WO2023077430A1 - High thermal-conductivity phase-change organic silicon rubber, and preparation method therefor and use thereof - Google Patents

High thermal-conductivity phase-change organic silicon rubber, and preparation method therefor and use thereof Download PDF

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WO2023077430A1
WO2023077430A1 PCT/CN2021/129011 CN2021129011W WO2023077430A1 WO 2023077430 A1 WO2023077430 A1 WO 2023077430A1 CN 2021129011 W CN2021129011 W CN 2021129011W WO 2023077430 A1 WO2023077430 A1 WO 2023077430A1
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coupling agent
silane coupling
silicone rubber
thermal conductivity
high thermal
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PCT/CN2021/129011
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French (fr)
Chinese (zh)
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王秀娟
王子威
时宪
朱鲜鹏
李春霞
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青岛科技大学
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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
    • 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
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the invention relates to the technical field of silicone rubber, in particular to a phase-change silicone rubber with high thermal conductivity and its preparation method and application.
  • silicone rubber is one of the best. It is odorless, non-toxic, not afraid of high temperature and can withstand severe cold. Ordinary silicone rubber still maintains its original strength and elasticity between 200°C and -50°C. At the same time, silicone rubber also has good electrical insulation, oxygen and aging resistance, light and aging resistance, mildew resistance, chemical stability, etc., so it is widely used in aerospace, automobiles, ships, office supplies, electronics, etc. and other industries.
  • the thermal conductivity of ordinary silicone rubber is generally not ideal, and the thermal conductivity is generally only 0.165W/(m ⁇ k).
  • the thermal conductivity can be improved by filling thermal conductive fillers.
  • the existing conductive fillers include alumina, zinc oxide, boron nitride, Titanium carbide and white carbon black, etc., but in the current industrial production, it is usually necessary to add a much larger amount of filler than rubber to improve its thermal conductivity, which will affect the processing performance of the material and bring many restrictions to the further application of silicone rubber materials.
  • the present invention provides a high thermal conductivity phase-change silicone rubber and its preparation method and application.
  • the high thermal conductivity phase-change silicone rubber provided by the invention has excellent properties without affecting the physical processing performance of silicone rubber. thermal conductivity.
  • the invention provides a phase-change silicone rubber with high thermal conductivity, comprising the following components in parts by mass:
  • vulcanized silicone rubber 100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, 10-20 parts of silane coupling agent modified boron nitride, and 30-60 parts of graphite/paraffin phase change material.
  • the particle size of the silane coupling agent-modified alumina is 75-150 nm.
  • the particle size of the boron nitride modified by the silane coupling agent is 1-10 ⁇ m.
  • the preparation method of the silane coupling agent modified alumina comprises the following steps:
  • the preparation method of described silane coupling agent modified boron nitride comprises the following steps:
  • silane coupling agent hydrolyzate a silane coupling agent hydrolyzate
  • the boron nitride aqueous dispersion and the silane coupling agent hydrolyzate are mixed for modification reaction to obtain the silane coupling agent modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ⁇ 0.02:1.
  • the preparation method of described graphite/paraffin phase change material comprises the following steps:
  • Graphite and molten paraffin are mixed and adsorbed to obtain the graphite/paraffin phase change material, and the mass ratio of the molten paraffin to graphite is ⁇ 0.6:1.
  • the mass percentage of the ethanol solution of the silane coupling agent is 4.5-9.5%; the temperature of the modification reaction is 55-70° C., and the time of the modification reaction is 1.5-3 hours.
  • the mass ratio of the silane coupling agent, ethanol and water is (15 ⁇ 25):(5 ⁇ 10):(70 ⁇ 75); the temperature of the modification reaction is 40 ⁇ 52°C, and the The modification reaction time is 0.5-1.2h.
  • the present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical solution, comprising the following steps:
  • the mixed material and curing agent are mixed and cured to obtain the high thermal conductivity phase change silicone rubber.
  • the present invention provides the application of the high thermal conductivity phase change silicone rubber described in the above technical solution or the high thermal conductivity phase change silicone rubber prepared by the preparation method described in the above technical solution in heat dissipation devices for electronic or semiconductor components.
  • the invention provides a high thermal conductivity phase-change silicone rubber, which comprises the following components in parts by mass: 100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, and silane coupling agent modified boron nitride 10-20 parts, graphite/paraffin phase change material 30-60 parts.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention adopts three fillers of silane coupling agent modified alumina, silane coupling agent modified boron nitride and graphite/paraffin phase change material to improve the thermal conductivity of vulcanized silicone rubber.
  • the thermal conductivity of boron nitride and aluminum oxide is high, and boron nitride and aluminum oxide modified by silane coupling agent can be highly dispersed in silicone rubber, thereby forming a thermal conductivity network in silicone rubber and improving silicon rubber
  • the thermal conductivity of rubber; at the same time, the graphite/paraffin phase change material improves the thermal conductivity of silicone rubber through the heat absorption performance of paraffin from solid to liquid phase change.
  • the invention provides that the above three fillers can improve the thermal conductivity of the silicone rubber with a small amount of addition, without affecting the physical processing performance of the silicone rubber.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention has a density of 1.068-1.074g/cm 3 , a phase-change latent heat of 7.274-18.37J/g, and a thermal conductivity of 0.178-0.214W/(m k).
  • the present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical scheme, comprising the following steps: vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, graphite/
  • the paraffin phase-change materials are mixed to obtain a mixed material; at room temperature, the mixed material and a curing agent are mixed and solidified to obtain the high thermal conductivity phase-change silicone rubber.
  • the preparation method provided by the invention can realize curing at room temperature, has simple reaction conditions, and is suitable for industrial production.
  • Fig. 1 is the physical picture of the high thermal conductivity phase-change silicone rubber prepared in Example 3 of the present invention
  • Fig. 2 is a DSC chart of the phase-change silicone rubber with high thermal conductivity prepared in Example 3 of the present invention.
  • the invention provides a phase-change silicone rubber with high thermal conductivity, comprising the following components in parts by mass:
  • vulcanized silicone rubber 100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, 10-20 parts of silane coupling agent modified boron nitride, and 30-60 parts of graphite/paraffin phase change material.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention includes 100 parts of vulcanized silicone rubber.
  • the present invention has no special requirements on the source of the vulcanized silicone rubber.
  • the vulcanized silicone rubber is Dow Corning 184 room temperature vulcanized silicone rubber.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention includes 20-30 parts of silane coupling agent-modified alumina, preferably 22-26 parts.
  • the particle size of the silane coupling agent-modified alumina is preferably 75-150 nm, more preferably 80-120 nm, and most preferably 85-100 nm.
  • the particle size of the silane coupling agent-modified alumina refers to the particle size of the alumina core.
  • the preparation method of the silane coupling agent modified alumina preferably comprises the following steps:
  • the ethanol solution of the silane coupling agent is mixed with alumina to obtain the alumina-silane coupling agent mixed liquid.
  • the silane coupling agent in the silane coupling agent ethanol solution is preferably KH-550 and/or KH-171.
  • the ethanol in the ethanol solution of the silane coupling agent is preferably absolute ethanol.
  • the mass percent of the ethanol solution of the silane coupling agent is preferably 4.5-9.5%, more preferably 4.76%.
  • the particle size of the alumina is preferably 75-150 nm, more preferably 80-120 nm, most preferably 85-100 nm.
  • the mass ratio of the silane coupling agent to the alumina is preferably ⁇ 0.02:1, more preferably (0.02 ⁇ 0.03):1.
  • the present invention has no special requirements on the specific implementation of mixing the ethanol solution of the silane coupling agent and alumina.
  • the present invention adopts an aqueous acid solution to adjust the pH value of the alumina-silane coupling agent mixed solution to ⁇ 4, and perform a modification reaction (hereinafter referred to as the first modification reaction),
  • the alumina modified by the silane coupling agent is obtained; the mass ratio of the silane coupling agent to the alumina is ⁇ 0.02:1.
  • the acid aqueous solution is preferably acetic acid, and the mass percentage of the acetic acid is preferably 1-5%.
  • the pH value of the alumina-silane coupling agent mixture is preferably ⁇ 4, more preferably 3-4.
  • the temperature of the first modification reaction is preferably 55-70°C, more preferably 58-65°C.
  • the time for the first modification reaction is preferably 1.5-3 hours, more preferably 2 hours.
  • the first modification reaction is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
  • the pH of the alumina-silane coupling agent mixed solution is preferably ⁇ 4
  • the silane coupling agent in the alumina-silane coupling agent mixed solution is hydrolyzed to obtain silanol bonds, silanol bonds and oxidation
  • the hydroxyl group on the surface of the aluminum undergoes a condensation dehydration condensation reaction to obtain a silane coupling agent modified alumina.
  • the first modification reaction liquid is obtained after the first modification reaction, and in the present invention, the first modification reaction liquid is preferably post-treated to obtain the silane coupling agent-modified alumina.
  • the post-treatment preferably includes: sequentially performing solid-liquid separation, washing, drying and grinding.
  • the method of solid-liquid separation is preferably vacuum filtration.
  • the solid product of solid-liquid separation is preferably washed.
  • the number of times of washing is preferably 3 to 5 times.
  • the washing solvent is preferably ethanol.
  • the solid-to-liquid ratio during each washing is preferably (10-20):1. The present invention removes the silane coupling agent remaining in the solid product by washing.
  • the washed solid product is preferably dried, and in the present invention, the drying temperature is preferably 110-125°C, more preferably 120°C. In the present invention, the drying time is preferably 4-5 hours.
  • the present invention has no special requirements on the specific implementation process of the grinding.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention includes 10-20 parts of silane coupling agent-modified boron nitride, preferably 12-15 parts.
  • the particle size of the boron nitride modified by the silane coupling agent is preferably 1-10 ⁇ m, more preferably 2-8 ⁇ m, and most preferably 5-6 ⁇ m.
  • the particle size of the boron nitride modified by the silane coupling agent refers to the particle size of the boron nitride core.
  • the preparation method of the silane coupling agent modified boron nitride preferably comprises the following steps:
  • silane coupling agent hydrolyzate a silane coupling agent hydrolyzate
  • the boron nitride aqueous dispersion and the silane coupling agent hydrolyzate are mixed for modification reaction to obtain the silane coupling agent modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ⁇ 0.02:1.
  • the silane coupling agent, ethanol and water are mixed and hydrolyzed to obtain a hydrolyzed solution of the silane coupling agent.
  • the silane coupling agent is preferably KH-550 and/or KH-171.
  • the ethanol is preferably absolute ethanol.
  • the mass ratio of the silane coupling agent, ethanol and water is preferably (15 ⁇ 25):(5 ⁇ 10):(70 ⁇ 75); more preferably (18 ⁇ 20):(6 ⁇ 8): (71 ⁇ 73).
  • the temperature of the mixed hydrolysis is preferably 45-55°C, more preferably 50°C.
  • the mixing hydrolysis time is preferably 20-50 minutes, more preferably 30 minutes.
  • the mixed hydrolysis is preferably carried out under the condition of stirring, and the present invention has no special requirements on the specific implementation process of the stirring.
  • the present invention mixes the boron nitride aqueous dispersion with the hydrolyzate of the silane coupling agent to carry out a modification reaction (hereinafter referred to as the second modification reaction) to obtain the silane coupling agent Modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ⁇ 0.02:1.
  • the particle size of boron nitride in the boron nitride aqueous dispersion is preferably 1-10 ⁇ m, more preferably 2-8 ⁇ m, and most preferably 5-6 ⁇ m.
  • the mass concentration of the boron nitride aqueous dispersion is preferably 0.15-0.25 g/mL, more preferably 0.2 g/mL.
  • the method for preparing the boron nitride aqueous dispersion preferably includes the following steps: dispersing the boron nitride in water to obtain the boron nitride aqueous dispersion.
  • the dispersion is preferably carried out under stirring conditions.
  • the present invention preferably heats the dispersion system of boron nitride and water to 80°C, and then stirs and disperses for 1-2 hours.
  • the present invention has no special requirements on the rate of heating.
  • the mass ratio of the silane coupling agent to the boron nitride is preferably ⁇ 0.02:1, more preferably (0.02 ⁇ 0.03):1.
  • the present invention has no special requirements on the specific implementation of mixing the boron nitride aqueous dispersion and the silane coupling agent hydrolyzate.
  • the temperature of the second modification reaction is preferably 40-52°C, more preferably 50°C.
  • the time for the second modification reaction is preferably 0.5-1.2 h, more preferably 1 h.
  • the second modification reaction is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
  • the silanol bond obtained by hydrolysis of the silane coupling agent in the hydrolyzed solution of the silane coupling agent undergoes condensation dehydration condensation reaction with the hydroxyl group on the surface of the boron nitride to obtain the boron nitride modified by the silane coupling agent.
  • the second modification reaction liquid is obtained after the second modification reaction, and in the present invention, the second modification reaction liquid is preferably post-treated to obtain the silane coupling agent-modified boron nitride.
  • the post-treatment preferably includes: sequentially performing solid-liquid separation, washing, drying and grinding.
  • the method of solid-liquid separation is preferably vacuum filtration.
  • the solid product of solid-liquid separation is preferably washed.
  • the number of times of washing is preferably 3 to 5 times.
  • the washing solvent is preferably ethanol.
  • the solid-to-liquid ratio during each washing is preferably (10-20):1. The present invention removes the silane coupling agent remaining in the solid product by washing.
  • the washed solid product is preferably dried, and in the present invention, the drying temperature is preferably 110-125°C, more preferably 120°C. In the present invention, the drying time is preferably 4-5 hours.
  • the present invention has no special requirements on the specific implementation process of the grinding.
  • the silane coupling agent-modified alumina with a particle size of 75-150 nm in nanometer size and the boron nitride modified with silane coupling agent with a particle size of 1-10 ⁇ m in micron size are preferably used as thermally conductive fillers, for the vulcanized silicone rubber Make modifications.
  • silane coupling agent-modified boron nitride with large particle size is stacked in vulcanized silicone rubber, the gaps generated are filled with silane coupling agent-modified alumina with small particle size.
  • the present invention preferably uses the above two modified fillers in A more effective thermally conductive connection network is formed in the vulcanized silicone rubber, which improves the thermal conductivity of the silicone rubber.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention includes 30-60 parts of graphite/paraffin phase-change material, preferably 35-50 parts.
  • the preparation method of the graphite/paraffin phase change material preferably comprises the following steps:
  • Graphite and molten paraffin are mixed and adsorbed to obtain the graphite/paraffin phase change material, and the mass ratio of the molten paraffin to graphite is ⁇ 0.6:1.
  • the particle size of the graphite is preferably 7-10 ⁇ m.
  • the solid-liquid phase transition temperature of the paraffin wax is preferably ⁇ 60°C. In a specific embodiment of the present invention, the solid-liquid phase transition temperature of the paraffin is preferably 44°C.
  • the present invention has no special requirements on the type and source of the paraffin.
  • the mass ratio of the molten paraffin to graphite is preferably ⁇ 0.6:1, more preferably (0.6 ⁇ 0.8):1.
  • the temperature of the mixed adsorption is preferably 60-65° C.
  • the time of the mixed adsorption is preferably 0.5-2 hours, more preferably 1 hour.
  • the mixed adsorption is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
  • the molten paraffin enters the pores of the graphite to obtain a graphite/paraffin phase change material.
  • a mixed adsorption system is obtained after the mixed adsorption, and in the present invention, the mixed adsorption system is preferably post-treated to obtain a graphite/paraffin phase change material.
  • the post-treatment preferably includes: sequentially performing solid-liquid separation, cooling and removing paraffin wax from the graphite surface.
  • the method of solid-liquid separation is preferably filtration, and the present invention has no special requirements on the specific implementation of the filtration.
  • the solid product of the solid-liquid separation is preferably cooled to room temperature to remove the solidified paraffin on the graphite surface.
  • the mass ratio of the silane coupling agent modified boron nitride, silane coupling agent modified alumina and graphite/paraffin phase change material is preferably (2 ⁇ 3):(1 ⁇ 2):( 3 ⁇ 5), more preferably 3:2:3.
  • the present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical solution, comprising the following steps:
  • the mixed material and curing agent are mixed and cured to obtain the high thermal conductivity phase change silicone rubber.
  • the invention mixes vulcanized silicon rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride and graphite/paraffin phase change material to obtain a mixed material.
  • the present invention has no special requirements on the mixing sequence and specific implementation process of the vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, graphite/paraffin phase change material.
  • the present invention mixes and cures the mixed material and the curing agent at room temperature to obtain the high thermal conductivity phase-change silicone rubber.
  • the curing agent is preferably a curing agent compatible with the vulcanized silicone rubber.
  • the curing agent is Dow Corning 184 silicone rubber curing agent.
  • the mass ratio of the curing agent to the vulcanized silicone rubber is preferably 1:10.
  • the material to be cured obtained after mixing the mixed material and the curing agent is vacuum-exhausted, and then the exhausted cured material is poured into a mold and cured at room temperature.
  • the present invention provides the application of the high thermal conductivity phase change silicone rubber described in the above technical solution or the high thermal conductivity phase change silicone rubber prepared by the preparation method described in the above technical solution in heat dissipation devices for electronic or semiconductor components.
  • the present invention has no special requirements on the specific application of the high thermal conductivity phase change silicone rubber.
  • the silane coupling agent KH-550 and absolute ethanol were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
  • FIG. 1 is a physical picture of the high thermal conductivity phase-change silicone rubber prepared in Example 1
  • FIG. 2 is a DSC chart of the high thermal conductivity phase-change silicone rubber prepared in Example 1.
  • the silane coupling agent KH-550 and absolute ethanol were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
  • the silane coupling agent KH-550 and absolute ethanol were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
  • the silane coupling agent KH-171 and absolute ethanol were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-171 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 3.5, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash with absolute ethanol 3 times to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
  • Fig. 2 is a DSC scan diagram of Example 3, using a thermal conductivity tester (DTC-300) to perform a thermal conductivity test, and the test results are shown in Table 1.
  • the high thermal conductivity phase-change silicone rubber provided by the present invention has Excellent thermal conductivity.
  • the thermal conductivity of the high thermal conductivity phase change silicone rubber prepared in the embodiment of the present invention is further improved, and the thermal conductivity of Example 1 is higher than that of Pure rubber has improved by 7.9%, the thermal conductivity of embodiment 2 has improved by 13.3% compared with pure rubber, and the thermal conductivity of embodiment 3 has improved by 29.7% than pure rubber.

Abstract

The present invention relates to a high thermal-conductivity phase-change organic silicon rubber, comprising 100 parts of vulcanized silicon rubber, 20-30 parts of aluminum oxide modified with a silane coupling agent, 10-20 parts of boron nitride modified with a silane coupling agent, and 30-60 parts of a graphite/paraffin phase-change material. By providing the three fillers, under the condition that the addition amount is small, the thermal conduction property of the silicon rubber is improved, and the physical processing property of the silicon rubber is not influenced.

Description

一种高导热相变有机硅橡胶及其制备方法和应用A kind of high thermal conductivity phase change silicone rubber and its preparation method and application
本申请要求于2021年11月3日提交中国专利局、申请号为CN202111295663.7、发明名称为“一种高导热相变有机硅橡胶及其制备方法和应用”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 submitted to the China Patent Office on November 3, 2021, with the application number CN202111295663.7, and the title of the invention "a high thermal conductivity phase-change silicone rubber and its preparation method and application", The entire contents of which are incorporated by reference in this application.
技术领域technical field
本发明涉及有机硅橡胶技术领域，尤其涉及一种高导热相变有机硅橡胶及其制备方法和应用。The invention relates to the technical field of silicone rubber, in particular to a phase-change silicone rubber with high thermal conductivity and its preparation method and application.
背景技术Background technique
在众多的合成橡胶中，硅橡胶是其中的佼佼者，它具有无味无毒，不怕高温和抵御严寒等特点，普通硅橡胶在200℃至-50℃之间仍不失原有的强度和弹性，同时，硅橡胶还有良好的电绝缘性、耐氧抗老化性、耐光抗老化性以及防霉性、化学稳定性等，因此其被广泛应用于航天航空、汽车、船舶、办公用品、电子等行业。Among many synthetic rubbers, silicone rubber is one of the best. It is odorless, non-toxic, not afraid of high temperature and can withstand severe cold. Ordinary silicone rubber still maintains its original strength and elasticity between 200°C and -50°C. At the same time, silicone rubber also has good electrical insulation, oxygen and aging resistance, light and aging resistance, mildew resistance, chemical stability, etc., so it is widely used in aerospace, automobiles, ships, office supplies, electronics, etc. and other industries.
随着机械设备和电子元件日益小型化，紧密化，产品的热设计也迎来考验。若无法及时将设备和元件在工作时产生的热量及时传导出去，将会对设备和元件的寿命产生严重影响，甚至发生事故。With the miniaturization and compactness of mechanical equipment and electronic components, the thermal design of products is also facing challenges. If the heat generated by the equipment and components during operation cannot be conducted in time, it will have a serious impact on the life of the equipment and components, or even cause an accident.
目前普通硅橡胶的导热性能普遍不理想，导热率一般只有0.165W/(m·k)，通过填充导热填料可提高其导热性能，现有的导电填料包括氧化铝、氧化锌、氮化硼、碳化钛和白炭黑等，但目前工业生产中通常需要加入填料量远大于橡胶量才能够改善其导热性能，这会影响材料的加工性能，给硅橡胶材料的进一步应用带来了诸多限制。At present, the thermal conductivity of ordinary silicone rubber is generally not ideal, and the thermal conductivity is generally only 0.165W/(m·k). The thermal conductivity can be improved by filling thermal conductive fillers. The existing conductive fillers include alumina, zinc oxide, boron nitride, Titanium carbide and white carbon black, etc., but in the current industrial production, it is usually necessary to add a much larger amount of filler than rubber to improve its thermal conductivity, which will affect the processing performance of the material and bring many restrictions to the further application of silicone rubber materials.
发明内容Contents of the invention
有鉴于此，本发明提供了一种高导热相变有机硅橡胶及其制备方法和应用，本发明提供的高导热相变有机硅橡胶在不影响硅橡胶的物理加工性能的条件下具备优异的导热性能。In view of this, the present invention provides a high thermal conductivity phase-change silicone rubber and its preparation method and application. The high thermal conductivity phase-change silicone rubber provided by the invention has excellent properties without affecting the physical processing performance of silicone rubber. thermal conductivity.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种高导热相变有机硅橡胶，包括以下质量份数的组分：The invention provides a phase-change silicone rubber with high thermal conductivity, comprising the following components in parts by mass:
硫化硅橡胶100份、硅烷偶联剂改性氧化铝20～30份、硅烷偶联剂改性氮化硼10～20份、石墨/石蜡相变材料30～60份。100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, 10-20 parts of silane coupling agent modified boron nitride, and 30-60 parts of graphite/paraffin phase change material.
优选的，所述硅烷偶联剂改性氧化铝的粒径为75～150nm。Preferably, the particle size of the silane coupling agent-modified alumina is 75-150 nm.
优选的，所述硅烷偶联剂改性氮化硼的粒径为1～10μm。Preferably, the particle size of the boron nitride modified by the silane coupling agent is 1-10 μm.
优选的，所述硅烷偶联剂改性氧化铝的制备方法包括以下步骤：Preferably, the preparation method of the silane coupling agent modified alumina comprises the following steps:
将硅烷偶联剂乙醇溶液和氧化铝混合，得到氧化铝-硅烷偶联剂混合液；mixing the ethanol solution of the silane coupling agent with alumina to obtain a mixed solution of alumina-silane coupling agent;
采用酸的水溶液调节所述氧化铝-硅烷偶联剂混合液的pH值≤4，进行改性反应，得到所述硅烷偶联剂改性氧化铝；所述硅烷偶联剂和所述氧化铝的质量比≥0.02:1。Adjust the pH value of the alumina-silane coupling agent mixed solution to ≤4 by using an aqueous acid solution, and perform a modification reaction to obtain the silane coupling agent-modified alumina; the silane coupling agent and the alumina The mass ratio of ≥0.02:1.
优选的，所述硅烷偶联剂改性氮化硼的制备方法包括以下步骤：Preferably, the preparation method of described silane coupling agent modified boron nitride comprises the following steps:
将所述硅烷偶联剂、乙醇和水混合水解，得到硅烷偶联剂水解液；Mixing and hydrolyzing the silane coupling agent, ethanol and water to obtain a silane coupling agent hydrolyzate;
将氮化硼水分散液和所述硅烷偶联剂水解液混合进行改性反应，得到所述硅烷偶联剂改性氮化硼；所述硅烷偶联剂和所述氮化硼的质量比≥0.02:1。The boron nitride aqueous dispersion and the silane coupling agent hydrolyzate are mixed for modification reaction to obtain the silane coupling agent modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ≥0.02:1.
优选的，所述石墨/石蜡相变材料的制备方法包括以下步骤：Preferably, the preparation method of described graphite/paraffin phase change material comprises the following steps:
将石墨和熔融态石蜡混合吸附，得到所述石墨/石蜡相变材料，所述熔融态石蜡和石墨的质量比≥0.6:1。Graphite and molten paraffin are mixed and adsorbed to obtain the graphite/paraffin phase change material, and the mass ratio of the molten paraffin to graphite is ≥0.6:1.
优选的，硅烷偶联剂乙醇溶液的质量百分比为4.5～9.5％；所述改性反应的温度为55～70℃，所述改性反应的时间为1.5～3h。Preferably, the mass percentage of the ethanol solution of the silane coupling agent is 4.5-9.5%; the temperature of the modification reaction is 55-70° C., and the time of the modification reaction is 1.5-3 hours.
优选的，所述硅烷偶联剂、乙醇和水的质量比为(15～25):(5～10):(70～75)；所述改性反应的温度为40～52℃，所述改性反应的时间为0.5～1.2h。Preferably, the mass ratio of the silane coupling agent, ethanol and water is (15～25):(5～10):(70～75); the temperature of the modification reaction is 40～52°C, and the The modification reaction time is 0.5-1.2h.
本发明提供了上述技术方案所述高导热相变有机硅橡胶的制备方法，包括以下步骤：The present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical solution, comprising the following steps:
将硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料混合，得到混合物料；Mix vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, and graphite/paraffin phase change material to obtain a mixed material;
在室温条件下，将所述混合物料和固化剂混合固化，得到所述高导热相变有机硅橡胶。At room temperature, the mixed material and curing agent are mixed and cured to obtain the high thermal conductivity phase change silicone rubber.
本发明提供了上述技术方案所述高导热相变有机硅橡胶或上述技术 方案所述的制备方法制备的高导热相变有机硅橡胶在电子或半导体元器件散热器件中的应用。The present invention provides the application of the high thermal conductivity phase change silicone rubber described in the above technical solution or the high thermal conductivity phase change silicone rubber prepared by the preparation method described in the above technical solution in heat dissipation devices for electronic or semiconductor components.
本发明提供一种高导热相变有机硅橡胶，包括以下质量份数的组分：硫化硅橡胶100份、硅烷偶联剂改性氧化铝20～30份、硅烷偶联剂改性氮化硼10～20份、石墨/石蜡相变材料30～60份。本发明提供的高导热相变有机硅橡胶采用硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼和石墨/石蜡相变材料三种填料协同对硫化硅橡胶进行导热性能的改性，氮化硼和氧化铝的导热系数较高，且通过硅烷偶联剂改性的氮化硼和氧化铝在有机硅橡胶中能够实现高度分散，从而在硅橡胶中形成导热网络，提高硅橡胶的导热系数；同时，石墨/石蜡相变材料通过石蜡由固态向液态相变吸热的性能提高硅橡胶的导热性能。本发明提供上述三种填料在添加量较小的情况下实现了对硅橡胶导热性能的改善，且不影响硅橡胶的物理加工性能。由实施例的结果表明，本发明提供的高导热相变有机硅橡胶的密度为1.068～1.074g/cm 3，相变潜热为7.274～18.37J/g，导热系数为0.178～0.214W/(m·k)。 The invention provides a high thermal conductivity phase-change silicone rubber, which comprises the following components in parts by mass: 100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, and silane coupling agent modified boron nitride 10-20 parts, graphite/paraffin phase change material 30-60 parts. The high thermal conductivity phase-change silicone rubber provided by the present invention adopts three fillers of silane coupling agent modified alumina, silane coupling agent modified boron nitride and graphite/paraffin phase change material to improve the thermal conductivity of vulcanized silicone rubber. The thermal conductivity of boron nitride and aluminum oxide is high, and boron nitride and aluminum oxide modified by silane coupling agent can be highly dispersed in silicone rubber, thereby forming a thermal conductivity network in silicone rubber and improving silicon rubber The thermal conductivity of rubber; at the same time, the graphite/paraffin phase change material improves the thermal conductivity of silicone rubber through the heat absorption performance of paraffin from solid to liquid phase change. The invention provides that the above three fillers can improve the thermal conductivity of the silicone rubber with a small amount of addition, without affecting the physical processing performance of the silicone rubber. The results of the examples show that the high thermal conductivity phase-change silicone rubber provided by the present invention has a density of 1.068-1.074g/cm 3 , a phase-change latent heat of 7.274-18.37J/g, and a thermal conductivity of 0.178-0.214W/(m k).
本发明提供了上述技术方案所述高导热相变有机硅橡胶的制备方法，包括以下步骤：将硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料混合，得到混合物料；在室温条件下，将所述混合物料和固化剂混合固化，得到所述高导热相变有机硅橡胶。本发明提供的制备方法能够在室温条件下实现固化，反应条件简单，适宜工业化生产。The present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical scheme, comprising the following steps: vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, graphite/ The paraffin phase-change materials are mixed to obtain a mixed material; at room temperature, the mixed material and a curing agent are mixed and solidified to obtain the high thermal conductivity phase-change silicone rubber. The preparation method provided by the invention can realize curing at room temperature, has simple reaction conditions, and is suitable for industrial production.
说明书附图Instructions attached
图1为本发明实施例3制备的高导热相变有机硅橡胶的实物图；Fig. 1 is the physical picture of the high thermal conductivity phase-change silicone rubber prepared in Example 3 of the present invention;
图2为本发明实施例3制备的高导热相变有机硅橡胶的DSC图。Fig. 2 is a DSC chart of the phase-change silicone rubber with high thermal conductivity prepared in Example 3 of the present invention.
具体实施方式Detailed ways
本发明提供了一种高导热相变有机硅橡胶，包括以下质量份数的组分：The invention provides a phase-change silicone rubber with high thermal conductivity, comprising the following components in parts by mass:
硫化硅橡胶100份、硅烷偶联剂改性氧化铝20～30份、硅烷偶联剂改性氮化硼10～20份、石墨/石蜡相变材料30～60份。100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, 10-20 parts of silane coupling agent modified boron nitride, and 30-60 parts of graphite/paraffin phase change material.
本发明提供的高导热相变有机硅橡胶包括100份的硫化硅橡胶。本发 明对所述硫化硅橡胶的来源没有特殊要求，在本发明的具体实施例中，所述硫化硅橡胶为道康宁184室温硫化硅橡胶。The high thermal conductivity phase-change silicone rubber provided by the present invention includes 100 parts of vulcanized silicone rubber. The present invention has no special requirements on the source of the vulcanized silicone rubber. In a specific embodiment of the present invention, the vulcanized silicone rubber is Dow Corning 184 room temperature vulcanized silicone rubber.
以硫化硅橡胶的质量份数100份为基准，本发明提供的高导热相变有机硅橡胶包括20～30份的硅烷偶联剂改性氧化铝，优选为22～26份。Based on 100 parts by mass of vulcanized silicone rubber, the high thermal conductivity phase-change silicone rubber provided by the present invention includes 20-30 parts of silane coupling agent-modified alumina, preferably 22-26 parts.
在本发明中，所述硅烷偶联剂改性氧化铝的粒径优选为75～150nm，更优选为80～120nm，最优选为85～100nm。在本发明中，所述硅烷偶联剂改性氧化铝的粒径指的是所述氧化铝核心的粒径。In the present invention, the particle size of the silane coupling agent-modified alumina is preferably 75-150 nm, more preferably 80-120 nm, and most preferably 85-100 nm. In the present invention, the particle size of the silane coupling agent-modified alumina refers to the particle size of the alumina core.
在本发明中，所述硅烷偶联剂改性氧化铝的制备方法优选包括以下步骤：In the present invention, the preparation method of the silane coupling agent modified alumina preferably comprises the following steps:
将硅烷偶联剂乙醇溶液和氧化铝混合，得到氧化铝-硅烷偶联剂混合液；mixing the ethanol solution of the silane coupling agent with alumina to obtain a mixed solution of alumina-silane coupling agent;
采用酸的水溶液调节所述氧化铝-硅烷偶联剂混合液的pH值≤4，进行改性反应，得到所述硅烷偶联剂改性氧化铝；所述硅烷偶联剂和所述氧化铝的质量比≥0.02:1。Adjust the pH value of the alumina-silane coupling agent mixed solution to ≤4 by using an aqueous acid solution, and perform a modification reaction to obtain the silane coupling agent-modified alumina; the silane coupling agent and the alumina The mass ratio of ≥0.02:1.
本发明将硅烷偶联剂乙醇溶液和氧化铝混合，得到氧化铝-硅烷偶联剂混合液。In the invention, the ethanol solution of the silane coupling agent is mixed with alumina to obtain the alumina-silane coupling agent mixed liquid.
在本发明中，所述将硅烷偶联剂乙醇溶液中的硅烷偶联剂优选为KH-550和/或KH-171。在本发明中，所述将硅烷偶联剂乙醇溶液中的乙醇优选为无水乙醇。In the present invention, the silane coupling agent in the silane coupling agent ethanol solution is preferably KH-550 and/or KH-171. In the present invention, the ethanol in the ethanol solution of the silane coupling agent is preferably absolute ethanol.
在本发明中，所述硅烷偶联剂乙醇溶液的质量百分比优选为4.5～9.5％，更优选为4.76％。In the present invention, the mass percent of the ethanol solution of the silane coupling agent is preferably 4.5-9.5%, more preferably 4.76%.
在本发明中，所述氧化铝的粒径优选为75～150nm，更优选为80～120nm，最优选为85～100nm。In the present invention, the particle size of the alumina is preferably 75-150 nm, more preferably 80-120 nm, most preferably 85-100 nm.
在本发明中，所述硅烷偶联剂和所述氧化铝的质量比优选≥0.02:1，更优选为(0.02～0.03):1。In the present invention, the mass ratio of the silane coupling agent to the alumina is preferably ≥0.02:1, more preferably (0.02˜0.03):1.
本发明对硅烷偶联剂乙醇溶液和氧化铝混合的具体实施方式没有特殊要求。The present invention has no special requirements on the specific implementation of mixing the ethanol solution of the silane coupling agent and alumina.
得到氧化铝-硅烷偶联剂混合液后，本发明采用酸的水溶液调节所述氧化铝-硅烷偶联剂混合液的pH值≤4，进行改性反应(以下成为第一改性反应)，得到所述硅烷偶联剂改性氧化铝；所述硅烷偶联剂和所述氧化 铝的质量比≥0.02:1。After the alumina-silane coupling agent mixed solution is obtained, the present invention adopts an aqueous acid solution to adjust the pH value of the alumina-silane coupling agent mixed solution to ≤4, and perform a modification reaction (hereinafter referred to as the first modification reaction), The alumina modified by the silane coupling agent is obtained; the mass ratio of the silane coupling agent to the alumina is ≥0.02:1.
在本发明中，所述酸的水溶液优选为醋酸，所述醋酸的质量百分比优选为1～5％。In the present invention, the acid aqueous solution is preferably acetic acid, and the mass percentage of the acetic acid is preferably 1-5%.
在本发明中，调节pH值后，所述氧化铝-硅烷偶联剂混合液的pH值优选≤4，更优选为3～4。In the present invention, after adjusting the pH value, the pH value of the alumina-silane coupling agent mixture is preferably ≤4, more preferably 3-4.
在本发明中，所述第一改性反应的温度优选为55～70℃，更优选为58～65℃。在本发明中，所述第一改性反应的时间优选为1.5～3h，更优选为2h。在本发明中，所述第一改性反应优选为在搅拌的条件下进行，本发明对所述搅拌的具体实施过程没有特殊要求。In the present invention, the temperature of the first modification reaction is preferably 55-70°C, more preferably 58-65°C. In the present invention, the time for the first modification reaction is preferably 1.5-3 hours, more preferably 2 hours. In the present invention, the first modification reaction is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
本发明通过调节所述氧化铝-硅烷偶联剂混合液的pH优选≤4时，所述氧化铝-硅烷偶联剂混合液中的硅烷偶联剂水解得到硅醇键，硅醇键和氧化铝表面的羟基发生缩合脱水缩合反应，得到硅烷偶联剂改性氧化铝。In the present invention, when the pH of the alumina-silane coupling agent mixed solution is preferably ≤4, the silane coupling agent in the alumina-silane coupling agent mixed solution is hydrolyzed to obtain silanol bonds, silanol bonds and oxidation The hydroxyl group on the surface of the aluminum undergoes a condensation dehydration condensation reaction to obtain a silane coupling agent modified alumina.
在本发明中，所述第一改性反应后得到第一改性反应液，本发明优选对所述第一改性反应液进行后处理，得到所述硅烷偶联剂改性氧化铝。在本发明中，所述后处理优选包括：依次进行固液分离、洗涤和干燥和研磨。在本发明中，所述固液分离的方式优选为真空抽滤，本发明优选对所述固液分离的固体产物进行洗涤，在本发明中，所述洗涤的次数优选为3～5次，所述洗涤用溶剂优选为乙醇，在本发明中，每次洗涤时的固液比优选为(10～20):1，本发明通过洗涤去除固体产物残留的硅烷偶联剂。本发明优选对洗涤后的固体产物进行干燥，在本发明中，所述干燥的温度优选为110～125℃，更优选为120℃。在本发明中，所述干燥的时间优选为4～5h。本发明对所述研磨的具体实施过程没有特殊要求。In the present invention, the first modification reaction liquid is obtained after the first modification reaction, and in the present invention, the first modification reaction liquid is preferably post-treated to obtain the silane coupling agent-modified alumina. In the present invention, the post-treatment preferably includes: sequentially performing solid-liquid separation, washing, drying and grinding. In the present invention, the method of solid-liquid separation is preferably vacuum filtration. In the present invention, the solid product of solid-liquid separation is preferably washed. In the present invention, the number of times of washing is preferably 3 to 5 times. The washing solvent is preferably ethanol. In the present invention, the solid-to-liquid ratio during each washing is preferably (10-20):1. The present invention removes the silane coupling agent remaining in the solid product by washing. In the present invention, the washed solid product is preferably dried, and in the present invention, the drying temperature is preferably 110-125°C, more preferably 120°C. In the present invention, the drying time is preferably 4-5 hours. The present invention has no special requirements on the specific implementation process of the grinding.
以硫化硅橡胶的质量份数为基准，本发明提供的高导热相变有机硅橡胶包括10～20份的硅烷偶联剂改性氮化硼，优选为12～15份。Based on the mass fraction of vulcanized silicone rubber, the high thermal conductivity phase-change silicone rubber provided by the present invention includes 10-20 parts of silane coupling agent-modified boron nitride, preferably 12-15 parts.
在本发明中，所述硅烷偶联剂改性氮化硼的粒径优选为1～10μm，更优选为2～8μm，最优选为5～6μm。在本发明中，所述硅烷偶联剂改性氮化硼的粒径指的是所述氮化硼核心的粒径。In the present invention, the particle size of the boron nitride modified by the silane coupling agent is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 5-6 μm. In the present invention, the particle size of the boron nitride modified by the silane coupling agent refers to the particle size of the boron nitride core.
在本发明中，所述硅烷偶联剂改性氮化硼的制备方法优选包括以下步骤：In the present invention, the preparation method of the silane coupling agent modified boron nitride preferably comprises the following steps:
将所述硅烷偶联剂、乙醇和水混合水解，得到硅烷偶联剂水解液；Mixing and hydrolyzing the silane coupling agent, ethanol and water to obtain a silane coupling agent hydrolyzate;
将氮化硼水分散液和所述硅烷偶联剂水解液混合进行改性反应，得到所述硅烷偶联剂改性氮化硼；所述硅烷偶联剂和所述氮化硼的质量比≥0.02:1。The boron nitride aqueous dispersion and the silane coupling agent hydrolyzate are mixed for modification reaction to obtain the silane coupling agent modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ≥0.02:1.
本发明将所述硅烷偶联剂、乙醇和水混合水解，得到硅烷偶联剂水解液。In the invention, the silane coupling agent, ethanol and water are mixed and hydrolyzed to obtain a hydrolyzed solution of the silane coupling agent.
在本发明中，所述硅烷偶联剂优选为KH-550和/或KH-171。在本发明中，所述乙醇优选为无水乙醇。In the present invention, the silane coupling agent is preferably KH-550 and/or KH-171. In the present invention, the ethanol is preferably absolute ethanol.
在本发明中，所述硅烷偶联剂、乙醇和水的质量比优选为(15～25):(5～10):(70～75)；更优选为(18～20):(6～8):(71～73)。In the present invention, the mass ratio of the silane coupling agent, ethanol and water is preferably (15～25):(5～10):(70～75); more preferably (18～20):(6～ 8): (71～73).
在本发明中，所述混合水解的温度优选为45～55℃，更优选为50℃。在本发明中，所述混合水解的时间优选为20～50min，更优选为30min。在本发明中，所述混合水解优选在搅拌的条件下进行，本发明对所述搅拌的具体实施过程没有特殊要求。In the present invention, the temperature of the mixed hydrolysis is preferably 45-55°C, more preferably 50°C. In the present invention, the mixing hydrolysis time is preferably 20-50 minutes, more preferably 30 minutes. In the present invention, the mixed hydrolysis is preferably carried out under the condition of stirring, and the present invention has no special requirements on the specific implementation process of the stirring.
得到硅烷偶联剂水解液后，本发明将氮化硼水分散液和所述硅烷偶联剂水解液混合进行改性反应(以下称为第二改性反应)，得到所述硅烷偶联剂改性氮化硼；所述硅烷偶联剂和所述氮化硼的质量比≥0.02:1。After obtaining the hydrolyzate of the silane coupling agent, the present invention mixes the boron nitride aqueous dispersion with the hydrolyzate of the silane coupling agent to carry out a modification reaction (hereinafter referred to as the second modification reaction) to obtain the silane coupling agent Modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ≥0.02:1.
在本发明中，所述氮化硼水分散液中氮化硼的粒径优选为1～10μm，更优选为2～8μm，最优选为5～6μm。In the present invention, the particle size of boron nitride in the boron nitride aqueous dispersion is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 5-6 μm.
在本发明中，所述氮化硼水分散液质量浓度优选为0.15～0.25g/mL，更优选为0.2g/mL。In the present invention, the mass concentration of the boron nitride aqueous dispersion is preferably 0.15-0.25 g/mL, more preferably 0.2 g/mL.
在本发明中，所述氮化硼水分散液的制备方法优选包括以下步骤：将所述氮化硼分散于水中，得到所述氮化硼水分散液。在本发明中，所述分散优选在搅拌的条件下进行，所述分散过程中，本发明优选将氮化硼和水的分散体系加热至80℃后，再搅拌分散1～2h。本发明对加热的速率没有特殊要求。In the present invention, the method for preparing the boron nitride aqueous dispersion preferably includes the following steps: dispersing the boron nitride in water to obtain the boron nitride aqueous dispersion. In the present invention, the dispersion is preferably carried out under stirring conditions. During the dispersion process, the present invention preferably heats the dispersion system of boron nitride and water to 80°C, and then stirs and disperses for 1-2 hours. The present invention has no special requirements on the rate of heating.
在本发明中，所述硅烷偶联剂和所述氮化硼的质量比优选≥0.02:1，更优选为(0.02～0.03):1。In the present invention, the mass ratio of the silane coupling agent to the boron nitride is preferably ≥0.02:1, more preferably (0.02˜0.03):1.
本发明对所述氮化硼水分散液和硅烷偶联剂水解液混合的具体实施方式没有特殊要求。The present invention has no special requirements on the specific implementation of mixing the boron nitride aqueous dispersion and the silane coupling agent hydrolyzate.
在本发明中，所述第二改性反应的温度优选为40～52℃，更优选为 50℃。在本发明中，所述第二改性反应的时间优选为0.5～1.2h，更优选为1h。在本发明中，所述第二改性反应优选为在搅拌的条件下进行，本发明对所述搅拌的具体实施过程没有特殊要求。In the present invention, the temperature of the second modification reaction is preferably 40-52°C, more preferably 50°C. In the present invention, the time for the second modification reaction is preferably 0.5-1.2 h, more preferably 1 h. In the present invention, the second modification reaction is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
本发明通过所述硅烷偶联剂水解液中的硅烷偶联剂水解得到的硅醇键，与氮化硼表面的羟基发生缩合脱水缩合反应，得到硅烷偶联剂改性氮化硼。In the present invention, the silanol bond obtained by hydrolysis of the silane coupling agent in the hydrolyzed solution of the silane coupling agent undergoes condensation dehydration condensation reaction with the hydroxyl group on the surface of the boron nitride to obtain the boron nitride modified by the silane coupling agent.
在本发明中，所述第二改性反应后得到第二改性反应液，本发明优选对所述第二改性反应液进行后处理，得到所述硅烷偶联剂改性氮化硼。在本发明中，所述后处理优选包括：依次进行固液分离、洗涤和干燥和研磨。在本发明中，所述固液分离的方式优选为真空抽滤，本发明优选对所述固液分离的固体产物进行洗涤，在本发明中，所述洗涤的次数优选为3～5次，所述洗涤用溶剂优选为乙醇，在本发明中，每次洗涤时的固液比优选为(10～20):1，本发明通过洗涤去除固体产物残留的硅烷偶联剂。本发明优选对洗涤后的固体产物进行干燥，在本发明中，所述干燥的温度优选为110～125℃，更优选为120℃。在本发明中，所述干燥的时间优选为4～5h。本发明对所述研磨的具体实施过程没有特殊要求。In the present invention, the second modification reaction liquid is obtained after the second modification reaction, and in the present invention, the second modification reaction liquid is preferably post-treated to obtain the silane coupling agent-modified boron nitride. In the present invention, the post-treatment preferably includes: sequentially performing solid-liquid separation, washing, drying and grinding. In the present invention, the method of solid-liquid separation is preferably vacuum filtration. In the present invention, the solid product of solid-liquid separation is preferably washed. In the present invention, the number of times of washing is preferably 3 to 5 times. The washing solvent is preferably ethanol. In the present invention, the solid-to-liquid ratio during each washing is preferably (10-20):1. The present invention removes the silane coupling agent remaining in the solid product by washing. In the present invention, the washed solid product is preferably dried, and in the present invention, the drying temperature is preferably 110-125°C, more preferably 120°C. In the present invention, the drying time is preferably 4-5 hours. The present invention has no special requirements on the specific implementation process of the grinding.
本发明优选将纳米级粒径为75～150nm硅烷偶联剂改性氧化铝和微米级粒径为1～10μm的硅烷偶联剂改性氮化硼协同作为导热填料，对所述硫化硅橡胶进行改性。大粒径的硅烷偶联剂改性氮化硼在硫化硅橡胶中堆叠时，产生的空隙由小粒径的硅烷偶联剂改性氧化铝填充，本发明优选以上述两种改性填料在硫化硅橡胶中形成更有效的导热连接网络，提高了硅橡胶的导热性能。In the present invention, the silane coupling agent-modified alumina with a particle size of 75-150 nm in nanometer size and the boron nitride modified with silane coupling agent with a particle size of 1-10 μm in micron size are preferably used as thermally conductive fillers, for the vulcanized silicone rubber Make modifications. When silane coupling agent-modified boron nitride with large particle size is stacked in vulcanized silicone rubber, the gaps generated are filled with silane coupling agent-modified alumina with small particle size. The present invention preferably uses the above two modified fillers in A more effective thermally conductive connection network is formed in the vulcanized silicone rubber, which improves the thermal conductivity of the silicone rubber.
以硫化硅橡胶的质量份数为基准，本发明提供的高导热相变有机硅橡胶包括30～60份的石墨/石蜡相变材料，优选为35～50份。Based on the mass fraction of vulcanized silicone rubber, the high thermal conductivity phase-change silicone rubber provided by the present invention includes 30-60 parts of graphite/paraffin phase-change material, preferably 35-50 parts.
在本发明中，所述石墨/石蜡相变材料的制备方法优选包括以下步骤：In the present invention, the preparation method of the graphite/paraffin phase change material preferably comprises the following steps:
将石墨和熔融态石蜡混合吸附，得到所述石墨/石蜡相变材料，所述熔融态石蜡和石墨的质量比≥0.6:1。Graphite and molten paraffin are mixed and adsorbed to obtain the graphite/paraffin phase change material, and the mass ratio of the molten paraffin to graphite is ≥0.6:1.
在本发明中，所述石墨的粒度优选为7～10μm。在本发明中，所述石蜡的固液相变温度优选≤60℃。在本发明的具体实施例中，所述石蜡的固液相变温度具体优选为44℃。本发明对所述石蜡的种类和来源没有特殊 要求。In the present invention, the particle size of the graphite is preferably 7-10 μm. In the present invention, the solid-liquid phase transition temperature of the paraffin wax is preferably ≤60°C. In a specific embodiment of the present invention, the solid-liquid phase transition temperature of the paraffin is preferably 44°C. The present invention has no special requirements on the type and source of the paraffin.
在本发明中，所述熔融态石蜡和石墨的质量比优选≥0.6:1，更优选为(0.6～0.8):1。In the present invention, the mass ratio of the molten paraffin to graphite is preferably ≥0.6:1, more preferably (0.6˜0.8):1.
在本发明中，所述混合吸附的温度优选为60～65℃，所述混合吸附的时间优选为0.5～2h，更优选为1h。在本发明中，所述混合吸附优选在搅拌的条件下进行，本发明对所述搅拌的具体实施过程没有特殊要求。In the present invention, the temperature of the mixed adsorption is preferably 60-65° C., and the time of the mixed adsorption is preferably 0.5-2 hours, more preferably 1 hour. In the present invention, the mixed adsorption is preferably carried out under stirring conditions, and the present invention has no special requirements on the specific implementation process of the stirring.
在本发明中，所述混合吸附时，熔融态石蜡进入所述石墨的孔径内，得到石墨/石蜡相变材料。In the present invention, during the mixed adsorption, the molten paraffin enters the pores of the graphite to obtain a graphite/paraffin phase change material.
在本发明中，所述混合吸附后得到混合吸附体系，本发明优选对所述混合吸附体系进行后处理，得到石墨/石蜡相变材料。在本发明中，所述后处理优选包括：依次进行固液分离、冷却和将石墨表面的石蜡清除。在本发明中，所述固液分离的方式优选为过滤，本发明对所述过滤的具体实施方式没有特殊要求。本发明优选将所述固液分离的固体产物冷却至室温后将石墨表面凝固后的石蜡清除。In the present invention, a mixed adsorption system is obtained after the mixed adsorption, and in the present invention, the mixed adsorption system is preferably post-treated to obtain a graphite/paraffin phase change material. In the present invention, the post-treatment preferably includes: sequentially performing solid-liquid separation, cooling and removing paraffin wax from the graphite surface. In the present invention, the method of solid-liquid separation is preferably filtration, and the present invention has no special requirements on the specific implementation of the filtration. In the present invention, the solid product of the solid-liquid separation is preferably cooled to room temperature to remove the solidified paraffin on the graphite surface.
在本发明中，所述硅烷偶联剂改性氮化硼、硅烷偶联剂改性氧化铝和石墨/石蜡相变材料的质量比优选为(2～3):(1～2):(3～5)，更优选为3:2:3。In the present invention, the mass ratio of the silane coupling agent modified boron nitride, silane coupling agent modified alumina and graphite/paraffin phase change material is preferably (2～3):(1～2):( 3～5), more preferably 3:2:3.
本发明提供了上述技术方案所述高导热相变有机硅橡胶的制备方法，包括以下步骤：The present invention provides a preparation method of high thermal conductivity phase-change silicone rubber described in the above technical solution, comprising the following steps:
将硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料混合，得到混合物料；Mix vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, and graphite/paraffin phase change material to obtain a mixed material;
在室温条件下，将所述混合物料和固化剂混合固化，得到所述高导热相变有机硅橡胶。At room temperature, the mixed material and curing agent are mixed and cured to obtain the high thermal conductivity phase change silicone rubber.
本发明将硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料混合，得到混合物料。The invention mixes vulcanized silicon rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride and graphite/paraffin phase change material to obtain a mixed material.
本发明对所述硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料的混合顺序和混合的具体实施过程没有特殊要求。The present invention has no special requirements on the mixing sequence and specific implementation process of the vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, graphite/paraffin phase change material.
得到混合物料后，本发明在室温条件下，将所述混合物料和固化剂混合固化，得到所述高导热相变有机硅橡胶。After the mixed material is obtained, the present invention mixes and cures the mixed material and the curing agent at room temperature to obtain the high thermal conductivity phase-change silicone rubber.
在本发明中，所述固化剂优选为与所述硫化硅橡胶相配的固化剂。在 本发明的具体实施例中，所述固化剂为道康宁184硅橡胶固化剂。在本发明中，所述固化剂和所述硫化硅橡胶的质量比优选为1:10。In the present invention, the curing agent is preferably a curing agent compatible with the vulcanized silicone rubber. In a specific embodiment of the present invention, the curing agent is Dow Corning 184 silicone rubber curing agent. In the present invention, the mass ratio of the curing agent to the vulcanized silicone rubber is preferably 1:10.
本发明将所述混合物料和固化剂混合后得到的待固化料进行真空排气，然后将排气后的带固化料倒入模具中，室温固化。In the present invention, the material to be cured obtained after mixing the mixed material and the curing agent is vacuum-exhausted, and then the exhausted cured material is poured into a mold and cured at room temperature.
本发明提供了上述技术方案所述高导热相变有机硅橡胶或上述技术方案所述制备方法制备的高导热相变有机硅橡胶在电子或半导体元器件散热器件中的应用。The present invention provides the application of the high thermal conductivity phase change silicone rubber described in the above technical solution or the high thermal conductivity phase change silicone rubber prepared by the preparation method described in the above technical solution in heat dissipation devices for electronic or semiconductor components.
本发明对所述高导热相变有机硅橡胶的具体应用没有特殊要求。The present invention has no special requirements on the specific application of the high thermal conductivity phase change silicone rubber.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.
实施例1Example 1
将10g石墨加入到6g石蜡(熔融温度为44℃)的烧杯中，在60℃的温度下熔融混合，搅拌吸附1h，过滤、将固体产物冷却至室温，将石墨表面的石蜡清除得到石墨/石蜡复合材料。Add 10g of graphite to a beaker of 6g of paraffin (melting temperature is 44°C), melt and mix at a temperature of 60°C, stir and adsorb for 1h, filter, cool the solid product to room temperature, and remove the paraffin on the surface of the graphite to obtain graphite/paraffin composite material.
将硅烷偶联剂KH-550与无水乙醇(质量比为1:20)配置成偶联剂溶液，加入粒径为80nm氧化铝(KH-550和氧化铝的质量比为0.02:1)，滴加1％的醋酸至氧化铝-硅烷偶联剂混合液的pH至为4后，在60℃水浴磁力搅拌器搅拌120min，然后真空泵抽过滤并用无水乙醇洗涤3遍，除去残留的偶联剂，在120℃烘箱内干燥5h，用研磨棒捣碎筛分，得到硅烷偶联剂改性氧化铝。The silane coupling agent KH-550 and absolute ethanol (mass ratio: 1:20) were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
将粒径为5μm的氮化硼分散在去离子水中，并在搅拌的同时加热至80℃后继续搅拌1h，得到质量浓度为0.2g/mL氮化硼分散。将硅烷偶联剂KH-550、水和乙醇按照质量比为20:8:72混合，然后加热至50℃并再保持搅拌30分钟以进行完全水解，得到硅烷偶联剂水解液。然后，将氮化硼分散液与硅烷偶联剂水解液混合(KH-550和氮化硼的质量比为0.02:1)，然后在50℃下保持搅拌1h。最后，过滤、KH-550过筛收集，得到硅烷偶联剂改性氮化硼。Disperse boron nitride with a particle size of 5 μm in deionized water, heat to 80° C. while stirring and continue stirring for 1 h to obtain a boron nitride dispersion with a mass concentration of 0.2 g/mL. Mix the silane coupling agent KH-550, water and ethanol at a mass ratio of 20:8:72, then heat to 50°C and keep stirring for 30 minutes to complete the hydrolysis to obtain the hydrolyzed solution of the silane coupling agent. Then, mix the boron nitride dispersion with the silane coupling agent hydrolyzate (the mass ratio of KH-550 and boron nitride is 0.02:1), and then keep stirring at 50°C for 1h. Finally, filter and collect through KH-550 sieve to obtain silane coupling agent modified boron nitride.
将30g道康宁184硫化硅橡胶、9g硅烷偶联剂改性氧化铝、6g硅烷偶联剂改性氮化硼、9g石墨/石蜡相变材料混合后加入康宁184硫化硅橡胶的固化剂(硫化硅橡胶和固化剂的质量比为10:1)，抽真空排除气泡， 倒入模具后固化，得到高导热相变有机硅橡胶。After mixing 30g Dow Corning 184 vulcanized silicone rubber, 9g silane coupling agent modified alumina, 6g silane coupling agent modified boron nitride, and 9g graphite/paraffin phase change material, add the curing agent (silicon vulcanized silicon) of Corning 184 vulcanized silicone rubber The mass ratio of rubber to curing agent is 10:1), vacuumize to remove air bubbles, pour into a mold and cure to obtain high thermal conductivity phase change silicone rubber.
图1为实施例制备的高导热相变有机硅橡胶的实物图，图2为实施例1制备的高导热相变有机硅橡胶的DSC图。FIG. 1 is a physical picture of the high thermal conductivity phase-change silicone rubber prepared in Example 1, and FIG. 2 is a DSC chart of the high thermal conductivity phase-change silicone rubber prepared in Example 1.
实施例2Example 2
将10g石墨加入到6g石蜡(熔融温度为44℃)的烧杯中，在60℃的温度下熔融混合，搅拌吸附1h，过滤、将固体产物冷却至室温，将石墨表面的石蜡清除得到石墨/石蜡复合材料。Add 10g of graphite to a beaker of 6g of paraffin (melting temperature is 44°C), melt and mix at a temperature of 60°C, stir and adsorb for 1h, filter, cool the solid product to room temperature, and remove the paraffin on the surface of the graphite to obtain graphite/paraffin composite material.
将硅烷偶联剂KH-550与无水乙醇(质量比为1:20)配置成偶联剂溶液，加入粒径为80nm氧化铝(KH-550和氧化铝的质量比为0.02:1)，滴加1％的醋酸至氧化铝-硅烷偶联剂混合液的pH至为4后，在60℃水浴磁力搅拌器搅拌120min，然后真空泵抽过滤并用无水乙醇洗涤3遍，除去残留的偶联剂，在120℃烘箱内干燥5h，用研磨棒捣碎筛分，得到硅烷偶联剂改性氧化铝。The silane coupling agent KH-550 and absolute ethanol (mass ratio: 1:20) were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
将粒径为5μm的氮化硼分散在去离子水中，并在搅拌的同时加热至80℃后继续搅拌1h，得到质量浓度为0.2g/mL氮化硼分散。将硅烷偶联剂KH-550、水和乙醇按照质量比为20:8:72混合，然后加热至50℃并再保持搅拌30分钟以进行完全水解，得到硅烷偶联剂水解液。然后，将氮化硼分散液与硅烷偶联剂水解液混合(KH-550和氮化硼的质量比为0.02:1)，然后在50℃下保持搅拌1h。最后，过滤、KH-550过筛收集，得到硅烷偶联剂改性氮化硼。Disperse boron nitride with a particle size of 5 μm in deionized water, heat to 80° C. while stirring and continue stirring for 1 h to obtain a boron nitride dispersion with a mass concentration of 0.2 g/mL. Mix the silane coupling agent KH-550, water and ethanol at a mass ratio of 20:8:72, then heat to 50°C and keep stirring for 30 minutes to complete the hydrolysis to obtain the hydrolyzed solution of the silane coupling agent. Then, mix the boron nitride dispersion with the silane coupling agent hydrolyzate (the mass ratio of KH-550 and boron nitride is 0.02:1), and then keep stirring at 50°C for 1h. Finally, filter and collect through KH-550 sieve to obtain silane coupling agent modified boron nitride.
将30g道康宁184硫化硅橡胶、9g硅烷偶联剂改性氧化铝、6g硅烷偶联剂改性氮化硼、10.5g石墨/石蜡相变材料混合后加入康宁184硫化硅橡胶的固化剂(硫化硅橡胶和固化剂的质量比为10:1)，抽真空排除气泡，倒入模具后固化，得到高导热相变有机硅橡胶。After mixing 30g Dow Corning 184 vulcanized silicone rubber, 9g silane coupling agent modified alumina, 6g silane coupling agent modified boron nitride, and 10.5g graphite/paraffin phase change material, add the curing agent (curing agent) of Corning 184 vulcanized silicone rubber The mass ratio of silicone rubber to curing agent is 10:1), vacuumize to remove air bubbles, pour into a mold and cure to obtain high thermal conductivity phase change silicone rubber.
实施例3Example 3
将10g石墨加入到6g石蜡(熔融温度为44℃)的烧杯中，在60℃的温度下熔融混合，搅拌吸附1h，过滤、将固体产物冷却至室温，将石墨表面的石蜡清除得到石墨/石蜡复合材料。Add 10g of graphite to a beaker of 6g of paraffin (melting temperature is 44°C), melt and mix at a temperature of 60°C, stir and adsorb for 1h, filter, cool the solid product to room temperature, and remove the paraffin on the surface of the graphite to obtain graphite/paraffin composite material.
将硅烷偶联剂KH-550与无水乙醇(质量比为1:20)配置成偶联剂溶液，加入粒径为80nm氧化铝(KH-550和氧化铝的质量比为0.02:1)， 滴加1％的醋酸至氧化铝-硅烷偶联剂混合液的pH至为4后，在60℃水浴磁力搅拌器搅拌120min，然后真空泵抽过滤并用无水乙醇洗涤3遍，除去残留的偶联剂，在120℃烘箱内干燥5h，用研磨棒捣碎筛分，得到硅烷偶联剂改性氧化铝。The silane coupling agent KH-550 and absolute ethanol (mass ratio: 1:20) were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-550 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 4, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash 3 times with absolute ethanol to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
将粒径为5μm的氮化硼分散在去离子水中，并在搅拌的同时加热至80℃后继续搅拌1h，得到质量浓度为0.2g/mL氮化硼分散。将硅烷偶联剂KH-550、水和乙醇按照质量比为20:8:72混合，然后加热至50℃并再保持搅拌30分钟以进行完全水解，得到硅烷偶联剂水解液。然后，将氮化硼分散液与硅烷偶联剂水解液混合(KH-550和氮化硼的质量比为0.02:1)，然后在50℃下保持搅拌1h。最后，过滤、KH-550过筛收集，得到硅烷偶联剂改性氮化硼。Disperse boron nitride with a particle size of 5 μm in deionized water, heat to 80° C. while stirring and continue stirring for 1 h to obtain a boron nitride dispersion with a mass concentration of 0.2 g/mL. Mix the silane coupling agent KH-550, water and ethanol at a mass ratio of 20:8:72, then heat to 50°C and keep stirring for 30 minutes to complete the hydrolysis to obtain the hydrolyzed solution of the silane coupling agent. Then, mix the boron nitride dispersion with the silane coupling agent hydrolyzate (the mass ratio of KH-550 and boron nitride is 0.02:1), and then keep stirring at 50°C for 1h. Finally, filter and collect through KH-550 sieve to obtain silane coupling agent modified boron nitride.
将30g道康宁184硫化硅橡胶、9g硅烷偶联剂改性氧化铝、6g硅烷偶联剂改性氮化硼、13.5g石墨/石蜡相变材料混合后加入康宁184硫化硅橡胶的固化剂(硫化硅橡胶和固化剂的质量比为10:1)，抽真空排除气泡，倒入模具后固化，得到高导热相变有机硅橡胶。After mixing 30g Dow Corning 184 vulcanized silicone rubber, 9g silane coupling agent modified alumina, 6g silane coupling agent modified boron nitride, and 13.5g graphite/paraffin phase change material, add the curing agent (curing agent) of Corning 184 vulcanized silicone rubber The mass ratio of silicone rubber to curing agent is 10:1), vacuumize to remove air bubbles, pour into a mold and cure to obtain high thermal conductivity phase change silicone rubber.
实施例4Example 4
将10g石墨加入到8g石蜡(熔融温度为44℃)的烧杯中，在60℃的温度下熔融混合，搅拌吸附1h，过滤、将固体产物冷却至室温，将石墨表面的石蜡清除得到石墨/石蜡复合材料。Add 10g of graphite to a beaker of 8g of paraffin (melting temperature is 44°C), melt and mix at a temperature of 60°C, stir and adsorb for 1h, filter, cool the solid product to room temperature, and remove the paraffin on the surface of the graphite to obtain graphite/paraffin composite material.
将硅烷偶联剂KH-171与无水乙醇(质量比为1:20)配置成偶联剂溶液，加入粒径为80nm氧化铝(KH-171和氧化铝的质量比为0.02:1)，滴加1％的醋酸至氧化铝-硅烷偶联剂混合液的pH至为3.5后，在60℃水浴磁力搅拌器搅拌120min，然后真空泵抽过滤并用无水乙醇洗涤3遍，除去残留的偶联剂，在120℃烘箱内干燥5h，用研磨棒捣碎筛分，得到硅烷偶联剂改性氧化铝。The silane coupling agent KH-171 and absolute ethanol (mass ratio: 1:20) were configured as a coupling agent solution, and alumina with a particle size of 80nm was added (the mass ratio of KH-171 and alumina was 0.02:1), Add 1% acetic acid dropwise to the pH of the alumina-silane coupling agent mixture to 3.5, stir for 120 minutes in a water bath with a magnetic stirrer at 60°C, then vacuum filter and wash with absolute ethanol 3 times to remove residual coupling agent, dried in an oven at 120°C for 5 hours, crushed and sieved with a grinding rod to obtain silane coupling agent modified alumina.
将粒径为5μm的氮化硼分散在去离子水中，并在搅拌的同时加热至80℃后继续搅拌1h，得到质量浓度为0.2g/mL氮化硼分散。将硅烷偶联剂KH-171、水和乙醇按照质量比为20:8:72混合，然后加热至50℃并再保持搅拌30分钟以进行完全水解，得到硅烷偶联剂水解液。然后，将氮化硼分散液与硅烷偶联剂水解液混合(KH-171和氮化硼的质量比为 0.02:1)，然后在50℃下保持搅拌1h。最后，过滤、KH-550过筛收集，得到硅烷偶联剂改性氮化硼。Disperse boron nitride with a particle size of 5 μm in deionized water, heat to 80° C. while stirring and continue stirring for 1 h to obtain a boron nitride dispersion with a mass concentration of 0.2 g/mL. Mix the silane coupling agent KH-171, water and ethanol at a mass ratio of 20:8:72, then heat to 50°C and keep stirring for 30 minutes for complete hydrolysis to obtain the hydrolyzed solution of the silane coupling agent. Then, mix the boron nitride dispersion with the silane coupling agent hydrolyzate (the mass ratio of KH-171 and boron nitride is 0.02:1), and then keep stirring at 50°C for 1h. Finally, filter and collect through KH-550 sieve to obtain silane coupling agent modified boron nitride.
将30g道康宁184硫化硅橡胶、9g硅烷偶联剂改性氧化铝、6g硅烷偶联剂改性氮化硼、9g石墨/石蜡相变材料混合后加入康宁184硫化硅橡胶的固化剂(硫化硅橡胶和固化剂的质量比为10:1)，抽真空排除气泡，倒入模具后固化，得到高导热相变有机硅橡胶。After mixing 30g Dow Corning 184 vulcanized silicone rubber, 9g silane coupling agent modified alumina, 6g silane coupling agent modified boron nitride, and 9g graphite/paraffin phase change material, add the curing agent (silicon vulcanized silicon) of Corning 184 vulcanized silicone rubber The mass ratio of rubber to curing agent is 10:1), vacuumize to remove air bubbles, pour into a mold and cure to obtain high thermal conductivity phase change silicone rubber.
测试例test case
对实施例1～3制备的高导热相变有机硅橡胶的密度、相变潜热和导热性能进行测试，使用电子天平(XB-220A)进行密度测试，使用差示扫描量热仪(DSC-1)进行相变潜热测试，其中图2为实施例3的DSC扫描图，使用热导率测试仪(DTC-300)进行导热性能测试，测试结果如表1所示。The density, latent heat of phase change and thermal conductivity of the high thermal conductivity phase change silicone rubber prepared in Examples 1 to 3 are tested, and an electronic balance (XB-220A) is used to carry out the density test, and a differential scanning calorimeter (DSC-1 ) to perform a phase change latent heat test, wherein Fig. 2 is a DSC scan diagram of Example 3, using a thermal conductivity tester (DTC-300) to perform a thermal conductivity test, and the test results are shown in Table 1.
表1 实施例1～3制备的高导热相变有机硅橡胶性能测试结果Table 1 Performance Test Results of High Thermal Conductivity Phase Change Silicone Rubber Prepared in Examples 1-3
序号serial number 密度/g/cm 3 Density/g/ cm3 相变潜热/J/gLatent heat of phase change/J/g 导热系数/W/(m·k)Thermal conductivity/W/(m k) 导热系数增长率/％Thermal conductivity growth rate/%
实施例1Example 1 1.0681.068 7.2747.274 0.1780.178 7.9％7.9%
实施例2Example 2 1.0701.070 11.3511.35 0.1870.187 13.3％13.3%
实施例3Example 3 1.0741.074 18.3718.37 0.2140.214 29.7％29.7%
由表1的结果可知，相较于纯有机硅橡胶的导热系数0.165W/(m·k)，本发明提供的高导热相变有机硅橡胶在不影响硅橡胶的物理加工性能的条件下具备优异的导热性能。通过对比实施例1～3的结果可知，随着石墨/石蜡相变材料的质量份数增加，本发明实施例制备的高导热相变有机硅橡胶的导热性能进一步提高，实施例1导热率比纯橡胶提高了7.9％，实施例2的导热率比纯橡胶提高了13.3％，实施例3导热率比纯橡胶提高29.7％。As can be seen from the results in Table 1, compared with the thermal conductivity of pure silicone rubber of 0.165W/(m k), the high thermal conductivity phase-change silicone rubber provided by the present invention has Excellent thermal conductivity. By comparing the results of Examples 1 to 3, it can be seen that as the mass fraction of graphite/paraffin phase change material increases, the thermal conductivity of the high thermal conductivity phase change silicone rubber prepared in the embodiment of the present invention is further improved, and the thermal conductivity of Example 1 is higher than that of Pure rubber has improved by 7.9%, the thermal conductivity of embodiment 2 has improved by 13.3% compared with pure rubber, and the thermal conductivity of embodiment 3 has improved by 29.7% than pure rubber.
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 is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种高导热相变有机硅橡胶，其特征在于，包括以下质量份数的组分：A high thermal conductivity phase change silicone rubber, characterized in that it includes the following components in parts by mass:
    硫化硅橡胶100份、硅烷偶联剂改性氧化铝20～30份、硅烷偶联剂改性氮化硼10～20份、石墨/石蜡相变材料30～60份。100 parts of vulcanized silicone rubber, 20-30 parts of silane coupling agent modified alumina, 10-20 parts of silane coupling agent modified boron nitride, and 30-60 parts of graphite/paraffin phase change material.
  2. 根据权利要求1所述的高导热相变有机硅橡胶，其特征在于，所述硅烷偶联剂改性氧化铝的粒径为75～150nm。The high thermal conductivity phase-change silicone rubber according to claim 1, characterized in that the particle size of the silane coupling agent-modified alumina is 75-150 nm.
  3. 根据权利要求1所述的高导热相变有机硅橡胶，其特征在于，所述硅烷偶联剂改性氮化硼的粒径为1～10μm。The high thermal conductivity phase change silicone rubber according to claim 1, characterized in that the particle size of the boron nitride modified by the silane coupling agent is 1-10 μm.
  4. 根据权利要求1所述的高导热相变有机硅橡胶，其特征在于，所述硅烷偶联剂改性氧化铝的制备方法包括以下步骤：The high thermal conductivity phase-change silicone rubber according to claim 1, wherein the preparation method of the silane coupling agent modified alumina comprises the following steps:
    将硅烷偶联剂乙醇溶液和氧化铝混合，得到氧化铝-硅烷偶联剂混合液；mixing the ethanol solution of the silane coupling agent with alumina to obtain a mixed solution of alumina-silane coupling agent;
    采用酸的水溶液调节所述氧化铝-硅烷偶联剂混合液的pH值≤4，进行改性反应，得到所述硅烷偶联剂改性氧化铝；所述硅烷偶联剂和所述氧化铝的质量比≥0.02:1。Adjust the pH value of the alumina-silane coupling agent mixed solution to ≤4 by using an aqueous acid solution, and perform a modification reaction to obtain the silane coupling agent-modified alumina; the silane coupling agent and the alumina The mass ratio of ≥0.02:1.
  5. 根据权利要求1所述的高导热相变有机硅橡胶，其特征在于，所述硅烷偶联剂改性氮化硼的制备方法包括以下步骤：The high thermal conductivity phase-change silicone rubber according to claim 1, wherein the preparation method of the silane coupling agent-modified boron nitride comprises the following steps:
    将所述硅烷偶联剂、乙醇和水混合水解，得到硅烷偶联剂水解液；Mixing and hydrolyzing the silane coupling agent, ethanol and water to obtain a silane coupling agent hydrolyzate;
    将氮化硼水分散液和所述硅烷偶联剂水解液混合进行改性反应，得到所述硅烷偶联剂改性氮化硼；所述硅烷偶联剂和所述氮化硼的质量比≥0.02:1。The boron nitride aqueous dispersion and the silane coupling agent hydrolyzate are mixed for modification reaction to obtain the silane coupling agent modified boron nitride; the mass ratio of the silane coupling agent to the boron nitride is ≥0.02:1.
  6. 根据权利要求1所述的高导热相变有机硅橡胶，其特征在于，所述石墨/石蜡相变材料的制备方法包括以下步骤：The high thermal conductivity phase-change silicone rubber according to claim 1, wherein the preparation method of the graphite/paraffin phase-change material comprises the following steps:
    将石墨和熔融态石蜡混合吸附，得到所述石墨/石蜡相变材料，所述熔融态石蜡和石墨的质量比≥0.6:1。Graphite and molten paraffin are mixed and adsorbed to obtain the graphite/paraffin phase change material, and the mass ratio of the molten paraffin to graphite is ≥0.6:1.
  7. 根据权利要求4所述的高导热相变有机硅橡胶，其特征在于，硅烷偶联剂乙醇溶液的质量百分比为4.5～9.5％；所述改性反应的温度为55～70℃，所述改性反应的时间为1.5～3h。The high thermal conductivity phase-change silicone rubber according to claim 4, characterized in that the mass percent of the ethanol solution of the silane coupling agent is 4.5-9.5%; the temperature of the modification reaction is 55-70°C, and the modified The time of sexual reaction is 1.5~3h.
  8. 根据权利要求5所述的高导热相变有机硅橡胶，其特征在于，所述硅烷偶联剂、乙醇和水的质量比为(15～25):(5～10):(70～75)；所述改性反应的温度为40～52℃，所述改性反应的时间为0.5～1.2h。The high thermal conductivity phase change silicone rubber according to claim 5, wherein the mass ratio of the silane coupling agent, ethanol and water is (15～25):(5～10):(70～75) ; The temperature of the modification reaction is 40-52°C, and the time of the modification reaction is 0.5-1.2h.
  9. 权利要求1～8任一项所述高导热相变有机硅橡胶的制备方法，其特征在于，包括以下步骤：The preparation method of the high thermal conductivity phase change silicone rubber according to any one of claims 1 to 8, characterized in that it comprises the following steps:
    将硫化硅橡胶、硅烷偶联剂改性氧化铝、硅烷偶联剂改性氮化硼、石墨/石蜡相变材料混合，得到混合物料；Mix vulcanized silicone rubber, silane coupling agent modified alumina, silane coupling agent modified boron nitride, and graphite/paraffin phase change material to obtain a mixed material;
    在室温条件下，将所述混合物料和固化剂混合固化，得到所述高导热相变有机硅橡胶。At room temperature, the mixed material and curing agent are mixed and cured to obtain the high thermal conductivity phase change silicone rubber.
  10. 权利要求1～8任一项所述高导热相变有机硅橡胶或权利要求9所述的制备方法制备的高导热相变有机硅橡胶在电子或半导体元器件散热器件中的应用。The application of the high thermal conductivity phase change silicone rubber according to any one of claims 1 to 8 or the high thermal conductivity phase change silicone rubber prepared by the preparation method of claim 9 in heat dissipation devices for electronic or semiconductor components.
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