WO2017036082A1 - Matériau composite polymère à haute conductivité thermique, son procédé de préparation et son utilisation - Google Patents

Matériau composite polymère à haute conductivité thermique, son procédé de préparation et son utilisation Download PDF

Info

Publication number
WO2017036082A1
WO2017036082A1 PCT/CN2016/072211 CN2016072211W WO2017036082A1 WO 2017036082 A1 WO2017036082 A1 WO 2017036082A1 CN 2016072211 W CN2016072211 W CN 2016072211W WO 2017036082 A1 WO2017036082 A1 WO 2017036082A1
Authority
WO
WIPO (PCT)
Prior art keywords
boron nitride
polymer composite
thermal conductivity
high thermal
treatment
Prior art date
Application number
PCT/CN2016/072211
Other languages
English (en)
Chinese (zh)
Inventor
孙蓉
曾小亮
王芳芳
许建斌
Original Assignee
中国科学院深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院深圳先进技术研究院 filed Critical 中国科学院深圳先进技术研究院
Publication of WO2017036082A1 publication Critical patent/WO2017036082A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • 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
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention belongs to the technical field of thermal conductive composite materials, and particularly relates to a high thermal conductivity polymer composite material and a preparation method and application thereof.
  • current three-dimensional boron nitride is usually prepared by chemical vapor deposition. Specifically, the precursor of the boron nitride is attached to the template (three-dimensional structure nickel or graphite) of the three-dimensional structure at a high temperature. After the reaction is completed, the template is removed by chemical etching to obtain a three-dimensional structure of boron nitride.
  • the Nanjing University of Aeronautics and Astronautics uses a foam metal as a template to obtain a three-dimensional boron nitride foam having excellent properties such as low density and high thermal stability by chemical vapor deposition and chemical etching.
  • the network of the foam metal prepared by the method has a pore size of several hundred micrometers, and the three-dimensional boron nitride foam prepared by using the template has a low bulk density, which is disadvantageous for its macro preparation.
  • Another method for preparing three-dimensional boron nitride disclosed in Fudan University is to use a chemical vapor deposition method to prepare a porous metal by a high-temperature reduction reaction using a transition metal elemental powder or a transition metal-containing compound as a catalyst.
  • the catalyst skeleton; the hexagonal boron nitride is grown by chemical vapor deposition to obtain a hexagonal boron nitride powder with a catalyst skeleton and three-dimensional boron nitride.
  • the method uses a transition metal element or a transition metal element-containing compound as a raw material, and replacing the conventional metal foam template with a porous catalyst template, the three-dimensional boron nitride obtained by using the foam metal as a catalytic skeleton has a higher porosity; Still using a combination of traditional chemical vapor deposition and chemical etching, resulting in a three-dimensional structure of boron nitride brittle, poor mechanical strength
  • the object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a high thermal conductivity polymer composite material and a preparation method thereof, so as to solve the problem that the existing polymer/thermal conductive ceramic composite material is difficult to be in a polymer matrix composite material. It is difficult to effectively improve the thermal conductivity of polymer/thermally conductive ceramic composites by forming a heat conduction network.
  • Another object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide an application of the high thermal conductive polymer composite material of the present invention to solve the problem that the existing polymer/thermal conductive ceramic composite material is used due to low thermal conductivity. Limited technical issues.
  • the high thermal conductivity polymer composite material comprises a polymer matrix and three-dimensional boron nitride filled in the polymer matrix, and the volume fraction of the three-dimensional boron nitride in the high thermal conductivity polymer composite is 5 -50%.
  • the preparation method of the high thermal conductive polymer composite material comprises the following steps:
  • the boron nitride nanosheet, water and water-soluble polymer are mixed at a mass ratio of 1: (1-50): 100 to obtain a mixture solution;
  • the mixture solution is subjected to a freeze treatment to form a frozen mixture, and the frozen mixture is subjected to freeze-drying treatment to obtain a three-dimensional boron nitride precursor;
  • the three-dimensional boron nitride precursor is subjected to sintering heat treatment to obtain three-dimensional boron nitride;
  • the three-dimensional boron nitride is immersed in a liquid prepolymer, subjected to a bubble removal treatment, and then subjected to a heat curing treatment to obtain a highly thermally conductive polymer composite material.
  • the highly thermally conductive polymer composite of the present invention in particular, the high thermal conductivity polymer composite in the field of motors, electronic packaging, LED packaging, and aerospace. Applications in the military field.
  • the above-mentioned high thermal conductive polymer composite material of the present invention uses a three-dimensional boron nitride to construct a stable three-dimensional network structure in a polymer matrix, and establishes a heat conduction channel in the polymer matrix, thereby imparting the present invention.
  • High thermal conductivity polymer composites have high thermal conductivity.
  • the method for preparing the high thermal conductivity polymer composite material of the present invention can be thermally cured by using three-dimensional boron nitride as a three-dimensional network structure and a liquid prepolymer, thereby realizing establishment of a heat conduction channel in the polymer body to impart high in the present invention.
  • Thermally conductive polymer composites have a high thermal conductivity.
  • the three-dimensional boron nitride is obtained by the ice template method, the preparation process is safe and environmentally friendly, the solvent used is an aqueous solution, and no organic solvent is involved; and the reaction conditions are mild and easy to control.
  • the process is simple, effectively avoids the use of harsh conditions such as high-temperature reaction and corrosive and explosive gas, such as the preparation of three-dimensional boron nitride by chemical vapor deposition, and reduces the three-dimensional boron nitride and the high thermal conductivity of the invention.
  • the production cost of polymer composites Secondly, the preparation of three-dimensional boron nitride has low density, high porosity, excellent three-dimensional structure size, good mechanical properties, and improved stability of the three-dimensional network structure in the high thermal conductivity polymer composite of the present invention, so that the present invention has high thermal conductivity.
  • the polymer composite has stable thermal conductivity.
  • the high thermal conductivity polymer composite material of the invention has high thermal conductivity and stable thermal conductivity. Therefore, it can be more widely used in the fields of electric motors, electronic packaging, LED packaging, and aerospace and military.
  • FIG. 1 is a flow chart of a method for preparing a highly thermally conductive polymer composite material according to an embodiment of the present invention
  • Example 2 is a scanning electron microscope (SEM) image of three-dimensional boron nitride prepared in Example 1.
  • Embodiments of the present invention provide a highly thermally conductive polymer composite having a thermally conductive network structure.
  • the high thermal conductivity polymer composite comprises a polymer matrix and three-dimensional boron nitride filled in the polymer matrix, and the three-dimensional boron nitride is in the high thermal conductivity polymer composite.
  • the volume fraction is 5 - 50%.
  • the high thermal conductivity polymer composite uses three-dimensional boron nitride to construct a three-dimensional network structure in the polymer matrix, and establishes a heat conduction channel in the polymer matrix, thereby imparting high thermal conductivity to the highly thermally conductive polymer composite of the present invention.
  • the volumetric content of the three-dimensional boron nitride can be relatively reduced. It has been determined that the high thermal conductivity polymer composite provided by the embodiment of the present invention has a thermal conductivity of 0.3-10 W/m.K.
  • the density of the three-dimensional boron nitride in the high thermal conductive polymer composite provided by the embodiment of the present invention is controlled to be 1.0 to 100 mg/cm 3 ; in another embodiment, the three-dimensional nitriding The pore diameter of boron is 2 to 200 ⁇ .
  • the three-dimensional network structure of the three-dimensional boron nitride has a better thermal conductivity and a more stable structure, thereby imparting the high thermal conductivity polymer composite provided by the embodiments of the present invention. High thermal conductivity and thermal stability.
  • the polymer is at least one liquid prepolymer of liquid epoxy resin, liquid cyanate, liquid bismaleimide, liquid polyimide prepolymer
  • the formed polymer is heat cured.
  • the liquid prepolymer is thermally cured into a stepwise heat curing process, the first step
  • the temperature of the ladder heat curing treatment is 80-140 ° C, and the temperature between the turns is 0.5-2 h;
  • the temperature of the second step heat curing treatment is 1 40-160 ° C, and the temperature between the turns is 0.5-2 h;
  • the temperature is 160-200 ° C, and the daytime is 0.5-2 h.
  • the heat curing treatment is a stepwise heat curing treatment
  • the temperature of the first step heat curing treatment is 140 ° C
  • the time between the turns is 2 h
  • the temperature of the second step heat curing treatment is 160 ° C
  • the daytime is 2h
  • the third step heat curing treatment temperature is 200 °C
  • the daytime is 2h.
  • the three-dimensional boron nitride can establish a high heat rate and a high stable heat conduction channel in the selected polymer, and the invention is provided.
  • High thermal conductivity polymer composites with high thermal conductivity and high stability can moderately reduce the volume content of three-dimensional boron nitride.
  • the high thermal conductivity polymer composite material in each of the above embodiments uses a three-dimensional boron nitride to construct a three-dimensional network structure in a polymer matrix, and a heat conduction channel having high thermal conductivity and high stability is established in the polymer matrix. Therefore, the high thermal conductive polymer composite material of the present invention has a high thermal conductivity, and the thermal conductivity is more than three times higher than that of the conventional polymer/thermal conductive ceramic composite, as described in the specific examples below. In addition, the volume content of the three-dimensional boron nitride can be relatively reduced.
  • embodiments of the present invention provide a method of preparing one of the highly thermally conductive polymer composites described above.
  • the process steps for preparing a high thermal conductivity polymer composite material according to an embodiment of the present invention are shown in FIG. 1 and include the following steps:
  • Step S01 mixing boron nitride nanosheets, water and water-soluble polymer according to a mass ratio of 1: (1-50): 100 to obtain a mixture solution;
  • Step S02 The mixture solution prepared in step S01 is subjected to freeze treatment to form a frozen mixed liquid, and the frozen mixed liquid is subjected to freeze-drying treatment to obtain a three-dimensional boron nitride precursor;
  • Step S03 performing the sintering heat treatment on the three-dimensional boron nitride precursor prepared in step S02 to obtain three-dimensional boron nitride;
  • Step S04 The three-dimensional boron nitride prepared in the step S03 is immersed in the liquid prepolymer, subjected to a heat removal treatment after the bubble removing treatment, to obtain a highly thermally conductive polymer composite material.
  • step S01 after the boron nitride nanosheet, water and the water-soluble polymer are mixed at a predetermined ratio, the boronized nanosheet forms a uniform dispersion system. Therefore, in step S01
  • the mixing treatment may be a conventional treatment such as stirring, sonication or the like.
  • the water-soluble polymer in the step S01 is at least one selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylamide, and polyvinylpyrrolidone.
  • the polymer can not only be effectively dissolved in water, but also can effectively ensure the uniform distribution of the boron nitride nanosheets in the subsequent final dried three-dimensional boron nitride precursor, and is favorable for the formation of three-dimensional boron nitride.
  • the water in step S01 is selected from deionized water.
  • the diameter of the boron nitride nanosheet in step S01 and the selection of the water-soluble polymer are set according to the above conditions to improve the stability of the dispersion solution of the mixture solution and the boron nitride nanometer. Dispersion uniformity of the sheet.
  • the boron nitride nanosheets in the above step S01 are prepared as follows:
  • SOU ultrasonic mixing treatment is carried out by mixing micron boron nitride with an organic solvent at a mass ratio of 1: (50-100) to obtain an initial mixed solution;
  • S012 performing solid-liquid separation on the primary mixed liquid to obtain the boron nitride nanosheet.
  • the micron boron nitride in the step S011 has a particle diameter of 2 ⁇ m to 18 ⁇ m.
  • the organic solvent is at least one of isopropyl alcohol, hydrazine, ⁇ '-dimethylformamide or hydrazine-methylpyrrolidone.
  • the ultrasonic power is 100 - 1000 W
  • the ultrasonic time is 12 to 24 h.
  • the solid-liquid separation in the step S012 can achieve separation of the boron nitride nanosheet from the organic solvent by a conventional method.
  • the solid-liquid separation is centrifugal separation, and the centrifugal rate is 1000.
  • the freezing treatment of the mixed solution prepared in the step S01 is to freeze the water in the mixed solution, which is advantageous for solidification of the polymer. Therefore, in one embodiment, the freezing temperature of the freezing treatment is controlled to be -20 to -40 ° C, and the freezing time is 12 to 24 hours.
  • the temperature of the freezing process and the control of the crucible not only can the water be frozen to facilitate sublimation in the subsequent freeze-drying process, but more importantly, the control of the temperature and the inter-turn can cause the boron nitride nanosheet to solidify.
  • the mixed solution can be uniformly dispersed to avoid agglomeration and collapse during the subsequent freeze-drying process, thereby ensuring uniform distribution of the boron nitride nanosheet in the three-dimensional boron nitride precursor.
  • the degree of vacuum of the freeze-drying treatment of the mixed solution is -20 Pa ⁇ -100 Pa, and the freezing temperature is -50-0 °C
  • the freeze-drying treatment has a vacuum of -40 Pa and a freezing temperature of -50 °C.
  • the freeze-drying temperature and the crucible By controlling the freeze-drying temperature and the crucible, the boron nitride nanosheets are uniformly distributed in the final dry three-dimensional boron nitride precursor while effectively removing moisture.
  • step S02 On the basis of the above step S02, after the three-dimensional boron nitride precursor obtained in step S03 is subjected to the sintering heat treatment in step S03, the water-soluble polymer in the three-dimensional boron nitride precursor is removed, thereby forming a porous structure.
  • Three-dimensional boron nitride In one embodiment, the temperature of the sintering heat treatment is 800-1200 ° C, and the sintering time is 4-8 h. In a specific embodiment, the temperature of the sintering heat treatment is
  • sintering time is 4h.
  • the sintering heat treatment effectively removes the polymer and imparts a stable three-dimensional structure to the three-dimensional boron nitride precursor.
  • the sintered three-dimensional boron nitride has a density of 1.0 to 100 mg/cm 3 and a pore diameter of 2 to 200 ⁇ m.
  • the density and the aperture of the three-dimensional boron nitride also make the three-dimensional network structure of the three-dimensional boron nitride have better thermal conductivity and more stable structure, thereby imparting high thermal conductivity to the high thermal conductivity polymer composite provided by the embodiments of the present invention. And thermal stability.
  • the liquid prepolymer coats the three-dimensional boron nitride and is filled into the porous structure of the three-dimensional boron nitride.
  • the liquid prepolymer polymer is at least one of a liquid epoxy resin, a liquid cyanate ester, a liquid bismaleimide, and a liquid polyimide prepolymer.
  • the liquid prepolymer polymer selected not only has good fluidity, but also heat-cured to enable three-dimensional boron nitride to establish a high heat rate and a highly stable heat conduction channel in the polymer, thereby imparting high thermal conductivity polymerization in the embodiment of the present invention.
  • the composite material has high thermal conductivity and high stability, and can simultaneously reduce the volume content of three-dimensional boron nitride.
  • a bubble removal treatment method is adopted. Process it. After the three-dimensional boron nitride is immersed in the liquid prepolymer, the bubble removal treatment is performed first, followed by thermal curing treatment.
  • the heat curing treatment of the liquid prepolymer polymer is set as above
  • the stepped thermal curing process described herein such as a three-step thermal curing process, the first step thermal curing process
  • the temperature is 80-140 ° C, 0.5-2 h between turns;
  • the second step heat curing temperature is 140-160 ° C, the daytime is 0.5-2 h;
  • the third step heat curing temperature is 160-200 ° C, daytime is 0.5-2h.
  • the heat curing treatment is a stepwise heat curing treatment
  • the temperature of the first step heat curing treatment is 140 ° C
  • the time between the turns is 2 h
  • the temperature of the second step heat curing treatment is 160 ° C
  • the interval is 2h
  • the temperature of the third step heat curing treatment is 200 ° C
  • the temperature between the turns is 2 h.
  • the preparation method of the high thermal conductivity polymer composite material of the embodiment of the present invention can be performed by thermally curing a three-dimensional boron nitride as a three-dimensional network structure and a liquid prepolymer, thereby realizing heat conduction in the polymer body.
  • the channels thereby impart high thermal conductivity to the highly thermally conductive polymer composite of the present invention.
  • the three-dimensional boron nitride is obtained by the ice template method, the preparation process is safe and environmentally friendly, the solvent used is an aqueous solution, and no organic solvent is involved; and the reaction conditions are mild, Easy to control, the process is simple, effectively avoiding the use of harsh conditions such as high temperature reaction and corrosive and explosive gases, such as the conventional chemical vapor deposition method for preparing three-dimensional boron nitride, and simultaneously reducing three-dimensional boron nitride and the present invention. Production cost of high thermal conductivity polymer composites.
  • the preparation of three-dimensional boron nitride has low density, high porosity, excellent three-dimensional structure size, good mechanical properties, and improved stability of the three-dimensional network structure in the high thermal conductivity polymer composite of the present invention.
  • the invention discloses that the high thermal conductivity polymer composite material has stable thermal conductivity.
  • the high thermal conductivity polymer composite provided by the embodiments of the present invention has high thermal conductivity, excellent thermal conductivity stability, mild preparation conditions, environmental protection and safety, and moderately saves three-dimensional nitrogen.
  • the amount of boron is used. Therefore, the high thermal conductivity polymer composite provided by the embodiments of the present invention can be widely applied in the fields of electric motors, electronic packaging, LED packaging, and aerospace military.
  • a high thermal conductivity polymer composite material and a preparation method thereof was prepared as follows:
  • S11 mixing boron nitride nanosheets, deionized water, and polyethylene glycol according to a mass ratio of 1:50:100;
  • S12 mixing the mixture of step S11 in a refrigerator at -20 ° C Frozen at 12h for a frozen mixture at temperature
  • the frozen mixture is subjected to a freeze vacuum drying process with a vacuum of -40 Pa and a freezing temperature of -50 °C. Obtaining a three-dimensional boron nitride precursor;
  • S13 a three-dimensional boron nitride precursor high-temperature sintering operation process, the sintering temperature is 1000 ° C, the sintering time is 4h, to obtain three-dimensional boron nitride;
  • the three-dimensional boron nitride prepared in the first embodiment was subjected to scanning electron microscopy (SEM) microscopic analysis, and its microscopic cross section is shown in Fig. 2, which is a porous structure having a density of 21 mg/cm3; and a pore diameter of 100 ⁇ m.
  • SEM scanning electron microscopy
  • the high thermal conductivity polymer composite prepared in the first embodiment was measured for thermal conductivity, and the thermal conductivity was measured.
  • the volume fraction of three-dimensional boron nitride in the high thermal conductivity polymer composite was 5%.
  • a highly thermally conductive polymer composite material and a method of preparing the same.
  • the highly thermally conductive polymer composite material provided in this Example 2 was prepared as follows:
  • S21 mixing boron nitride nanosheets, deionized water, and polyvinyl alcohol according to a mass ratio of 1:30:100;
  • S22 mixing the mixture of step S21 in a refrigerator at -20 ° C Under, frozen for 12h to get a frozen mixture
  • the frozen mixture is subjected to a freeze vacuum drying process with a vacuum of -40 Pa and a freezing temperature of -50 ° C to obtain a three-dimensional boron nitride precursor;
  • S23 a high-temperature sintering operation of the three-dimensional boron nitride precursor, the sintering temperature is 1000 ° C, and the sintering time is 4 h to obtain three-dimensional boron nitride;
  • the three-dimensional boron nitride prepared in the second embodiment was subjected to scanning electron microscopy (SEM) microscopic analysis, and its microscopic cross section is similar to that shown in FIG. 2, which is a porous structure having a density of 30 mg/cm 3 and a pore diameter of 150 ⁇ m.
  • SEM scanning electron microscopy
  • the high thermal conductivity polymer composite prepared in the second embodiment was measured for thermal conductivity, and the thermal conductivity was measured.
  • the volume fraction of three-dimensional boron nitride in the high thermal conductivity polymer composite was 30%.
  • Example 3 A high thermal conductivity polymer composite material and a preparation method thereof.
  • the highly thermally conductive polymer composite provided in Example 3 was prepared as follows:
  • S32 The mixture of the step S31 is frozen in a refrigerator at a temperature of -20 ° C for 12 hours to obtain a frozen mixture, and the frozen mixture is subjected to a freeze vacuum drying process, the degree of vacuum is -40 Pa, and the freezing temperature is - At 50 ° C, a three-dimensional boron nitride precursor is obtained;
  • S33 a three-dimensional boron nitride precursor high-temperature sintering operation process, the sintering temperature is 1000 ° C, the sintering time is 4h, to obtain three-dimensional boron nitride;
  • the three-dimensional boron nitride prepared in the third embodiment was subjected to scanning electron microscopy (SEM) microscopic analysis, and its microscopic cross section is similar to that shown in FIG. 2, which is a porous structure having a density of 45 mg/cm 3 and a pore diameter of 200 ⁇ m.
  • SEM scanning electron microscopy
  • the volume fraction of three-dimensional boron nitride in the high thermal conductivity polymer composite was measured to be 40%.
  • a high thermal conductivity polymer composite material and a preparation method thereof was prepared as follows:
  • S41 mixing boron nitride nanosheets, deionized water, and polyacrylamide according to a mass ratio of 1:1:100;
  • S42 placing the mixture of step S41 in the refrigerator at -20 ° At a temperature of C, the frozen mixture was obtained by freezing for 12 hours, and the frozen mixture was subjected to a freeze vacuum drying process with a vacuum of -40 Pa and a freezing temperature of -50.
  • S43 a high-temperature sintering operation of the three-dimensional boron nitride precursor, the sintering temperature is 1000 ° C, and the sintering time is 4 h to obtain three-dimensional boron nitride;
  • S44 impregnating the three-dimensional boron nitride with the liquid polyimide prepolymer, and removing bubbles under vacuum. The mixture is thermally cured by stepwise to obtain a highly thermally conductive polymer composite, that is, thermally cured to obtain three-dimensional nitrogen. Boron-polymer composite, wherein the curing temperature is 140 ° C, 160
  • the daytime is 2h.
  • the three-dimensional boron nitride prepared in the fourth embodiment was subjected to scanning electron microscopy (SEM) microscopic analysis, and its microscopic cross section is similar to that shown in FIG. 2, which is a porous structure having a density of 50 mg/cm 3 and a pore diameter of 50 ⁇ m.
  • SEM scanning electron microscopy
  • the high thermal conductivity polymer composite prepared in the fourth embodiment was measured for thermal conductivity, and the thermal conductivity thereof was measured.
  • the volume fraction of three-dimensional boron nitride in the high thermal conductivity polymer composite was measured to be 50%.
  • the boron nitride nanosheets are dispersed in a liquid epoxy resin by ultrasonic technology, and bubbles are removed under vacuum.
  • the mixture was subjected to stepwise heat curing at a curing temperature of 140 ° C, 160
  • the boron nitride nanosheets are dispersed in a liquid cyanate by ultrasonic technology, and bubbles are removed under vacuum.
  • the mixture was subjected to stepwise heat curing at a temperature of 140 ° C, 160 ° C and 200 ° C, respectively, for 2 h.
  • Thermal curing gives boron nitride nanosheet-polymer composites.
  • the volume fraction of boron nitride nanosheets is controlled to 20%, and the thermal conductivity of the composite is only 0.3 W/m.K.
  • the boron nitride nanosheets were dispersed in liquid bismaleimide by ultrasonic technique, and bubbles were removed under vacuum. The mixture was subjected to stepwise heat curing at a temperature of 140 ° C, 160 ° C and 200 ° C, respectively, for 2 h. Thermal curing gives boron nitride nanosheet-polymer composites. The volume fraction of boron nitride nanosheets is controlled to 30%, and the thermal conductivity of the composite is only 0.4 W/m.K.
  • the boron nitride nanosheets were dispersed in a liquid polyimide prepolymer by ultrasonic technology, and the bubbles were removed under vacuum. The mixture was subjected to stepwise heat curing at 140 ° C, 160 ° C and 200 ° C, respectively, for 2 h. Thermal curing gives boron nitride nanosheet-polymer composites. The volume fraction of the boron nitride nanosheet is controlled to 50%, and the thermal conductivity of the composite is only 2.8 W/m.K.
  • the three-dimensional boron nitride provided by the embodiment of the present invention constructs a three-dimensional network structure in a polymer matrix, and establishes a heat conduction channel in the polymer matrix, thereby imparting the high thermal conductive polymer composite material of the present invention. Has a high thermal conductivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un matériau composite polymère à haute conductivité thermique comprenant une matrice polymère remplie de nitrure de bore tridimensionnel. La fraction volumétrique du nitrure de bore tridimensionnel dans le matériau composite polymère à haute conductivité thermique est comprise entre 5 et 50 %. Selon le matériau composite polymère à haute conductivité thermique, le nitrure de bore tridimensionnel sert à construire une structure de réseau tridimensionnelle dans la matrice polymère, et une trajectoire de conduction thermique se forme dans la matrice polymère. Ainsi, le matériau composite polymère à haute conductivité thermique a un coefficient de conduction thermique élevé, et les conditions du procédé de préparation associées sont modérées et faciles à contrôler, et la technologie est simple, sûre et respectueuse de l'environnement.
PCT/CN2016/072211 2015-08-31 2016-01-26 Matériau composite polymère à haute conductivité thermique, son procédé de préparation et son utilisation WO2017036082A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510548716.X 2015-08-31
CN201510548716.XA CN105062007B (zh) 2015-08-31 2015-08-31 高导热聚合物复合材料及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2017036082A1 true WO2017036082A1 (fr) 2017-03-09

Family

ID=54491544

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/072211 WO2017036082A1 (fr) 2015-08-31 2016-01-26 Matériau composite polymère à haute conductivité thermique, son procédé de préparation et son utilisation

Country Status (2)

Country Link
CN (1) CN105062007B (fr)
WO (1) WO2017036082A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105062007B (zh) * 2015-08-31 2017-09-26 中国科学院深圳先进技术研究院 高导热聚合物复合材料及其制备方法和应用
CN105733191B (zh) * 2016-03-21 2018-10-09 中南大学 不同维度高导热材料增强聚合物基复合材料及制备方法
EP3532539B1 (fr) * 2016-10-28 2022-01-19 Nanyang Technological University Matériau composite et procédé de formation associé, et composant électrique comprenant le matériau composite
CN108250677B (zh) * 2016-12-29 2022-10-14 中国科学院深圳先进技术研究院 一种包含填料粒子三维网络的聚合物基复合材料及其制备方法
CN106977773B (zh) * 2017-04-21 2019-11-26 深圳先进技术研究院 一种氮化硼纳米管-纳米纤维素纤维复合材料及其制备方法
CN107722157B (zh) * 2017-10-10 2019-06-28 西安科技大学 一种轻质、导热绝缘聚合物硬质泡沫材料及其制备方法
CN110894338B (zh) * 2018-09-12 2022-05-24 天津理工大学 基于超弹性网络的可控形变精准调控复合材料及其制备方法和应用
CN112111176B (zh) * 2020-09-28 2022-04-29 常州中英科技股份有限公司 一种氮化硼包覆聚四氟乙烯复合填料及其制备的半固化片和高导热型碳氢覆铜板
CN112552690B (zh) * 2020-12-10 2022-04-22 苏州鸿凌达电子科技有限公司 一种低介电常数高导热系数硅胶片
CN112993142B (zh) * 2021-02-08 2021-11-30 华中科技大学 一种三维高导热白光led及其制备方法
CN113072797B (zh) * 2021-03-26 2022-05-13 清华大学 环氧树脂基复合材料及其制备方法
CN114103125B (zh) * 2021-09-30 2022-06-28 哈尔滨工业大学（威海） 一种高导热微型器件的制备方法
CN114250064A (zh) * 2022-01-17 2022-03-29 湖南大学 一种柔性高导热聚合物基复合材料及其制备方法
CN115368734B (zh) * 2022-08-29 2024-01-26 南昌大学共青城光氢储技术研究院 一种高导热聚酰亚胺复合薄膜材料的制备方法
CN115322749A (zh) * 2022-08-30 2022-11-11 中国科学院深圳先进技术研究院 六方氮化硼-二氧化钒复合材料及其制备方法和应用
CN115505255A (zh) * 2022-09-22 2022-12-23 浙江大学 一种氮化硼聚合物复合材料及其制备方法、应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010157563A (ja) * 2008-12-26 2010-07-15 Mitsubishi Electric Corp 熱伝導性シート及びパワーモジュール
WO2012070289A1 (fr) * 2010-11-26 2012-05-31 三菱電機株式会社 Feuille thermoconductrice et module de puissance
CN103958400A (zh) * 2011-11-29 2014-07-30 三菱化学株式会社 氮化硼凝聚粒子、含有该粒子的组合物、及具有包含该组合物的层的三维集成电路
CN104788959A (zh) * 2015-03-31 2015-07-22 中国科学院化学研究所 一种具有取向结构的导热复合材料及其制备方法
CN105062007A (zh) * 2015-08-31 2015-11-18 中国科学院深圳先进技术研究院 高导热聚合物复合材料及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010153538A (ja) * 2008-12-25 2010-07-08 Sumitomo Electric Ind Ltd 放熱材料とその製法
CN103172924A (zh) * 2013-04-17 2013-06-26 天津大学 高导热聚合物复合材料及其制备方法
EP3035778B1 (fr) * 2013-08-14 2018-10-03 Denka Company Limited Substrat de circuit composite nitrure de bore - résine, et substrat de circuit à dissipateur thermique composite nitrure de bore - résine intégré
CN104479291A (zh) * 2014-12-04 2015-04-01 中国科学院过程工程研究所 一种导热绝缘环氧树脂组合物、制备方法及其用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010157563A (ja) * 2008-12-26 2010-07-15 Mitsubishi Electric Corp 熱伝導性シート及びパワーモジュール
WO2012070289A1 (fr) * 2010-11-26 2012-05-31 三菱電機株式会社 Feuille thermoconductrice et module de puissance
CN103958400A (zh) * 2011-11-29 2014-07-30 三菱化学株式会社 氮化硼凝聚粒子、含有该粒子的组合物、及具有包含该组合物的层的三维集成电路
CN104788959A (zh) * 2015-03-31 2015-07-22 中国科学院化学研究所 一种具有取向结构的导热复合材料及其制备方法
CN105062007A (zh) * 2015-08-31 2015-11-18 中国科学院深圳先进技术研究院 高导热聚合物复合材料及其制备方法和应用

Also Published As

Publication number Publication date
CN105062007B (zh) 2017-09-26
CN105062007A (zh) 2015-11-18

Similar Documents

Publication Publication Date Title
WO2017036082A1 (fr) Matériau composite polymère à haute conductivité thermique, son procédé de préparation et son utilisation
Li et al. Sol-gel derived porous ultra-high temperature ceramics
Wei et al. Enhanced thermal conductivity of epoxy composites by constructing aluminum nitride honeycomb reinforcements
Wu et al. A review of three-dimensional graphene networks for use in thermally conductive polymer composites: construction and applications
CN108251076B (zh) 碳纳米管-石墨烯复合散热膜、其制备方法与应用
CN107434905B (zh) 导热聚合物复合材料及其制备方法与应用
Tang et al. Nitrogen-doped hollow carbon spheres with large mesoporous shells engineered from diblock copolymer micelles
Shen et al. Achieving vertically aligned SiC microwires networks in a uniform cold environment for polymer composites with high through-plane thermal conductivity enhancement
CN107522475B (zh) 一种仿贝壳陶瓷基复合材料及其制备方法
CN103588482B (zh) 一种高孔隙率及高强度钇硅氧多孔陶瓷的制备方法
CN112542577B (zh) 一种纳米铋/氮掺杂碳泡沫纳米片二维复合材料及其制备方法和应用
CN110157931B (zh) 一种具有三维网络结构的纳米碳增强金属基复合材料及其制备方法
JP2011032490A (ja) 多孔質体の製造方法
CN106633652A (zh) 一种双连续相氧化铝/环氧树脂复合材料的制备方法
CN105506341B (zh) Mg合金/Al2O3复合材料及制备方法
CN105293452A (zh) 三维结构氮化硼及其制备方法和应用
CN108218467B (zh) 一种高孔隙率及低热导率多孔纳米碳化硅陶瓷的制备方法
CN104164208A (zh) 一种石墨烯/聚酰亚胺复合胶黏剂的制备方法
CN112553494B (zh) 一种冷冻装置及其制备高强韧层状多孔钛合金材料的方法
CN105601316A (zh) 一种碳化硅气凝胶及其制备方法
CN105801163A (zh) 低温固相烧成碳化硅泡沫陶瓷及其制备方法
CN111479791B (zh) 制备氮化铝泡沫的方法
JP5429526B2 (ja) セラミックス多孔体の製造方法
CN109180186B (zh) 仿生珍珠层max相碳化物陶瓷基复合材料的制备方法
CN112280541A (zh) 一种基于石墨化聚多巴胺包覆金属粒子的高导热复合材料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16840518

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 08/05/2018

122 Ep: pct application non-entry in european phase

Ref document number: 16840518

Country of ref document: EP

Kind code of ref document: A1