fillers (referring to graphene oxide) can be arranged in an orderly manner in the polyvinyl alcohol matrix, which can effectively reduce phonon scattering, build a thermal conduction network, and improve the thermal conduction of the composite material. performance.

在本发明中，所述静置的时间优选为25～40℃，更优选为30～35℃，时间优选为1～2h，更优选为1.5h。In the present invention, the standing time is preferably 25-40° C., more preferably 30-35° C., and the time is preferably 1-2 h, more preferably 1.5 h.

本发明优选在恒温箱中进行所述加热干燥；在本发明中，所述加热干 燥的温度优选为60～100℃，更优选为70～90℃；时间优选为8～16h，更优选为10～14h。本发明通过对加热干燥的温度和时间进行控制，能够使所得的复合薄膜具有稳定、界面清晰的三层结构。In the present invention, the heating and drying are preferably carried out in a constant temperature oven; in the present invention, the temperature of the heating and drying is preferably 60-100°C, more preferably 70-90°C; the time is preferably 8-16h, more preferably 10 ~14h. By controlling the temperature and time of heating and drying, the invention can make the obtained composite film have a three-layer structure with stable and clear interface.

在本发明中，在静置和加热干燥的过程中，刮膜后湿膜层中的水溶剂会不断蒸发，在溶剂蒸发的过程中，由于还原氧化石墨烯片层中的共价键强于还原氧化石墨烯与聚乙烯醇之间氢键，还原氧化石墨烯会发生团聚，同时膜层中的少量聚乙烯醇趋向于分布于复合薄膜的两侧，从而使膜层具有聚乙烯醇/聚乙烯醇-石墨烯/聚乙烯醇的三明治结构。In the present invention, in the process of standing and heating and drying, the water solvent in the wet film layer will evaporate continuously after scraping the film. During the process of solvent evaporation, the covalent bond in the reduced graphene oxide sheet layer is stronger than The hydrogen bond between graphene oxide and polyvinyl alcohol is reduced, and the reduced graphene oxide will agglomerate, and a small amount of polyvinyl alcohol in the film layer tends to be distributed on both sides of the composite film, so that the film layer has polyvinyl alcohol/polyvinyl alcohol. Vinyl alcohol-graphene/polyvinyl alcohol sandwich structure.

下面结合实施例对本发明提供的绝缘聚乙烯醇复合导热薄膜及其制备方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The insulating polyvinyl alcohol composite thermally conductive film provided by the present invention and its preparation method will be described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

实施例1Example 1

(1)将9g聚乙烯醇颗粒(聚合度为1700)分散于90mL水中，室温下磁力搅拌至溶液均匀透明，之后加入1g甘油，在90℃下磁力搅拌2h，得到聚乙烯醇溶液；(1) Disperse 9g of polyvinyl alcohol particles (polymerization degree of 1700) in 90mL of water, stir magnetically at room temperature until the solution is uniform and transparent, then add 1g of glycerol, and magnetically stir at 90°C for 2h to obtain a polyvinyl alcohol solution;

(2)将0.7g片层厚度为0.8～1.3nm的氧化石墨烯(GO)与99.3mL去离子水混合，在100W下超声2min得到0.7wt％的氧化石墨烯分散液；(2) Mixing 0.7 g of graphene oxide (GO) with a sheet thickness of 0.8 to 1.3 nm and 99.3 mL of deionized water, and ultrasonicating for 2 min at 100 W to obtain a 0.7 wt% graphene oxide dispersion;

(3)将100mL步骤(1)所得的聚乙烯醇溶液和13mL步骤(2)所得的氧化石墨烯分散液混合并在高频超声下超声分散2min，得到均匀分散的聚乙烯醇/氧化石墨烯混合液；(3) 100 mL of the polyvinyl alcohol solution obtained in step (1) and 13 mL of the graphene oxide dispersion obtained in step (2) were mixed and ultrasonically dispersed for 2 min under high-frequency ultrasound to obtain uniformly dispersed polyvinyl alcohol/graphene oxide mixture;

(4)将步骤(3)所得的混合液与抗坏血酸(质量比GO：Vc＝1:6)在室温200rpm下磁力搅拌2h混合均匀，得到聚乙烯醇/氧化石墨烯/还原剂混合液；(4) mixing the mixed solution obtained in step (3) with ascorbic acid (mass ratio GO: Vc=1:6) under magnetic stirring for 2 h at room temperature 200 rpm to obtain a polyvinyl alcohol/graphene oxide/reducing agent mixed solution;

(5)将上述聚乙烯醇/氧化石墨烯/还原剂混合液倒在不锈钢板上，室温下用自动涂膜机刮膜，先30℃下恒温静置1h，再放置于80℃的恒温箱中干燥12h，得到石墨烯含量为1wt％的绝缘聚乙烯醇复合导热薄膜。(5) Pour the above polyvinyl alcohol/graphene oxide/reducing agent mixture on a stainless steel plate, scrape the film with an automatic film coating machine at room temperature, let it stand at a constant temperature of 30 °C for 1 hour, and then place it in a constant temperature box of 80 °C After drying for 12 hours, an insulating polyvinyl alcohol composite thermal conductive film with a graphene content of 1 wt % was obtained.

本发明使用的氧化石墨烯的AFM图如图1所示，氧化石墨烯的片层厚度如图2所示。The AFM diagram of the graphene oxide used in the present invention is shown in FIG. 1 , and the sheet thickness of the graphene oxide is shown in FIG. 2 .

对所得绝缘聚乙烯醇复合导热薄膜的截面进行透射电镜(TEM)测试，所得结果如图3所示，由图3可以看出，本发明提供的绝缘聚乙烯醇 复合导热薄膜具有“三明治”形结构，具有位于中间的聚乙烯醇-石墨烯层和位于所述聚乙烯醇-石墨烯层两侧的聚乙烯醇层，其中聚乙烯醇-石墨烯层的厚度约为6～100μm，聚乙烯层的厚度约为0.1～3μm。A transmission electron microscope (TEM) test is carried out on the cross section of the obtained insulating polyvinyl alcohol composite thermally conductive film, and the obtained results are shown in Figure 3. It can be seen from Figure 3 that the insulating polyvinyl alcohol composite thermally conductive film provided by the present invention has a "sandwich" shape. The structure has a polyvinyl alcohol-graphene layer located in the middle and a polyvinyl alcohol layer located on both sides of the polyvinyl alcohol-graphene layer, wherein the thickness of the polyvinyl alcohol-graphene layer is about 6-100 μm, and the polyethylene The thickness of the layer is about 0.1 to 3 μm.

实施例2Example 2

实施例2与实施例1的区别在于，步骤(3)中氧化石墨烯分散液的体积为40mL，最终得到石墨烯含量为3wt％的绝缘聚乙烯醇复合导热薄膜。The difference between Example 2 and Example 1 is that in step (3), the volume of the graphene oxide dispersion liquid is 40 mL, and finally an insulating polyvinyl alcohol composite thermal conductive film with a graphene content of 3 wt % is obtained.

对所得绝缘聚乙烯醇复合导热薄膜进行TEM测试，结果与图3相似。The obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .

实施例3Example 3

实施例3与实施例1的区别在于，步骤(3)中氧化石墨烯分散液的体积为67mL，最终得到石墨烯含量为5wt％的绝缘聚乙烯醇复合导热薄膜。The difference between Example 3 and Example 1 is that in step (3), the volume of the graphene oxide dispersion liquid is 67 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 5 wt % is obtained.

对所得绝缘聚乙烯醇复合导热薄膜进行TEM测试，结果与图3相似。The obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .

实施例4Example 4

实施例4与实施例1的区别在于，步骤(3)中氧化石墨烯分散液的体积为97mL，最终得到石墨烯含量为7wt％的绝缘聚乙烯醇复合导热薄膜。The difference between Example 4 and Example 1 is that the volume of the graphene oxide dispersion in step (3) is 97 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 7 wt % is obtained.

对所得绝缘聚乙烯醇复合导热薄膜进行TEM测试，结果与图3相似。The obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .

实施例5Example 5

实施例5与实施例1的区别在于，步骤(3)中氧化石墨烯分散液的体积为142mL，最终得到石墨烯含量为10wt％的绝缘聚乙烯醇复合导热薄膜。The difference between Example 5 and Example 1 is that the volume of the graphene oxide dispersion in step (3) is 142 mL, and finally an insulating polyvinyl alcohol composite thermally conductive film with a graphene content of 10 wt % is obtained.

对所得绝缘聚乙烯醇复合导热薄膜进行TEM测试，结果与图3相似。The obtained insulating polyvinyl alcohol composite thermally conductive film was tested by TEM, and the results were similar to those shown in FIG. 3 .

对比例1Comparative Example 1

(1)将9g聚乙烯醇颗粒(聚合度为1700)分散于90mL水中，室温下磁力搅拌至溶液均匀透明，之后加入1g甘油，在90℃下磁力搅拌2h，得到聚乙烯醇溶液；(1) Disperse 9g of polyvinyl alcohol particles (polymerization degree of 1700) in 90mL of water, stir magnetically at room temperature until the solution is uniform and transparent, then add 1g of glycerol, and magnetically stir at 90°C for 2h to obtain a polyvinyl alcohol solution;

(2)将上述聚乙烯醇溶液倒在不锈钢板上，用自动涂膜机刮膜，先30℃下恒温静置1h，再放置于80℃的恒温箱中干燥12h，得到聚乙烯醇薄膜，此薄膜中石墨烯的含量为0。(2) Pour the above-mentioned polyvinyl alcohol solution on a stainless steel plate, scrape the film with an automatic film coating machine, first let it stand at a constant temperature of 30 °C for 1 hour, and then place it in a constant temperature oven of 80 °C to dry for 12 hours to obtain a polyvinyl alcohol film, The graphene content in this film is 0.

性能测试Performance Testing

分别对实施例1～5及对比例1所得薄膜的热导率、抗拉强度、电绝缘性能进行测试，所得结果列于表1中。其中，薄膜的热导率图如图4所示，抗拉强度图如图5所示，体积电阻率图如图6所示。The thermal conductivity, tensile strength and electrical insulation properties of the films obtained in Examples 1 to 5 and Comparative Example 1 were tested respectively, and the results obtained are listed in Table 1. The thermal conductivity diagram of the film is shown in Figure 4, the tensile strength diagram is shown in Figure 5, and the volume resistivity diagram is shown in Figure 6.

表1 薄膜的热导率、抗拉强度、电绝缘性能数据Table 1 Thermal conductivity, tensile strength, and electrical insulation performance data of thin films

项目project 热导率/Wm -1K -1 Thermal conductivity/Wm -1 K -1 抗拉强度/MPaTensile strength/MPa 体积电阻率/Ω·cmVolume resistivity/Ω·cm 实施例1Example 1 0.9300.930 50.350.3 4.51×10 9 4.51×10 9 实施例2Example 2 3.133.13 54.154.1 3.66×10 9 3.66×10 9 实施例3Example 3 4.004.00 55.755.7 3.26×10 9 3.26×10 9 实施例4Example 4 3.913.91 60.060.0 2.47×10 9 2.47×10 9 实施例5Example 5 3.443.44 71.871.8 1.53×10 9 1.53×10 9 对比例1Comparative Example 1 0.4100.410 6.796.79 ----

由表1可以看出，本发明所制得的绝缘聚乙烯醇复合导热薄膜具有良好的电绝缘性能，其体积电阻率均>10 9Ω，而且在石墨烯含量为5wt％时，复合薄膜热导率达到最大值4.00Wm -1K -1，相比于纯的聚乙烯醇薄膜0.4125Wm -1K -1的热导率提升了971％，极大地拓展了聚合物材料在热管理领域的应用范围。 As can be seen from Table 1, the insulating polyvinyl alcohol composite thermally conductive film prepared by the present invention has good electrical insulation properties, and its volume resistivity is all >10 9 Ω, and when the graphene content is 5wt%, the composite film thermally The conductivity reaches the maximum value of 4.00Wm -1 K -1 , which is 971% higher than that of pure polyvinyl alcohol film 0.4125Wm -1 K -1 , which greatly expands the application of polymer materials in the field of thermal management. Scope of application.

将实施例3所得绝缘聚乙烯醇复合导热薄膜卷曲折成小船形状，如图7所示。由图7可以看出，在卷曲、折叠的过程中均未在薄膜表面发现裂痕，表明本发明所制备的薄膜具有良好的柔性，其在柔性电子器件方面具有很大的应用潜力。The insulating polyvinyl alcohol composite thermally conductive film obtained in Example 3 was rolled and folded into a boat shape, as shown in FIG. 7 . It can be seen from FIG. 7 that no cracks are found on the surface of the film during the process of rolling and folding, indicating that the film prepared by the present invention has good flexibility and has great application potential in flexible electronic devices.

以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (13)

一种绝缘聚乙烯醇复合导热薄膜，包括聚乙烯醇-石墨烯层和位于所述聚乙烯醇-石墨烯层两侧的聚乙烯醇层；An insulating polyvinyl alcohol composite thermally conductive film, comprising a polyvinyl alcohol-graphene layer and a polyvinyl alcohol layer on both sides of the polyvinyl alcohol-graphene layer; 所述聚乙烯醇-石墨烯层的厚度为6～100μm；所述聚乙烯醇层的厚度独立为0.1～3μm。The thickness of the polyvinyl alcohol-graphene layer is 6-100 μm; the thickness of the polyvinyl alcohol layer is independently 0.1-3 μm. 根据权利要求1所述的绝缘聚乙烯醇复合导热薄膜，其特征在于，所述绝缘聚乙烯醇复合导热薄膜中石墨烯的含量为1～10wt％。The insulating polyvinyl alcohol composite thermally conductive film according to claim 1, wherein the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 1-10 wt%. 根据权利要求2所述的绝缘聚乙烯醇复合导热薄膜，其特征在于，所述绝缘聚乙烯醇复合导热薄膜中石墨烯的含量为4～8wt％。The insulating polyvinyl alcohol composite thermally conductive film according to claim 2, wherein the content of graphene in the insulating polyvinyl alcohol composite thermally conductive film is 4-8 wt%. 权利要求1～3所述的绝缘聚乙烯醇复合导热薄膜的制备方法，包括以下步骤：The preparation method of the insulating polyvinyl alcohol composite thermally conductive film according to claims 1 to 3, comprising the following steps: (1)将聚乙烯醇、成膜助剂和水混合，得到聚乙烯醇溶液；(1) polyvinyl alcohol, film-forming aid and water are mixed to obtain polyvinyl alcohol solution; (2)提供氧化石墨烯水分散液；(2) providing graphene oxide aqueous dispersion; (3)将所述聚乙烯醇溶液、氧化石墨烯水分散液和还原剂混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液；(3) mixing described polyvinyl alcohol solution, graphene oxide aqueous dispersion and reducing agent, obtains polyvinyl alcohol/graphene oxide/reducing agent mixed solution; (4)将所述聚乙烯醇/氧化石墨烯/还原剂混合液依次进行刮膜、静置和加热干燥，得到绝缘聚乙烯醇复合导热薄膜；所述加热干燥的温度为60～100℃，时间为8～16h；(4) The polyvinyl alcohol/graphene oxide/reducing agent mixed solution is sequentially scraped, left to stand and heat-dried to obtain an insulating polyvinyl alcohol composite thermally conductive film; the temperature of the heat-drying is 60-100° C., The time is 8 to 16h; 所述步骤(1)～(2)没有时间顺序的限制。The steps (1) to (2) are not limited in time sequence. 根据权利要求4所述的制备方法，其特征在于，所述步骤(1)中聚乙烯醇的聚合度为1500～2400。The preparation method according to claim 4, wherein the degree of polymerization of the polyvinyl alcohol in the step (1) is 1500-2400. 根据权利要求4或5所述的制备方法，其特征在于，所述步骤(1)中的成膜助剂为甘油、海藻酸钠、丙二醇和多巴胺中的一种或几种。The preparation method according to claim 4 or 5, wherein the film-forming aid in the step (1) is one or more of glycerol, sodium alginate, propylene glycol and dopamine. 根据权利要求4或5所述的制备方法，其特征在于，所述聚乙烯醇、成膜助剂和水的质量比为5～9:0.5～2:100。The preparation method according to claim 4 or 5, wherein the mass ratio of the polyvinyl alcohol, the film-forming aid and the water is 5-9:0.5-2:100. 根据权利要求4所述的制备方法，其特征在于，所述步骤(2)中氧化石墨烯水分散液的质量浓度为0.1～2wt％；所述氧化石墨烯的片层厚度为0.8～1.3nm。The preparation method according to claim 4, wherein the mass concentration of the graphene oxide aqueous dispersion in the step (2) is 0.1-2 wt %; the sheet thickness of the graphene oxide is 0.8-1.3 nm . 根据权利要求4所述的制备方法，其特征在于，所述步骤(3)中的还原剂为抗坏血酸、水合肼和碘化氢中的一种或几种。The preparation method according to claim 4, wherein the reducing agent in the step (3) is one or more of ascorbic acid, hydrazine hydrate and hydrogen iodide. 根据权利要求4所述的制备方法，其特征在于，所述聚乙烯醇/氧化石墨烯/还原剂混合液中，聚乙烯醇与氧化石墨烯的质量比为100：1～10；所述还原剂与氧化石墨烯的质量比为1～13:1。The preparation method according to claim 4, wherein, in the polyvinyl alcohol/graphene oxide/reducing agent mixed solution, the mass ratio of polyvinyl alcohol to graphene oxide is 100:1-10; The mass ratio of the agent to graphene oxide is 1-13:1. 根据权利要求4所述的制备方法，其特征在于，所述步骤(3)包括以下步骤：The preparation method according to claim 4, wherein the step (3) comprises the following steps: (31)将聚乙烯醇溶液和氧化石墨烯水分散液进行超声混合，得到聚乙烯醇/氧化石墨烯混合液；(31) ultrasonic mixing is carried out with polyvinyl alcohol solution and graphene oxide aqueous dispersion to obtain polyvinyl alcohol/graphene oxide mixed solution; (32)将所述聚乙烯醇/氧化石墨烯混合液与还原剂进行磁力搅拌混合，得到聚乙烯醇/氧化石墨烯/还原剂混合液。(32) The polyvinyl alcohol/graphene oxide mixed solution and the reducing agent are magnetically stirred and mixed to obtain the polyvinyl alcohol/graphene oxide/reducing agent mixed solution. 根据权利要求11所述的制备方法，其特征在于，所述超声混合的功率为100W，时间为1～5min；The preparation method according to claim 11, wherein the power of the ultrasonic mixing is 100W, and the time is 1-5min; 所述磁力搅拌混合的转速为200～500转/分钟，时间为0.5～2h。The rotating speed of the magnetic stirring and mixing is 200-500 rpm, and the time is 0.5-2h. 根据权利要求4所述的制备方法，其特征在于，所述步骤(4)中静置的温度为25～40℃，时间为1～2h。The preparation method according to claim 4, characterized in that, in the step (4), the temperature for standing still is 25-40° C., and the time is 1-2 h.
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