CN116535860A - Heat-conducting insulating liquid silicone rubber and preparation method and application thereof - Google Patents
Heat-conducting insulating liquid silicone rubber and preparation method and application thereof Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 96
- 239000004944 Liquid Silicone Rubber Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000945 filler Substances 0.000 claims abstract description 52
- 239000004945 silicone rubber Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229910052582 BN Inorganic materials 0.000 claims abstract description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002545 silicone oil Polymers 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- -1 dimethyl vinyl Chemical group 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 35
- 239000011787 zinc oxide Substances 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 25
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 14
- 229940000635 beta-alanine Drugs 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- CCLNWKPQPZBSEI-UHFFFAOYSA-N 2,3-diethoxypropan-1-ol Chemical compound CCOCC(CO)OCC CCLNWKPQPZBSEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000017525 heat dissipation Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000009413 insulation Methods 0.000 description 21
- 229920000106 Liquid crystal polymer Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- LOSWWGJGSSQDKH-UHFFFAOYSA-N 3-ethoxypropane-1,2-diol Chemical compound CCOCC(O)CO LOSWWGJGSSQDKH-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The application relates to the technical field of silicon rubber, and particularly discloses heat-conducting insulating liquid silicon rubber, a preparation method and application thereof. The heat-conducting insulating liquid silicone rubber comprises 5-7 parts of dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler and titanate coupling agent; the preparation method comprises mixing and vulcanizing. The heat-conducting insulating liquid silicone rubber can be applied to preparing a thermal interface material, has good mechanical property and ageing resistance, has good insulating heat-conducting property, and can meet the heat dissipation and application requirements of high-power electronic devices.
Description
Technical Field
The application relates to the technical field of silicone rubber, in particular to a heat-conducting insulating liquid silicone rubber and a preparation method and application thereof.
Background
At present, the circuit design of the electronic product is more and more complex, and the circuit design is in a trend of densification and miniaturization. The electronic and electric equipment can generate a large amount of heat, and if the heat cannot be timely discharged, the heat is accumulated to a certain degree, so that damage to components of the electronic and electric equipment and the equipment is likely to be caused. The excess heat generated by it must be transferred to the surrounding environment in a timely and efficient manner. Conventional metallic materials in the heat dissipation industry are more and more easily replaced by some thermal interface materials because of the limited geometry of the article and the clearance between such heat sinks and the electronic component surface.
The heat conducting rubber is a rubber-based composite material with a focus on heat conducting performance, and the heat conducting rubber is mainly made of silicon rubber, has the characteristics of good elasticity, good electrical insulation, low-voltage deformation easiness, good sealing performance and the like, can effectively fill gaps between interfaces when used for radiating components and parts, can expel air between cold and hot interfaces, and can improve the efficacy of the radiator by about 40%. Therefore, research on a heat conductive rubber having high heat conductivity is important for miniaturization, densification, improvement of precision and life of electronic and electric equipment.
The heat-conducting filler used in the conventional heat-conducting silicon rubber composite material is mostly metal powder such as silver, aluminum and the like, and alumina, silicon carbide, quartz powder and the like, so that the cost of the heat-conducting powder is relatively high, the heat conductivity coefficient of the prepared heat-conducting silicon rubber is not improved well, and the comprehensive performance is relatively poor.
Disclosure of Invention
In order to improve the heat conduction and insulation performance of the silicone rubber, the application provides a heat conduction and insulation liquid silicone rubber, and a preparation method and application thereof.
In a first aspect, the present application provides a thermally conductive and insulating liquid silicone rubber, which adopts the following technical scheme:
the heat-conducting insulating liquid silicone rubber comprises the following raw materials in parts by weight:
100 parts of dimethyl vinyl silicone rubber;
8-15 parts of hydroxyl-terminated silicone oil;
10-20 parts of liquid crystal high molecular polymer;
10-15 parts of hexagonal boron nitride;
50-70 parts of modified graphene-based filler;
1-3 parts of vulcanizing agent;
5-7 parts of titanate coupling agent;
the modified graphene-based filler is obtained by loading zinc oxide particles on the graphene-based filler.
Through adopting above-mentioned technical scheme, through hexagonal boron nitride and modified graphene based packing compound use as heat conduction filler, hexagonal boron nitride and modified graphene based filler can form three-dimensional crosslinked heat conduction network in the silicone rubber to improve the heat conductivility of silicone rubber, modified graphene based filler can increase the heat conduction passageway figure in the silicone rubber after loading zinc oxide particle, compare in single graphene based filler, adopt modified graphene based filler to improve packing density more easily, form dense piling, improve thermal conductivity, thermal resistance has positive temperature coefficient, thereby effectively improve the heat conductivility of silicone rubber.
The liquid crystal high polymer is added, so that the coverage area and the extension path of the heat conduction network in the silicon rubber can be further improved through the liquid crystal high polymer, the heat conduction performance of the silicon rubber is greatly enhanced, the liquid crystal high polymer has good insulation performance, the liquid crystal high polymer can enter an interlayer structure of graphene, the electric conductivity of the graphene is reduced, the liquid crystal high polymer is embedded in the heat conduction network, the insulation performance of the heat conduction network can be effectively enhanced, and the insulation performance of the silicon rubber can be further improved. The liquid silicone rubber prepared from the raw materials has good mechanical property and ageing resistance, has good insulating heat conduction property, and can meet the heat dissipation and application requirements of high-power electronic devices.
Optionally, the graphene-based filler is a reduced graphene oxide filler.
By adopting the technical scheme, the reduced graphene oxide contains a large number of oxygen-containing functional groups, so that good dispersibility and reactivity of the reduced graphene oxide are provided, the reduced graphene oxide is uniformly dispersed in the silicon rubber, and a three-dimensional crosslinked heat conduction network with a uniform and stable structure is formed in the silicon rubber, and the heat conduction performance of the silicon rubber is improved.
Optionally, the modified graphene-based filler is prepared by a method comprising the following steps:
s1: mixing the reduced graphene oxide powder with a zinc oxide colloid solution, heating to 60-70 ℃, and then stirring at constant temperature for 1-1.5h to obtain a mixed solution;
s2: and adding 20-25% beta-alanine solution into the mixed solution, heating to 60-70 ℃, stirring at constant temperature for 2-3h, filtering, and calcining to obtain the modified graphene-based filler.
Through the technical scheme, in the reaction process, the oxygen-containing functional group on the surface of the reduced graphene oxide can react with the beta-alanine containing amino and carboxyl groups, so that stable covalent bonds are formed between the reduced graphene oxide and the beta-alanine crystals, and the beta-alanine molecules have a pair of unshared electrons due to N atoms, so that covalent bonds are easily formed with residual Zn2+, and a relatively stable complex is formed by complexing with Zn2+, so that the stability of zinc oxide particles in the load of the reduced graphene oxide is improved, and the modified graphene-based filler can exert the best heat conduction and insulation effects.
Optionally, the mass ratio of the reduced graphene oxide powder to the zinc oxide colloidal solution in the step S1 is 1: (1-1.5); the mass ratio of the mixed solution to the beta-alanine solution in the S2 is 1: (0.3-0.5).
By adopting the technical scheme, the modified graphene-based filler is prepared by selecting the raw materials with the proportion, so that a layer of uniformly dispersed zinc oxide particles are loaded on the surface of the reduced graphene oxide, and the modified graphene-based filler has a better heat conduction and insulation effect.
Optionally, the zinc oxide colloid solution is prepared by the following method: dissolving zinc acetate solution in glycerol diethyl ether, stirring for 20-30min, adding ethylenediamine with the same mole number as that of the zinc acetate solution, and stirring at constant temperature of 70-80deg.C for 0.5-1 hr to obtain zinc oxide colloid solution.
By adopting the technical scheme, the prepared zinc oxide colloid solution has the advantages of good dispersibility and uniform ground, and waste gas and waste liquid cannot be generated in the preparation process, so that the environment friendliness of the production process is improved.
Optionally, the molecular weight of the hydroxyl-terminated silicone oil is 1.5-2.0 ten thousand, and the hydroxyl content is 0.17-0.23%.
In a second aspect, the present application provides a method for preparing a heat-conducting and insulating liquid silicone rubber, which adopts the following technical scheme:
a preparation method of heat-conducting insulating liquid silicone rubber comprises the following steps:
step one: mixing: mixing dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, a liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler, a vulcanizing agent and a titanate coupling agent according to a proportion, and then mixing on a mixing mill, and standing at room temperature for 6-8 hours after mixing uniformly to obtain a mixed rubber;
step two: vulcanizing: vulcanizing the rubber compound obtained in the step one at 170-180 ℃ and 6-8Mpa for 10-20min, and then cooling at room temperature and 4-6Mpa for 10-20min to obtain the silicone rubber.
By adopting the technical scheme, the three-dimensional cross-linked heat conduction network is formed in the silicon rubber through the modified graphene-based filler, so that the heat conduction and insulation properties of the silicon rubber can be effectively improved, and the preparation method is simple and easy to operate and can be suitable for large-scale industrial production.
In a third aspect, the present application provides an application of a thermally conductive and insulating liquid silicone rubber in preparing a thermal interface material.
Through adopting above-mentioned technical scheme, the heat conduction insulating liquid silicone rubber that this application provided has better mechanical properties and ageing resistance to have better insulating heat conductivility, can satisfy high-power electronic device's heat dissipation and application requirement.
1. According to the preparation method, the modified graphene-based filler is adopted, the hexagonal boron nitride and the modified graphene-based filler can form a three-dimensional cross-linked heat conduction network in the silicon rubber, so that the heat conduction performance of the silicon rubber is improved, the number of heat conduction paths in the silicon rubber can be increased after zinc oxide particles are loaded, the heat conduction performance of the silicon rubber is effectively improved, the liquid crystal high-molecular polymer is added, the coverage area and the extension path of the heat conduction network in the silicon rubber can be further improved through the liquid crystal high-molecular polymer, the heat conduction performance of the silicon rubber is greatly improved, the liquid crystal high-molecular polymer has good insulation performance, the liquid crystal high-molecular polymer can enter an interlayer structure of graphene, the electric conductivity of the graphene is reduced, the liquid crystal high-molecular polymer is embedded in the heat conduction network, the insulation performance of the heat conduction network can be effectively enhanced, and the insulation performance of the silicon rubber can be further improved.
2. In the application, the reduced graphene oxide filler is preferably used as a modified carrier, and the reduced graphene oxide contains a large amount of oxygen-containing functional groups, so that the reduced graphene oxide is endowed with good dispersibility and reactivity, uniform dispersion of the reduced graphene oxide in the silicone rubber is facilitated, and a three-dimensional crosslinked heat conduction network with uniform and stable structure is formed in the silicone rubber, so that the heat conduction performance of the silicone rubber is improved.
3. According to the preparation method, the three-dimensional cross-linked heat conduction network is formed in the silicon rubber through the modified graphene-based filler, so that the heat conduction and insulation properties of the silicon rubber can be effectively improved, and the preparation method is simple and easy to operate and can be suitable for large-scale industrial production.
Detailed Description
The present application is described in further detail below with reference to examples.
The reduced graphene oxide powder, the beta-alanine solution, the zinc acetate solution, the glycerol ethyl ether and the ethylenediamine reagent in the embodiment of the application are all obtained through the market;
the average particle diameter of the hexagonal boron nitride and the liquid crystal high molecular polymer in the embodiment of the application is 25 micrometers, and the specific surface area is 0.24m 2 /g; the vulcanizing agent is double 25.
Preparation example of modified graphene-based filler
Preparation example 1
S1: dissolving 1kg of zinc acetate solution with the mass concentration of 37% in 1.5kg of glycerol diethyl ether, centrifugally stirring for 20min, then adding 0.305mol of ethylenediamine, and stirring at a constant temperature of 70 ℃ for 0.5h to obtain zinc oxide colloid solution;
s2: mixing 2kg of reduced graphene oxide powder with 2kg of zinc oxide colloidal solution, heating to 60 ℃, and stirring at constant temperature for 1h to obtain a mixed solution;
s3: and adding 1.2kg of 20% beta-alanine solution into the mixed solution, heating to 60 ℃, stirring at constant temperature for 2 hours, filtering, and calcining filter residues at 250 ℃ to obtain the modified graphene-based filler.
Preparation example 2
S1: dissolving 1kg of zinc acetate solution with the mass concentration of 37% in 1.5kg of glycerol diethyl ether, centrifugally stirring for 25min, then adding 0.305mol of ethylenediamine, and stirring at a constant temperature of 75 ℃ for 0.7h to obtain zinc oxide colloid solution;
s2: mixing 2kg of reduced graphene oxide powder with 2.5kg of zinc oxide colloidal solution, heating to 65 ℃, and stirring at constant temperature for 1.2h to obtain a mixed solution;
s3: and adding 1.8kg of beta-alanine solution with the mass concentration of 22% into the mixed solution, heating to 65 ℃, stirring at constant temperature for 2.5h, filtering, and calcining filter residues at 250 ℃ to obtain the modified graphene-based filler.
Preparation example 3
S1: dissolving 1kg of zinc acetate solution with the mass concentration of 37% in 1.5kg of glycerol diethyl ether, centrifugally stirring for 30min, then adding 0.305mol of ethylenediamine, and stirring at the constant temperature of 80 ℃ for 1h to obtain zinc oxide colloid solution;
s2: mixing 2kg of reduced graphene oxide powder with 3kg of zinc oxide colloidal solution, heating to 60 ℃, and stirring at constant temperature for 1h to obtain a mixed solution;
s3: and adding 2.5kg of beta-alanine solution with the mass concentration of 25% into the mixed solution, heating to 70 ℃, stirring at constant temperature for 3 hours, filtering, and calcining filter residues at 250 ℃ to obtain the modified graphene-based filler.
Preparation example 4
S1: dissolving 1kg of zinc acetate solution with the mass concentration of 37% in 1.5kg of glycerol diethyl ether, centrifugally stirring for 30min, then adding 0.305mol of ethylenediamine, and stirring at the constant temperature of 80 ℃ for 1h to obtain zinc oxide colloid solution;
s2: mixing 2kg of reduced graphene oxide powder with 3kg of zinc oxide colloidal solution, heating to 60 ℃, and stirring at constant temperature for 1h to obtain a mixed solution;
s3: heating the mixed solution to 70 ℃, stirring at constant temperature for 3 hours, filtering, and calcining filter residues at 250 ℃ to obtain the modified graphene-based filler.
Examples
Example 1
The heat-conducting insulating liquid silicone rubber comprises the following raw material components and corresponding weights shown in table 1:
step one: mixing: mixing dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, a liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler, a vulcanizing agent and a titanate coupling agent according to a proportion, and then mixing on a mixing mill, and standing at room temperature for 6 hours after mixing uniformly to obtain a mixed rubber;
step two: vulcanizing: vulcanizing the rubber compound obtained in the step one at 170 ℃ and 6Mpa for 10min, and then cooling at room temperature and 4Mpa for 10min to obtain the silicone rubber.
Wherein the modified graphene-based filler is prepared by the preparation example 1.
Example 2
The heat-conducting insulating liquid silicone rubber comprises the following raw material components and corresponding weights shown in table 1:
step one: mixing: mixing dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, a liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler, a vulcanizing agent and a titanate coupling agent according to a proportion, and then mixing on a mixing mill, and standing at room temperature for 7 hours after mixing uniformly to obtain a mixed rubber;
step two: vulcanizing: vulcanizing the rubber compound obtained in the step one at 175 ℃ and 7Mpa for 15min, and then cooling at room temperature and 5Mpa for 15min to obtain the silicone rubber.
Wherein the modified graphene-based filler is prepared by using the modified graphene-based filler prepared in preparation example 2
Example 3
The heat-conducting insulating liquid silicone rubber comprises the following raw material components and corresponding weights shown in table 1:
step one: mixing: mixing dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, a liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler, a vulcanizing agent and a titanate coupling agent according to a proportion, and then mixing on a mixing mill, and standing at room temperature for 8 hours after mixing uniformly to obtain a mixed rubber;
step two: vulcanizing: vulcanizing the rubber compound obtained in the step one at 180 ℃ and 8Mpa for 20min, and then cooling at room temperature and 6Mpa for 20min to obtain the silicone rubber.
Wherein the modified graphene-based filler is prepared by using the modified graphene-based filler prepared in preparation example 3.
TABLE 1 weight (kg) of the raw materials in examples 1-3
| Raw material name | Example 1 | Example 2 | Example 3 |
| Dimethyl vinyl silicone rubber | 10 | 10 | 10 |
| Hydroxyl-terminated silicone oil | 0.8 | 1.2 | 1.5 |
| Liquid crystalline polymer | 1.0 | 1.5 | 2.0 |
| Hexagonal boron nitride | 1.0 | 1.2 | 1.5 |
| Modified graphene-based filler | 7.0 | 6.0 | 5.0 |
| Vulcanizing agent | 1.0 | 2.0 | 3.0 |
| Titanate coupling agent | 0.5 | 0.6 | 0.7 |
Example 4
A thermally conductive, insulating liquid silicone rubber differing from example 3 in that: the modified graphene-based filler prepared in preparation example 4 is selected.
Comparative example
Comparative example 1
JC-819 type heat-conducting insulating liquid silicone rubber purchased from Guangdong new materials company.
Comparative example 2
A thermally conductive, insulating liquid silicone rubber differing from example 3 in that: the raw materials are reduced graphene oxide powder with equal quantity instead of modified graphene-based filler.
Comparative example 3
A thermally conductive, insulating liquid silicone rubber differing from example 3 in that: the raw materials are modified graphene-based filler prepared in preparation example 3 to replace liquid crystal high polymer in equal quantity.
Comparative example 4
A thermally conductive, insulating liquid silicone rubber differing from example 3 in that: the raw material contains 0.9kg of modified graphene-based filler and 0.5kg of liquid crystal high polymer.
Performance test
The thermally conductive and insulating liquid silicone rubbers prepared in examples 1 to 4 and comparative examples 1 to 4 were injection molded, cured, and subjected to performance test by the following specific test methods:
thermal conductivity coefficient: according to ASTM-D5470.
Volume resistivity: according to GB/T1410 test.
The specific detection results are shown in table 2:
TABLE 2 Performance test results
| Project | Thermal conductivity/W/(m.K) | Volume resistivity/Ω·cm |
| Example 1 | 3.24 | 6.25×10 12 |
| Example 2 | 3.23 | 6.22×10 12 |
| Example 3 | 3.25 | 6.28×10 12 |
| Example 4 | 2.85 | 4.32×10 12 |
| Comparative example 1 | 0.17 | 1.02×10 11 |
| Comparative example 2 | 2.55 | 1.25×10 11 |
| Comparative example 3 | 3.20 | 1.20×10 11 |
| Comparative example 4 | 3.33 | 2.24×10 12 |
As can be seen from the combination of examples 1 to 3, comparative examples 1 and Table 2, the thermal conductivity of the thermal conductive and insulating liquid silicone rubber prepared in examples 1 to 3 of the present application was stabilized at 3.24W/(m.K), and the volume resistivity was about 6.25X10 12 Omega cm, whereas the JC-819 type heat conductive insulating liquid silicone rubber of comparative example 1 has a heat conductivity of 0.17W/(m.K) and a volume resistivity of 1.02X10 11 The method comprises the steps of carrying out a first treatment on the surface of the Obviously, the heat conduction and insulation liquid silicone rubber prepared by the method has better heat conduction and insulation performance.
As can be seen from the combination of example 3, comparative example 2 and table 2, the thermal conductivity and insulation properties of the thermal conductive insulating liquid silicone rubber of comparative example 2 are far inferior to those of the thermal conductive insulating liquid silicone rubber of example 3, and since the thermal conductive insulating liquid silicone rubber of comparative example 2 uses unmodified reduced graphene oxide powder, although there is some improvement in the thermal conductivity of the thermal conductive insulating liquid silicone rubber, the number of thermal conductive paths in the silicone rubber is smaller, and thus the thermal conductivity is inferior to that of example 3, and the unmodified reduced graphene oxide powder has better electrical conductivity, resulting in poor insulation properties of the thermal conductive insulating liquid silicone rubber of comparative example 2.
As can be seen from the combination of example 3, comparative example 3 and table 2, since the liquid crystalline polymer is not used in the raw material of comparative example 3, the thermal conductivity of the silicone rubber is less different from that of example 3, but the volume resistivity of comparative example 3 is much smaller than that of example 3, and since the liquid crystalline polymer is not used, the thermal conductive network in the silicone rubber has better thermal conductivity and better electrical conductivity, thus resulting in poor insulation of the silicone rubber of comparative example 3.
As can be seen from the combination of example 3, comparative example 4 and table 2, the heat conductive property of the silicone rubber of comparative example 4 is superior to that of example 3, but the insulation property is inferior to that of example 3, the modified graphene-based filler used in the silicone rubber raw material of comparative example 4 is more, and the amount of the liquid crystal polymer is reduced, resulting in improper compounding ratio of the silicone rubber, and the liquid crystal polymer is not uniformly embedded in the interlayer structure of graphene, thereby resulting in a decrease in the insulation property of the silicone rubber.
As can be seen from the combination of example 3, example 4 and table 2, the heat conduction performance and insulation performance of the silicone rubber prepared in example 3 are better than those of example 4, since the silicone rubber prepared in example 4 uses the modified graphene-based filler prepared in preparation example 4, and the modified graphene-based filler prepared in preparation example 4 is not added with the β -alanine solution, the stability of the zinc oxide particles on the reduced graphene oxide load is poor, the zinc oxide particles are very easy to fall off and free, the continuity of the heat conduction network is damaged, the heat conduction performance of the silicone rubber is poor, and the electrical conductivity of the reduced graphene oxide is improved after the zinc oxide particles fall off, so that the insulation performance of the silicone rubber is reduced.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The heat-conducting insulating liquid silicone rubber is characterized by comprising the following raw materials in parts by weight:
100 parts of dimethyl vinyl silicone rubber;
8-15 parts of hydroxyl-terminated silicone oil;
10-20 parts of liquid crystal high molecular polymer;
10-15 parts of hexagonal boron nitride;
50-70 parts of modified graphene-based filler;
1-3 parts of vulcanizing agent;
5-7 parts of titanate coupling agent;
the modified graphene-based filler is obtained by loading zinc oxide particles on the graphene-based filler.
2. The thermally conductive and electrically insulating liquid silicone rubber of claim 1, wherein: the graphene-based filler is a reduced graphene oxide filler.
3. The thermally conductive and electrically insulating liquid silicone rubber of claim 1, wherein: the modified graphene-based filler is prepared by a method comprising the following steps:
s1: mixing the reduced graphene oxide powder with a zinc oxide colloid solution, heating to 60-70 ℃, and then stirring at constant temperature for 1-1.5h to obtain a mixed solution;
s2: and adding 20-25% beta-alanine solution into the mixed solution, heating to 60-70 ℃, stirring at constant temperature for 2-3h, filtering, and calcining to obtain the modified graphene-based filler.
4. A thermally conductive and electrically insulating liquid silicone rubber as set forth in claim 3 wherein: in the S1, the mass ratio of the reduced graphene oxide powder to the zinc oxide colloidal solution is 1: (1-1.5); the mass ratio of the mixed solution to the beta-alanine solution in the S2 is 1: (0.3-0.5).
5. A thermally conductive and electrically insulating liquid silicone rubber as set forth in claim 3 wherein: the zinc oxide colloid solution is prepared by the following method: dissolving zinc acetate solution in glycerol diethyl ether, stirring for 20-30min, adding ethylenediamine with the same mole number as that of the zinc acetate solution, and stirring at constant temperature of 70-80deg.C for 0.5-1 hr to obtain zinc oxide colloid solution.
6. The thermally conductive and electrically insulating liquid silicone rubber of claim 1, wherein: the molecular weight of the hydroxyl-terminated silicone oil is 1.5-2.0 ten thousand, and the hydroxyl content is 0.17-0.23%.
7. A method for preparing a thermally conductive and insulating liquid silicone rubber as claimed in any one of claims 1 to 6, comprising the steps of:
step one: mixing: mixing dimethyl vinyl silicone rubber, hydroxyl-terminated silicone oil, a liquid crystal high molecular polymer, hexagonal boron nitride, modified graphene-based filler, a vulcanizing agent and a titanate coupling agent according to a proportion, and then mixing on a mixing mill, and standing at room temperature for 6-8 hours after mixing uniformly to obtain a mixed rubber;
step two: vulcanizing: vulcanizing the rubber compound obtained in the step one at 170-180 ℃ and 6-8Mpa for 10-20min, and then cooling at room temperature and 4-6Mpa for 10-20min to obtain the silicone rubber.
8. Use of the thermally conductive and insulating liquid silicone rubber according to any one of claims 1 to 6 or the thermally conductive and insulating liquid silicone rubber according to claim 7 in the preparation of thermal interface materials.
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| CN117645795A (en) * | 2024-01-30 | 2024-03-05 | 北京泰派斯特电子技术有限公司 | Elastomer composition, high-elasticity heat-conducting insulating gasket and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117645795A (en) * | 2024-01-30 | 2024-03-05 | 北京泰派斯特电子技术有限公司 | Elastomer composition, high-elasticity heat-conducting insulating gasket and preparation method thereof |
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