WO2020107599A1 - Matériau de protection thermoconducteur à base d'organosilicium et procédé de préparation s'y rapportant - Google Patents

Matériau de protection thermoconducteur à base d'organosilicium et procédé de préparation s'y rapportant Download PDF

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Publication number
WO2020107599A1
WO2020107599A1 PCT/CN2018/123398 CN2018123398W WO2020107599A1 WO 2020107599 A1 WO2020107599 A1 WO 2020107599A1 CN 2018123398 W CN2018123398 W CN 2018123398W WO 2020107599 A1 WO2020107599 A1 WO 2020107599A1
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WIPO (PCT)
Prior art keywords
film
graphite
graphene
core material
thermally conductive
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PCT/CN2018/123398
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English (en)
Chinese (zh)
Inventor
张保坦
孙蓉
朱朋莉
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深圳先进技术研究院
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Publication of WO2020107599A1 publication Critical patent/WO2020107599A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the field of silicone materials, in particular to a thermally conductive shielding multifunctional silicone material and a preparation method thereof.
  • 5G Fifth generation mobile communication
  • 5G is a new generation mobile communication system facing the needs of the information society in 2020. It has the characteristics of high spectrum utilization rate, large data flow, low network energy consumption, high reliability and short delay, etc. , Unmanned driving, telemedicine, artificial intelligence and other new technology application innovation foundations.
  • the breakthrough of 5G communication technology and the expansion of application scenarios will promote the revolutionary development of smart terminals and bring new opportunities to the development of the multifunctional polymer composite industry.
  • miniaturization and high density especially after the three-dimensional integrated packaging technology has been widely recognized, high-performance thermally conductive, electrically conductive, shielding performance polymer composite materials have become more and more widely s concern.
  • polymer composite materials have been more and more widely used in various fields, such as thermal interface materials, conductive rubber materials and electromagnetic shielding materials. This is because polymer composites have advantages such as light weight, flexibility, compressibility, and corrosion resistance compared to metal materials.
  • polymer composite materials are prepared by adding fillers with desired properties (such as thermal conductivity, electrical conductivity, and electromagnetic shielding) to the polymer substrate.
  • desired properties such as thermal conductivity, electrical conductivity, and electromagnetic shielding
  • the volume fraction of fillers should be more than 60% to ensure that the fillers are in contact with each other to form a connected thermally and electrically conductive network.
  • the addition of a large amount of thermally conductive filler not only increases the cost and weight, but also reduces the elasticity of the material and increases the hardness, but it is difficult to significantly improve the thermal conductivity.
  • the preparation technology of the existing silicone thermal interface material is mainly by adding a relatively high density of thermally conductive inorganic powder to the silicone material, or then constructing a thermal conduction channel by close packing between the particles, which requires a large amount of powder with different particle sizes
  • the thermal conductivity can only be achieved by the body, and there is more contact thermal resistance between the thermally conductive particles, which makes it impossible to obtain a lightweight thermal interface material with high thermal conductivity.
  • the present invention abandons the traditional method of directly mixing the thermally conductive powder and the silicone to prepare the silicone thermal interface material, and proposes to construct a corrugated graphite/graphene skeleton with high thermal conductivity, and then fill in the gap Soft silicone, this method effectively reduces and eliminates the contact thermal resistance of the heat conduction network channel between the powders, achieving high thermal conductivity in the vertical direction; at the same time, due to the compactness of the graphite/graphene film, the conductive absorption baud To obtain a silicone graphite film composite material with high thermal conductivity and shielding performance.
  • Another object of the present invention is to provide a method for preparing a multi-functional silicone thermal interface material with high thermal conductivity shielding.
  • one aspect of the present invention provides a thermally conductive and shielded silicone composite film material, which includes a thermally conductive flexible material, and the thermally conductive flexible material has a graphite film core material and/or a graphene film core material, which is characterized by graphite
  • the core material of the film or graphene film is a wavy or corrugated graphite film or graphene film, and the extending direction of the graphite film or graphene film and the composite film material is parallel.
  • the heat conductive flexible material is liquid silicone rubber.
  • liquid silicone rubber is made of polyvinyl siloxane, cross-linking agent, catalyst, inhibitor and surface treatment agent.
  • the thermal shielding silicone composite film material has a shielding efficiency of 10 MHz to 1 GHz higher than 30 dB, preferably higher than 50 dB, and more preferably higher than 55 dB.
  • the thermal conductivity shielded silicone composite film material has a thermal conductivity higher than 5W/m ⁇ K, preferably higher than 5W/m ⁇ K, preferably higher than 10W/m ⁇ K.
  • the dimension of the graphene membrane core material in the extending direction is the same as the dimension of the silicone composite membrane material in the extending direction, so as to ensure better shielding effect.
  • the dimension of the graphite film core material and/or graphene film core material in the vertical direction is 0.20 mm to 100 mm, preferably 1 mm to 20 mm.
  • the thickness of the graphite film core material and/or the graphene film core material is 0.20 mm to 100 mm, preferably 5 ⁇ m to 500 ⁇ m, preferably 12 ⁇ m to 30 ⁇ m.
  • the invention constructs a high thermal conductivity corrugated graphite/graphene skeleton through a folding and pressing process, which not only effectively reduces and eliminates the contact thermal resistance between particles in the heat conduction network channel between powders, but also utilizes the folding of graphene to achieve The best heat conduction path in the vertical direction; at the same time, due to the compactness of the graphite/graphene film and the characteristics of conductive wave absorption, an organic silicon graphene composite material with high thermal conductivity and shielding performance is obtained.
  • Another method of the present invention provides a method for preparing a thermally conductive and shielded silicone composite film material, which includes the following steps:
  • Graphite film or graphene film is used as raw material film to make wavy or corrugated graphite film or graphene film core material;
  • the graphite film or graphene film is one layer or more than one layer. It is preferably one layer, two layers, three layers, four layers, and five layers.
  • the raw material film is a graphite film or a graphene film with high thermal conductivity, and the thickness is 5 to 500 ⁇ m.
  • the vertical dimension of the graphite membrane core material or the graphene membrane core material is the same as the vertical length of the heat-shielding silicone composite membrane material, or 10%-100% of the vertical length of the silicone composite membrane material For example, it can be 99%, 98%, 97%, 96%, 95%, 90%, 80%, 70%, 60%, 50%, usually 0.20mm-100mm.
  • liquid silicone rubber is composed of polyvinyl siloxane, cross-linking agent, catalyst, inhibitor and surface treatment agent, according to the weight of 100:1-25:0.01-2.5:0.2-3.0:0.5-8.0 Served together.
  • polyvinyl siloxane is linear, branched, dendritic or micro-crosslinked polysiloxane, and any one molecular structure contains at least two or more aliphatic Saturated double bond, viscosity range from 300 to 500,000 mPa ⁇ s, its chain end or side chain contains at least two vinyl groups.
  • the cross-linking agent is a linear hydrogen-containing silicone oil, a ring-shaped or branched cross-linked hydrogen-containing silicone resin, and its molecular structure contains at least two or more silicon-hydrogen bonds; the viscosity range is 10 to 10000mPa ⁇ s, the hydrogen content is 0.02 ⁇ 1.52%, of which 100 ⁇ 3000mPa ⁇ S is the best, and one or more curing agents can be mixed among them.
  • the catalyst is selected from metal compounds or complexes of groups VIII and VII and some rare earth metal compounds, mainly including platinum series catalysts (Speier catalysts, Karstedt catalysts), rhodium catalysts (Wilkinson catalysts), and palladium catalysts Etc., in which the chloroplatinic acid complex catalyst is the best, and the Pt content is between 100 and 5000 ppm.
  • the inhibitor is one of acetylene alcohol compounds and polyvinyl silicone oil.
  • the surface treatment agent is selected from vinyl silane coupling agent, epoxy coupling agent, acryloxy silane coupling agent, phthalate coupling agent, zirconate coupling agent, aluminum Acid ester coupling agent and its hydrolysate, such as: ⁇ -methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-(2,3 ring Oxypropyloxy)propylmethyl diethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, isopropyl titanate tristearate, n-butyl titanate , Bis (acetylacetonyl) ethoxy isopropoxy titanate, bis (triethanolamine) diisopropyl titanate, tetra-n-propyl zirconate, etc., of which 3-glycidyl ether oxypropyl Trimethoxysilane is preferred, especially with its mixed hydro
  • Another aspect of the present invention provides the use of thermally conductive and shielded silicone composite film materials in the field of consumer electronics.
  • corrugated and “wavy” all mean that the graphite film or graphite film has ups and downs in the upper and lower plane directions of the composite film material.
  • the graphite/graphene film is dense and continuous, it has a good plane shielding effect, and its wave folding makes the graphite/graphene film form an ordered arrangement in the vertical direction, which can give the composite material a higher thermal conductivity and maintain a certain degree.
  • the compressibility of the heat conduction shield realizes multiple effects of heat conduction shielding, which can effectively solve the heat dissipation and shielding problems of electronic industrial products, simplify the assembly structure and volume of electronic components, and further reduce production costs.
  • the present invention uses a graphite/graphene with a corrugated structure as a skeleton to realize the integration and verticalization of the heat conduction path, significantly reduce the contact thermal resistance between particles in the traditional technology, and realize the heat conduction path.
  • the shortest greatly reducing the amount of thermally conductive materials, so as to obtain a lightweight and high thermal conductivity shielding multifunctional silicone graphite composite material.
  • the method of the invention not only overcomes the problems of low thermal conductivity and poor shielding of the existing organosilicon graphite composite materials, but also maintains the high flexibility and tight fit of the organosilicon, and is especially suitable for heat conduction of new energy vehicles, 5G communication equipment, etc. Multifunctional application requirements for conductive shielding.
  • the invention provides a novel structured organosilicon thermal conductive shielding material and a preparation method thereof.
  • the preparation method is simple and the preparation materials are easy to obtain, which provides stable and reliable operation of power devices on terminal devices such as the Internet of Things, new energy vehicles, smart phones, etc. Ideas.
  • FIG. 1 is a schematic diagram of a side view of a silicone heat conductive shielding material. Among them, 1 is silicone rubber, and 2 is wavy or corrugated graphite film or graphene film.
  • a wave-shaped foldable and retractable core material is made by a wave folding device
  • composition and weight ratio of the liquid silicone rubber are as follows: 1000 parts by weight of 1000 mPa ⁇ s vinyl-terminated polysiloxane, 5.5 parts by weight of methyl hydrogen-containing polysiloxane crosslinking agent, 0.3 parts by weight of platinum catalyst, 0.2 By weight parts of butynol inhibitor and 1.5 parts by weight of KH-560 surface treatment agent are mixed to form liquid silica gel.
  • the thermal conductivity of the tile-shaped organosilicon graphene composite material prepared by this method is 17.95W/m ⁇ K, and the shielding efficiency of 10MHz ⁇ 1GHz is 62dB.
  • a wave-shaped foldable and retractable core material is made by a wave folding device
  • composition and weight ratio of liquid silicone rubber are as follows: 5000 mPa ⁇ s vinyl-terminated polysiloxane 100 parts by weight, 2.5 parts by weight of methyl hydrogen-containing polysiloxane crosslinking agent, 0.2 parts by weight of platinum catalyst, 0.1 By weight parts of butynol inhibitor and 3.0 parts by weight of KH-560 surface treatment agent are mixed to form liquid silica gel.
  • the thermal conductivity of the rib-like organosilicon graphite composite thermal material prepared by this method is 13.32W/m ⁇ K, and the shielding efficiency of 10MHz ⁇ 1GHz is 60dB.
  • a 17 ⁇ m graphene film is used as the raw paper, and a wave-shaped foldable and retractable core material is made by a wave folding device;
  • thermoly conductive silicone composite material Compress the wave-shaped folded core material in a mold, press and shape, then pour liquid silicone rubber, evacuate the bubble, and cure at 150 °C for 30 minutes to obtain a thermally conductive silicone composite material.
  • the composition of liquid silicone rubber and the proportion by weight are as follows: 100 parts by weight of 3000 mPa ⁇ s vinyl terminated polysiloxane, 3.5 parts by weight of methyl hydrogen-containing polysiloxane crosslinking agent, 0.5 parts by weight of platinum catalyst, 0.1 By weight parts of butynol inhibitor and 2.0 parts by weight of KH-560 surface treatment agent are mixed to form liquid silica gel.
  • the thermal conductivity of the rib-like organosilicon graphite composite thermal material prepared by this method is 10.41W/m ⁇ K, and the shielding efficiency of 10MHz ⁇ 1GHz is 56dB.
  • the frame-shaped mold is an open-top mold to facilitate the solidification and molding of the upper surface of the material. After the material loaded into the frame mold is leveled, the excess material is scraped out with a scraper. Put the mold containing the mixture into the oven and cure at 150°C for 15 minutes. After curing and molding, a sheet with a thickness of 2 mm is obtained. Thermal conductivity 4.10W/m ⁇ K, shielding effectiveness 26dB from 10MHz to 1GHz.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un matériau de protection thermoconducteur à base d'organosilicium et un procédé de préparation s'y rapportant. L'invention concerne plus précisément un matériau de protection thermoconducteur sous forme de film composite à base d'organosilicium. Le matériau de protection thermoconducteur sous forme de film composite à base d'organosilicium comprend un matériau flexible thermoconducteur ; le matériau flexible thermoconducteur comprend un matériau d'âme sous forme de film de graphite et/ou un matériau d'âme sous forme de film de graphène ; le matériau d'âme sous forme de film de graphite ou de film de graphène est un film de graphite ou un film de graphène de forme ondulée ou de forme cannelée et le film de graphite ou le film de graphène est parallèle à la direction d'extension du matériau sous forme de film composite ; de préférence, le matériau flexible thermoconducteur est un caoutchouc de silicone liquide ; de préférence encore, le caoutchouc de silicone liquide est préparé à partir de poly(vinylsiloxane), d'un agent de réticulation, d'un catalyseur, d'un inhibiteur et d'un agent de traitement de surface. Selon la présente invention, le procédé de préparation est simple, les matériaux sont faciles à obtenir et d'excellents effets thermoconducteurs et de protection sont obtenus.
PCT/CN2018/123398 2018-11-29 2018-12-25 Matériau de protection thermoconducteur à base d'organosilicium et procédé de préparation s'y rapportant WO2020107599A1 (fr)

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CN201811443493.0A CN109608884B (zh) 2018-11-29 2018-11-29 一种导热屏蔽有机硅材料及其制备方法
CN201811443493.0 2018-11-29

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