CN112500705A - Low-viscosity low-modulus high-thermal-conductivity single-component gel and preparation method thereof - Google Patents

Low-viscosity low-modulus high-thermal-conductivity single-component gel and preparation method thereof Download PDF

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Publication number
CN112500705A
CN112500705A CN202011277212.6A CN202011277212A CN112500705A CN 112500705 A CN112500705 A CN 112500705A CN 202011277212 A CN202011277212 A CN 202011277212A CN 112500705 A CN112500705 A CN 112500705A
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China
Prior art keywords
silicone oil
parts
stirring
hydrogen
gel
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Pending
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CN202011277212.6A
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Chinese (zh)
Inventor
王正
万炜涛
陈田安
郭呈毅
王红玉
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Shenzhen Darbond Interface Materials Co ltd
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Shenzhen Darbond Interface Materials Co ltd
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Priority to CN202011277212.6A priority Critical patent/CN112500705A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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

Abstract

The invention discloses a low-viscosity low-modulus high-thermal conductivity single-component gel, which comprises the following components in parts by weight: 100 parts of vinyl silicone oil, 5-30 parts of hydrogen-containing silicone oil, 0-10 parts of coupling agent, 0-10 parts of dispersing agent, 0.01-2 parts of platinum catalyst, 0.01-2 parts of inhibitor and 1500 parts of heat-conducting filler 600-.

Description

Low-viscosity low-modulus high-thermal-conductivity single-component gel and preparation method thereof
Technical Field
The invention relates to the field of heat conduction materials, in particular to a low-viscosity low-modulus high-heat-conduction single-component gel and a preparation method thereof.
Background
The heat dissipation process for electronic components is the transfer of heat from the device across the interface to the heat sink, which then dissipates the heat to the environment. Due to the microscopically rough and uneven surfaces of the device and the radiator, effective surface contact between the device and the radiator is difficult to form, the actual contact only occupies 1% -5% of the apparent area, and the formed gap is occupied by air with heat insulation capacity, so that interface thermal resistance is large. Therefore, reducing the interface thermal resistance is important for improving the heat dissipation efficiency of electronic components, and especially, along with the higher integration level and performance of electronic components (such as chips), the heat productivity is also higher and higher.
The thermally conductive gel, especially a low-viscosity thermally conductive gel, has fluidity of a thermally conductive paste before curing and wetting and filling properties to microscopically rough interfaces, and has shape-retaining ability of a thermally conductive pad after curing without running out and drying. In addition, the low-viscosity low-modulus heat-conducting gel has the advantages that the thickness of a curing adhesive layer can be smaller than 100 micrometers even smaller than 20 micrometers (determined by the maximum particle size of powder) under smaller pressure and is far lower than the thickness of a gasket, so that the interface thermal resistance can be greatly reduced as the heat-conducting paste, and the bulk thermal resistance of a thermal interface material can be reduced under the condition of not changing the proportion of the powder; meanwhile, the low modulus can release the thermal stress generated in the using process of the product, and the stability and the reliability of the product can be improved. The improvement of thermal conductivity can also reduce the bulk thermal resistance, and the viscosity and the modulus can be greatly improved along with the improvement of the powder proportion, so that the low-viscosity low-modulus high-thermal conductivity gel needs a systematized design to improve the comprehensive performance.
Disclosure of Invention
The existing low-modulus heat-conducting gel uses high-viscosity linear vinyl silicone oil as a main body to carry out chain extension and crosslinking to reduce the modulus, or reduces the modulus by external plasticization of dimethyl silicone oil, the former causes higher viscosity, and the latter has the problem of oil seepage of the dimethyl silicone oil, and in addition, the existing low-modulus heat-conducting gel selects a sacrifice powder filling ratio to reduce the modulus, so the heat conductivity coefficient is mostly less than 3W/m.K. Aiming at the problem, the invention provides a low-viscosity low-modulus high-thermal conductivity single-component gel which comprises the following components in parts by weight: 100 parts of vinyl silicone oil, 5-30 parts of hydrogen-containing silicone oil, 0-10 parts of coupling agent, 0-10 parts of dispersing agent, 0.01-2 parts of platinum catalyst, 0.01-2 parts of inhibitor and 1500 parts of heat-conducting filler 600-.
Wherein the viscosity of the vinyl silicone oil is 50-1000 mPa.s, the vinyl content is 0.05-2.5%, and the vinyl silicone oil is selected from one or more of polyvinyl silicone oil, divinyl silicone oil or monovinyl silicone oil; the viscosity of the hydrogen-containing silicone oil is 30-500 mPa.s, the hydrogen content is 0.01-0.3%, and the hydrogen-containing silicone oil is selected from one or more of side chain hydrogen-containing silicone oil, double-end hydrogen-containing silicone oil, single-end hydrogen-containing silicone oil or end-side mixed hydrogen-containing silicone oil. In the vinyl silicone oil and the hydrogen-containing silicone oil used in the invention, the vinyl silicone oil, the side chain hydrogen-containing oil and the end side mixed hydrogen-containing oil provide branching and crosslinking points to form a crosslinking network, so that the gel has shape retention capability, the divinyl silicone oil and the double-end hydrogen-containing oil can be used for chain extension, the crosslinking density is reduced, the modulus is reduced, the monovinyl silicone oil and the single-end hydrogen-containing oil can form a branching chain, and the internal plasticization effect is realized in the crosslinking network, so that the modulus can be further reduced.
The coupling agent is a coupling agent containing an alkyl chain with 1-20 carbons, comprises a silane coupling agent, a phthalate ester coupling agent, an aluminate coupling agent and the like, and can be single-chain or multi-chain, wherein the alkyl chain has better compatibility with organic silicon. The preferred single-chain, 8-16 carbon alkyl coupling agent has a carbon chain length that may be linear or branched, and may contain double or triple bonds or other relatively less polar functional groups. In the performance expression of surface treatment on the powder, the multi-chain, the overlong carbon chain and the over-short carbon chain are not beneficial to reducing the viscosity of the gel before curing and the modulus of the gel after curing, wherein the interaction force between the powder and a silica gel matrix is easily increased by the multi-chain, the overlong carbon chain or the high regularity, and the coating thickness of the coupling agent on the powder is easily reduced and the interaction force between the powder and the powder is not favorably reduced by the over-short alkyl chain.
The dispersing agent is graft type or block type polydimethylsiloxane, and the viscosity is 100-500mPa & s. The grafted chain or the block chain preferably has a short chain with certain polarity, including but not limited to a polyether chain, a polyacrylate chain, a polyester chain and the like, wherein the dimethyl siloxane chain segment has good compatibility with the silica gel matrix, and the short chain with certain polarity has proper binding force with the powder, so that the powder can be well dispersed in the organic silicon matrix. The dispersing agent only has intermolecular force on the silica gel matrix and the filler, so that the viscosity of the filler is reduced by dispersing the filler before curing, and the force between the cross-linked silica gel matrix and the filler can be reduced after curing, thereby achieving the purpose of reducing the modulus.
In the invention, the coupling agent and the dispersing agent can be respectively and independently used, and both can effectively disperse powder, reduce the viscosity before curing and the modulus after curing, and have better effect on reducing the viscosity and the modulus when the coupling agent and the dispersing agent are simultaneously used.
The inhibitor is alkynol, such as methylbutynol, ethynl cyclohexanol, or polyvinyl siloxane, such as tetramethyl divinyl disiloxane, tetramethyl tetravinylcyclotetrasiloxane.
The particle size of the heat-conducting filler is 0.1-60 mu m, and the heat-conducting filler is selected from one or more of alumina powder, aluminum powder and silver powder. The heat-conducting filler can improve the filling volume to improve the heat conductivity and reduce the thermal resistance, and more preferably high-sphericity and high-purity powder, wherein the high sphericity is favorable for reducing the viscosity and the modulus, and the high purity is favorable for improving the heat conductivity and reducing the thermal resistance.
The preparation method of the low-viscosity low-modulus high-thermal conductivity single-component gel comprises the following steps: weighing the components in parts by weight, adding vinyl silicone oil, a coupling agent and a dispersing agent into a double-planet stirrer, stirring for 0.1h at the rotating speed of 30-50rpm, adding a heat-conducting filler after uniformly mixing, stirring for 0.5h, heating to 60-90 ℃, stirring for 1h, vacuumizing, continuously stirring for 1h, stirring and cooling to room temperature, adding hydrogen-containing silicone oil, vacuumizing, stirring for 0.5h, adding an inhibitor, stirring for 0.5h, adding a platinum catalyst, stirring for 0.5h, vacuumizing, and continuously stirring for 0.5h to obtain the catalyst.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
Adding 100 parts of low-viscosity vinyl silicone oil and 10 parts of hexadecyl trimethoxy silane coupling agent into a stirring kettle, stirring for 0.1h at the rotating speed of 30rpm, adding 1100 parts of spherical alumina powder after uniformly mixing, stirring for 0.5h, heating to 90 ℃, stirring for 1h, vacuumizing, continuing stirring for 1h at 80 ℃, stirring for cooling to room temperature, adding 30 parts of low-viscosity low-hydrogen silicone oil, vacuumizing, stirring for 0.5h, then adding 0.01 part of methylbutinol, stirring for 0.5h, finally adding 0.01 part of platinum catalyst, stirring for 0.5h, vacuumizing, continuing stirring for 0.5h, and thus obtaining the low-viscosity low-modulus high-thermal-conductivity gel.
Example 2
Adding 100 parts of low-viscosity vinyl silicone oil and 10 parts of dispersing agent into a stirring kettle, stirring for 0.1h at the rotating speed of 50rpm, uniformly mixing, adding 600 parts of spherical aluminum powder, stirring for 0.5h, heating to 60 ℃, stirring for 1h, vacuumizing, continuously stirring for 1h at 80 ℃, stirring, cooling to room temperature, adding 5 parts of low-viscosity low-hydrogen-containing silicone oil, vacuumizing, stirring for 0.5h, adding 2 parts of ethynl cyclohexanol, stirring for 0.5h, finally adding 2 parts of platinum catalyst, stirring for 0.5h, vacuumizing, and continuously stirring for 0.5h to obtain the low-viscosity low-modulus high-thermal conductivity gel.
Example 3
Adding 100 parts of low-viscosity vinyl silicone oil, 5 parts of octyl trimethoxy silane coupling agent and 5 parts of dispersing agent into a stirring kettle, stirring for 0.1h at the rotating speed of 40rpm, adding 1500 parts of spherical silver powder after uniformly mixing, stirring for 0.5h, heating to 80 ℃, stirring for 1h, vacuumizing, continuing to stir for 1h at 80 ℃, stirring for cooling to room temperature, adding 15 parts of low-viscosity low-hydrogen silicone oil, vacuumizing, stirring for 0.5h, then adding 1 part of tetramethyl divinyl disiloxane, stirring for 0.5h, finally adding 1 part of platinum catalyst, stirring for 0.5h, vacuumizing, continuing to stir for 0.5h, and obtaining the low-viscosity low-modulus high-thermal conductivity gel.
The thermal conductivity of the low-viscosity low-modulus single-component high-thermal-conductivity gel obtained in examples 1 to 3 was measured according to the standard of astm d5470, and the rheological properties were measured by a haake rheometer, wherein the viscosity was measured at 25 ℃ and 1rpm, the storage modulus and the loss modulus were measured at 1% strain and 1Hz in an oscillation-controlled strain mode, and the gel was cured at 125 ℃ for 2 hours. As can be seen from the data in the table, the single-component thermal gels obtained in examples 1 to 3 have the characteristics of high thermal conductivity, low viscosity and low modulus.
TABLE 1 examination of the properties of the gels obtained in examples 1 to 3
Item Example 1 Example 2 Example 3
Thermal conductivity W/m.K 3.23 4.122 6.053
Viscosity Pa s 35 48 43
Storage modulus KPa 22 39 61
Loss modulus KPa 15 28 55
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. The low-viscosity low-modulus high-thermal conductivity single-component gel is characterized by comprising the following components in parts by weight:
100 parts of vinyl silicone oil, 5-30 parts of hydrogen-containing silicone oil, 0-10 parts of coupling agent, 0-10 parts of dispersing agent, 0.01-2 parts of platinum catalyst, 0.01-2 parts of inhibitor and 1500 parts of heat-conducting filler 600-.
2. The gel according to claim 1, wherein said vinyl silicone oil has a viscosity of 50 to 1000 mPa-s and a vinyl content of 0.05 to 2.5%, and is selected from one or more of polyvinyl silicone oil, divinyl silicone oil, or monovinyl silicone oil.
3. The gel according to claim 1, wherein the hydrogen-containing silicone oil has a viscosity of 30 to 500 mPa-s and a hydrogen content of 0.01 to 0.3%, and is one or more selected from a side chain hydrogen-containing silicone oil, a both-end hydrogen-containing silicone oil, a single-end hydrogen-containing silicone oil, or a mixture of end-side hydrogen-containing silicone oils.
4. The gel of claim 1, wherein the coupling agent is a coupling agent comprising an alkyl chain of 1-20 carbons.
5. The gel of claim 1, wherein the dispersant is a grafted or blocked polydimethylsiloxane having a viscosity of 100-500 mPa-s.
6. The gel of claim 1, wherein said inhibitor is one or more of methylbutynol, ethynylcyclohexanol, tetramethyldivinyldisiloxane, or tetramethyltetravinylcyclotetrasiloxane.
7. The gel of claim 1, wherein the thermally conductive filler has a particle size of 0.1 to 60 μm and is selected from one or more of alumina powder, aluminum powder and silver powder.
8. A process for the preparation of a gel according to any one of claims 1 to 7, characterized in that it comprises the steps of: weighing the components in parts by weight, adding vinyl silicone oil, a coupling agent and a dispersing agent into a double-planet stirrer, stirring for 0.1h at the rotating speed of 30-50rpm, adding a heat-conducting filler after uniformly mixing, stirring for 0.5h, heating to 60-90 ℃, stirring for 1h, vacuumizing, continuously stirring for 1h, stirring and cooling to room temperature, adding hydrogen-containing silicone oil, vacuumizing, stirring for 0.5h, adding an inhibitor, stirring for 0.5h, adding a platinum catalyst, stirring for 0.5h, vacuumizing, and continuously stirring for 0.5h to obtain the catalyst.
CN202011277212.6A 2020-11-16 2020-11-16 Low-viscosity low-modulus high-thermal-conductivity single-component gel and preparation method thereof Pending CN112500705A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292857A (en) * 2021-05-25 2021-08-24 福建臻璟新材料科技有限公司 Heat-conducting gel containing whiskers and preparation method thereof
CN113527893A (en) * 2021-08-13 2021-10-22 深圳先进电子材料国际创新研究院 High-hysteresis thermal interface material and preparation method and application thereof
CN113563851A (en) * 2021-07-20 2021-10-29 深圳先进电子材料国际创新研究院 In-situ modified low-viscosity high-performance heat-conducting gel and preparation method and application thereof
CN113773649A (en) * 2021-09-26 2021-12-10 中国科学院深圳先进技术研究院 High-reliability low-viscosity high-heat-conductivity heat-conducting gel and preparation method and application thereof
CN113817178A (en) * 2021-10-18 2021-12-21 深圳市德镒盟电子有限公司 Low-oil-permeability high-heat-conductivity heat-conducting gel and preparation method thereof
CN114031944A (en) * 2021-12-01 2022-02-11 深圳先进电子材料国际创新研究院 Low-hysteresis heat-conducting gel and preparation method thereof
CN114045036A (en) * 2021-11-30 2022-02-15 广州市白云化工实业有限公司 Heat-conducting gel composition and preparation method thereof
CN114479476A (en) * 2022-02-23 2022-05-13 深圳先进电子材料国际创新研究院 Wide-frequency-band wide-temperature-range high-damping heat-conducting gel and preparation method and application thereof
CN114539782A (en) * 2022-01-18 2022-05-27 深圳先进电子材料国际创新研究院 Method for reducing contact thermal resistance heat-conducting gel and application thereof
CN115926474A (en) * 2022-12-29 2023-04-07 深圳德邦界面材料有限公司 Low-modulus high-elongation organic silicon heat-conducting gel
CN115960463A (en) * 2022-09-21 2023-04-14 深圳市安伯斯科技有限公司 Preparation process of low-viscosity low-modulus high-thermal-conductivity single-component gel

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CN107043541A (en) * 2017-02-22 2017-08-15 厦门安耐伟业新材料有限公司 Thermal conductive silicon gel combination and preparation method thereof
CN111019357A (en) * 2019-12-27 2020-04-17 广州市白云化工实业有限公司 High-performance silicon-based heat-conducting mud and preparation method thereof

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CN106398226A (en) * 2016-05-05 2017-02-15 厦门安耐伟业新材料有限公司 Heat-conducting silica gel and preparation method thereof
CN107043541A (en) * 2017-02-22 2017-08-15 厦门安耐伟业新材料有限公司 Thermal conductive silicon gel combination and preparation method thereof
CN111019357A (en) * 2019-12-27 2020-04-17 广州市白云化工实业有限公司 High-performance silicon-based heat-conducting mud and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292857A (en) * 2021-05-25 2021-08-24 福建臻璟新材料科技有限公司 Heat-conducting gel containing whiskers and preparation method thereof
CN113563851A (en) * 2021-07-20 2021-10-29 深圳先进电子材料国际创新研究院 In-situ modified low-viscosity high-performance heat-conducting gel and preparation method and application thereof
CN113527893A (en) * 2021-08-13 2021-10-22 深圳先进电子材料国际创新研究院 High-hysteresis thermal interface material and preparation method and application thereof
CN113773649A (en) * 2021-09-26 2021-12-10 中国科学院深圳先进技术研究院 High-reliability low-viscosity high-heat-conductivity heat-conducting gel and preparation method and application thereof
CN113817178A (en) * 2021-10-18 2021-12-21 深圳市德镒盟电子有限公司 Low-oil-permeability high-heat-conductivity heat-conducting gel and preparation method thereof
CN114045036A (en) * 2021-11-30 2022-02-15 广州市白云化工实业有限公司 Heat-conducting gel composition and preparation method thereof
CN114045036B (en) * 2021-11-30 2024-02-20 广州白云科技股份有限公司 Heat-conducting gel composition and preparation method thereof
CN114031944A (en) * 2021-12-01 2022-02-11 深圳先进电子材料国际创新研究院 Low-hysteresis heat-conducting gel and preparation method thereof
CN114539782A (en) * 2022-01-18 2022-05-27 深圳先进电子材料国际创新研究院 Method for reducing contact thermal resistance heat-conducting gel and application thereof
CN114479476A (en) * 2022-02-23 2022-05-13 深圳先进电子材料国际创新研究院 Wide-frequency-band wide-temperature-range high-damping heat-conducting gel and preparation method and application thereof
CN115960463A (en) * 2022-09-21 2023-04-14 深圳市安伯斯科技有限公司 Preparation process of low-viscosity low-modulus high-thermal-conductivity single-component gel
CN115926474A (en) * 2022-12-29 2023-04-07 深圳德邦界面材料有限公司 Low-modulus high-elongation organic silicon heat-conducting gel

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Application publication date: 20210316