CN111961255B - Heat-conducting gel and preparation method thereof - Google Patents
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Abstract
The invention discloses a heat-conducting gel and a preparation method thereof. The metal hybrid heat-conducting filler can reduce the interface thermal resistance between the metal heat-conducting fillers, and the heat-conducting gel has high heat conductivity coefficient.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a heat-conducting gel and a preparation method thereof.
Background
The demand for high performance electronics is increasing and the high packaging and high power density components of modern electronic devices inevitably lead to thermal failure. Effective heat dissipation is a key technology that affects the life and performance of electronic devices. Thermal interface materials are the best choice to help solve the heat dissipation problem. The thermal interface material is divided into forms of heat-conducting gel, heat-conducting gasket, heat-conducting paste, heat-conducting phase change and the like. The heat-conducting gel is curable heat-conducting paste and a heat-conducting gasket capable of being glued, has the advantages of easiness in operation, low interface contact thermal resistance and the like, is considered to be a material meeting the development requirement of a future thermal interface material, and is widely concerned in domestic and foreign industrial fields.
CN 109415619 a discloses a thermal interface material comprising at least one polysiloxane; at least one thermally conductive filler; and at least one adhesion promoter containing both amine and alkyl functional groups. The aim is to address the problem of dripping and cracking of thermally conductive gel products during temperature cycling tests, including products that may potentially be more likely to fail in extreme cases. However, the patent does not mention the value of the thermal conductivity.
CN 105419339A discloses a high-performance silicon-based heat-conducting gel and a preparation method thereof. The silicon-based heat-conducting gel consists of organic silicon gel, hydrogen-containing silicone oil, hydroxyl silicone oil and heat-conducting powder. The heat conducting powder is prepared by compounding different kinds of powder according to three particle sizes of large, medium and small. However, the thermal conductivity coefficient of the thermal conductive gel obtained in the patent is not more than 4.5W/mK, and the viscosity is high.
CN106398226A discloses a heat-conducting silica gel and a preparation method thereof, which comprises a base polymer, a cross-linking agent, a filler and a silane coupling agent. According to the technical scheme, the thermal interface material with higher stability than the silicone grease, the silicone grease and the heat-conducting mud which are commonly used in the market at present can be obtained, the problem that the silicone grease, the silicone grease and the heat-conducting mud which are commonly used in the market at present can become dry after being used at high temperature for a long time is solved, and the heat-conducting efficiency of the heat-conducting interface material used for a long time is further ensured. However, the thermal conductivity of the thermally conductive gel does not exceed 4.0W/mK.
Therefore, the development of a heat-conducting gel with high heat conductivity coefficient is a problem to be solved in the field.
Disclosure of Invention
In order to solve the problems of the background art, the present invention provides a thermally conductive gel and a method for preparing the same.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: in one aspect, the invention provides a metal hybrid heat-conducting filler, wherein the metal hybrid heat-conducting filler is a metal filler surface loaded with a nano metal filler;
the metal filler is selected from at least one of aluminum powder, silver powder and copper powder; the nano metal filler is at least one selected from aluminum powder, silver powder and copper powder.
Further, the mass ratio of the nano metal filler to the metal filler is 5:95-20: 80;
preferably, the particle size of the metal filler is 0.5 to 30 μm; the grain diameter of the nano metal filler is 0.05-500 nm.
On the other hand, the invention provides a preparation method of any one of the metal hybrid heat-conducting fillers, which is characterized in that a nano metal filler is deposited on the surface of a metal filler by a chemical reduction method;
preferably, the preparation method specifically comprises: adding a metal filler into absolute ethyl alcohol, then adding a reducing agent, and uniformly stirring to obtain a first solution; adding a precursor of the nano metal filler into absolute ethyl alcohol, and uniformly stirring to obtain a second solution; adding the second solution into the first solution at 25-90 ℃ in a dropwise adding mode under a stirring state, and continuing to react for 1-6 hours after dropwise adding is finished to obtain the metal hybrid heat-conducting filler; more preferably, the precursor of the nano metal filler is Al (NO)3)3、AgNO3、Cu(NO3)2At least one reducing agent selected from N, N-dimethylformamide, sodium borohydride, ascorbic acid and hydrazine hydrate.
In another aspect, the invention provides an application of any one of the metal hybrid heat-conducting fillers in preparation of a heat-conducting gel.
In another aspect, the invention provides a heat-conducting gel, which is prepared from the following raw materials in parts by mass:
(A) 100 parts of organopolysiloxane containing at least two vinyl groups;
(B) 10-90 parts of polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms;
(C) 0.1-10 parts of a hydrosilylation catalyst;
(D) 0.1-0.5 part of hydrosilylation inhibitor;
(E) 800-1200 parts of metal hybrid heat-conducting filler;
preferably, the metal hybrid heat-conducting filler consists of the metal hybrid heat-conducting filler with large, medium and small particle sizes according to the weight ratio of 8:2:1-5:4:1, wherein the large particle size is 10-30 μm; the medium particle size is 1-10 μm, and the small particle size is 500nm-1.0 μm;
preferably, the mass fraction of the metal hybrid heat-conducting filler is 80% -91%, preferably 85% -91%.
Further, the organopolysiloxane containing at least two vinyl groups has a molecular structural formula of
Wherein R is methyl (CH)3) Phenyl (C)6H5) Ethyl (C)2H5) At least one of (i.e., R in the molecular structural formula may be the same or different), m is 0 to 100, n is 1 to 2000;
preferably, the organopolysiloxane containing at least two vinyl groups has a viscosity of 20 to 1000mpa.s at 25 ℃;
preferably, the polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms has a molecular structure of
Wherein R is a hydrogen atom, or a hydrogen atom and a methyl group (CH)3) Phenyl (C)6H5) Ethyl (C)2H5) At least one (i.e., R in the molecular structural formula may be the same or different);
preferably, the polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms has a viscosity of 20 to 100mPa.s at 25 ℃.
Further, the hydrosilylation reaction catalyst is a hydrosilylation reaction catalyst capable of initiating a hydrosilylation reaction of components (a) and (B); preferably, the hydrosilylation reaction catalyst is selected from platinum-containing catalysts;
preferably, the platinum-containing catalyst has a general structural formula
More preferably, the platinum-containing catalyst comprises at least one of platinum cyclovinylmethylsiloxane complex, platinum carbonyl cyclovinylmethylsiloxane complex, platinum divinyltetramethyldisiloxane dimethylfumarate complex, platinum divinyltetramethyldisiloxane dimethylmaleate complex;
preferably, the hydrosilylation reaction inhibitor is a hydrosilylation reaction inhibitor capable of inhibiting the hydrosilylation reaction of components (a) and (B); preferably, the hydrosilylation reaction inhibitor is selected from alkynols;
preferably, the alkynol comprises at least one of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 2-ethynyl-isopropanol, 2-ethynyl-butan-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, silylethynyl alcohol.
Further, the additive also comprises a raw material component (F);
preferably, the additive comprises a silane coupling agent;
preferably, the additive further comprises a plasticizer, a flame retardant and a colorant;
preferably, the additive includes 0 to 1.0 part by mass of a plasticizer, 0.5 to 1.0 part by mass of a silane coupling agent, 0 to 1.0 part by mass of a flame retardant, and 0 to 0.5 part by mass of a colorant.
Furthermore, the thermal conductivity coefficient of the thermal conductive gel is 3.0-15W/mK, and the viscosity is 200-500 Pa.s.
In another aspect, the present invention provides a method for preparing any one of the above thermal conductive gels, including the following steps:
1) compounding of metal hybrid heat-conducting filler (by compounding, the content of the filler is improved, and further the effects of improving the heat conductivity coefficient and reducing the viscosity are achieved)
Preparing metal hybrid heat-conducting filler with three particle sizes of large, medium and small, wherein the particle size of the large particle is 10-30 mu m; the medium particle size is 1-10 μm, and the small particle size is 500nm-1.0 μm;
compounding the metal hybrid heat-conducting filler with particle sizes, and weighing and premixing the metal hybrid heat-conducting filler with large, medium and small particle sizes according to the weight ratio of 8:2:1-5:4: 1;
2) solvent-free mixing
Stirring and mixing the compound metal hybrid heat-conducting filler obtained in the step 1) with organopolysiloxane containing at least two vinyl groups, polyorganosiloxane with at least 2 silicon-bonded hydrogen atoms, a catalyst and an inhibitor for 30-60 minutes to obtain the heat-conducting gel, wherein the mixing temperature is preferably 25-50 ℃.
The invention further provides a heat-conducting gel layer, wherein the heat-conducting gel layer is obtained by curing the prepared heat-conducting gel;
preferably, the curing temperature is 100-150 ℃, and the curing time is 1-2 hours.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the nano metal filler is loaded on the surface of the metal heat-conducting filler, so that the interface thermal resistance between the metal heat-conducting fillers is reduced, and the high heat conductivity coefficient of the heat-conducting gel is realized. Meanwhile, the heat-conducting gel prepared by the invention has low viscosity (200-500Pa.s), so that the heat-conducting gel can be operated by a dispenser, and the production efficiency is improved. The heat-conducting gel provided by the invention has the advantages of high heat conductivity coefficient (15W/mK), low viscosity (200-500Pa.s), simple preparation method and easy operation, and is a novel heat-conducting gel with large-scale industrial production prospect.
Drawings
Fig. 1 is a schematic structural diagram of the metal hybrid heat-conducting filler of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Preparing the large-particle-size aluminum powder @ silver hybrid heat-conducting filler: adding aluminum powder (100g) with the particle size of 30 mu m into an absolute ethyl alcohol solvent, then adding 0.5g N, and uniformly stirring N-dimethylformamide to obtain a first solution; 2.0g of AgNO3Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; and adding the second solution into the first solution at 25 ℃ in a dropwise adding mode under a stirring state, after dropwise adding is finished for 2 hours, and then carrying out heat preservation reaction for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with large particle size.
Preparing the medium-particle-size aluminum powder @ silver hybrid heat-conducting filler: adding aluminum powder (100g) with the particle size of 10 mu m into an absolute ethyl alcohol solvent, then adding 0.5g of sodium borohydride, and uniformly stirring to obtain a first solution; 2.0g of AgNO3Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; adding the second solution into the first solution at 25 deg.C under stirring, dropwise adding for 2 hr, and keeping the temperatureAnd reacting for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with medium particle size.
Preparation of small-particle-size aluminum powder @ silver hybrid heat-conducting filler: adding aluminum powder (100g) with the particle size of 1.0 mu m into an absolute ethyl alcohol solvent, then adding 0.5g of ascorbic acid, and uniformly stirring to obtain a first solution; 2.0g of AgNO3Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; and adding the second solution into the first solution at 25 ℃ in a dropwise adding mode under a stirring state, after dropwise adding is finished for 2 hours, and then carrying out heat preservation reaction for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with small particle size.
Preparing a heat conducting gel:
vinyl-terminated polydimethylsiloxane (Nantong) Limited company, model number Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Nantong) Limited company, model number Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g)10 parts, hydrosilylation catalyst platinum ring vinyl methyl siloxane complex 10 parts, hydrosilylation reaction inhibitor 1-ethynyl-1-cyclohexanol 0.5 part, silane coupling agent decyl trimethoxy silane 1.0 part, large, medium and small metal aluminum powder and silver metal heat-conducting filler 1200 parts compounded according to the weight ratio of 8:2:1 are mixed in a high-speed mixer for 30 minutes, and the mixing temperature is 25 ℃, so that the heat-conducting gel is obtained. And curing the prepared heat-conducting gel at 150 ℃ for 1 hour to obtain the heat-conducting gel layer.
Example 2
Preparing the large-particle-size aluminum powder @ copper hybrid heat-conducting filler: adding aluminum powder (100g) with the particle size of 30 mu m into an absolute ethyl alcohol solvent, then adding 0.5g N, and uniformly stirring N-dimethylformamide to obtain a first solution; 4.0g of Cu (NO)3)2Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; and adding the second solution into the first solution at 25 ℃ in a dropwise adding mode under a stirring state, after dropwise adding is finished for 2 hours, and then carrying out heat preservation reaction for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with large particle size.
Preparation of the aluminum powder @ copper hybrid heat-conducting filler with medium particle size: the particle diameter is 10 muAdding 100g of aluminum powder m into an absolute ethyl alcohol solvent, adding 0.5g of sodium borohydride, and uniformly stirring to obtain a first solution; 2.0g of Cu (NO)3)2Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; and adding the second solution into the first solution at 25 ℃ in a dropwise adding mode under a stirring state, after dropwise adding is finished for 2 hours, and then carrying out heat preservation reaction for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with medium particle size.
Preparation of the small-particle-size aluminum powder @ copper hybrid heat-conducting filler: adding aluminum powder (100g) with the particle size of 1.0 mu m into an absolute ethyl alcohol solvent, then adding 0.5g of ascorbic acid, and uniformly stirring to obtain a first solution; 2.0g of Cu (NO)3)2Dissolving in 20mL of absolute ethyl alcohol to obtain a second solution; and adding the second solution into the first solution at 25 ℃ in a dropwise adding mode under a stirring state, after dropwise adding is finished for 2 hours, and then carrying out heat preservation reaction for 2 hours to obtain the aluminum powder @ silver metal hybrid heat-conducting filler with small particle size.
Preparing a heat conducting gel:
vinyl-terminated polydimethylsiloxane (Anbia Special Silicone (Nantong) Co., Ltd., model number Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 silicon-bonded hydrogen-atom-containing polyorganosiloxane (Anbia Special Silicone (Nantong) Co., Ltd., model number Andii XL-11, viscosity: 45cst, silicon hydrogen content 4.35mmoles/g)50 parts, hydrosilylation catalyst platinum cyclovinylmethylsiloxane complex 0.1 part, hydrosilylation reaction inhibitor 2-methyl-3-butyn-2-ol 0.1 part, silane coupling agent decyltrimethoxysilane 1.0 part, 900 parts of large, medium and small metal aluminum powder @ copper metal hybrid heat-conducting filler compounded according to the weight ratio of 5:4:1, mixing in a high-speed mixer for 60 minutes at 25 ℃ to obtain the heat-conducting gel. And curing the prepared heat-conducting gel at 100 ℃ for 2 hours to obtain a heat-conducting gel layer.
Example 3
The preparation of the aluminum powder @ silver hybrid heat-conducting filler is the same as that of example 1.
Preparing a heat conducting gel:
vinyl-terminated polydimethylsiloxane (Nantong) No. 100 parts of Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g), 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Nantong) No. 2 Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g), 100 parts of hydrosilylation catalyst platinum divinyl tetramethyl disiloxane dimethyl fumarate complex, 0.3 part of hydrosilylation reaction inhibitor 2-phenyl-3-butyn-2-ol, 1.0 part of silane coupling agent decyl trimethoxy silane, 1000 parts of large, medium and small metal aluminum powder and silver metal hybrid heat-conducting filler compounded according to the weight ratio of 7:2:1, mixing for 60 minutes in a high-speed mixer at the mixing temperature of 25 ℃, a thermally conductive gel was obtained. And curing the prepared heat-conducting gel at 100 ℃ for 2 hours to obtain a heat-conducting gel layer.
Example 4
The preparation of the aluminum powder @ copper hybrid heat-conducting filler is the same as that of example 2.
Preparing a heat conducting gel:
vinyl-terminated polydimethylsiloxane (Nantong) No. 100 parts of Andii Special Silicone (Nantong) No. VS500, viscosity: 500cst, vinyl content 0.15mmoles/g), 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Nantong) No. 2 Andii Special Silicone (Nantong) No. XL-13, viscosity: 100cst, and silicon hydrogen content 3.80mmoles/g), 100 parts of hydrosilylation catalyst platinum divinyl tetramethyl disiloxane dimethyl fumarate complex, 0.3 part of hydrosilylation reaction inhibitor 2-phenyl-3-butyn-2-ol, 1.0 part of silane coupling agent decyl trimethoxy silane, 1200 parts of large, medium and small metal aluminum powder compounded according to the weight ratio of 6:2:1, mixing for 60 minutes in a high-speed mixer at a mixing temperature of 25 ℃, a thermally conductive gel was obtained. And curing the prepared heat-conducting gel at 100 ℃ for 2 hours to obtain a heat-conducting gel layer.
Example 5
The preparation of the aluminum powder @ silver hybrid heat-conducting filler is the same as that of example 1.
Preparing a heat conducting gel:
vinyl-terminated polydimethylsiloxane (Nantong) No. 100 parts of Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g), 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Nantong) No. 2 Andii XL-13, viscosity: 100cst, and silicon hydrogen content 3.80mmoles/g), 50 parts of hydrosilylation catalyst platinum divinyl tetramethyl disiloxane dimethyl fumarate complex, 0.3 part of hydrosilylation reaction inhibitor 2-phenyl-3-butyn-2-ol, 1.0 part of silane coupling agent decyl trimethoxy silane, 800 parts of large, medium and small metal aluminum powder and hybrid heat-conducting copper filler compounded according to the weight ratio of 6:3:1, mixing in a high-speed mixer for 60 minutes at the mixing temperature of 25 ℃, a thermally conductive gel was obtained. And curing the prepared heat-conducting gel at 100 ℃ for 2 hours to obtain a heat-conducting gel layer.
Comparative example 1 ordinary aluminum powder filling
Vinyl-terminated polydimethylsiloxane (Nantong) No. Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 polyorganosiloxanes with silicon-bonded hydrogen atoms (Nantong) No. Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g)10 parts, hydrosilylation catalyst platinum cyclovinylmethylsiloxane complex 10 parts, hydrosilylation reaction inhibitor 1-ethynyl-1-cyclohexanol 0.5 part, silane coupling agent decyltrimethoxysilane 1.0 part, and large-particle aluminum powder (30 μm), medium-particle aluminum powder (10 μm), and small-particle aluminum powder (1.0 μm) were mixed in a weight ratio of 8:2:1 to 1200 parts. And (3) mixing the materials in a high-speed mixer for 30 minutes at the mixing temperature of 25 ℃ to obtain the heat-conducting gel. And curing the prepared heat-conducting gel at 150 ℃ for 1 hour to obtain the heat-conducting gel layer.
Comparative example 2 large-particle-size aluminum powder @ silver hybrid thermal conductive filler filling
The preparation of the large-particle-size aluminum powder @ silver hybrid heat-conducting filler is the same as that of example 1.
Vinyl-terminated polydimethylsiloxane (Andius special silicone (Nantong) Co., Ltd., model number Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Andius special silicone (Nantong) Co., Ltd., model number Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g)10 parts, hydrosilylation catalyst platinum ring vinyl methyl siloxane complex 10 parts, hydrosilylation reaction inhibitor 1-ethynyl-1-cyclohexanol 0.5 part, silane coupling agent decyl trimethoxy silane 1.0 part, and large-particle-size aluminum powder @ silver hybrid heat-conducting filler (30 μm)1200 parts. And (3) mixing the materials in a high-speed mixer for 30 minutes at the mixing temperature of 25 ℃ to obtain the heat-conducting gel. And curing the prepared heat-conducting gel at 150 ℃ for 1 hour to obtain the heat-conducting gel layer.
Comparative example 3 aluminum powder @ silver hybrid heat-conducting filler filling with particle size
The preparation of the medium-particle-size aluminum powder @ silver hybrid heat-conducting filler is the same as that of example 1.
Vinyl-terminated polydimethylsiloxane (Andius special silicone (Nantong) Co., Ltd., model number Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Andius special silicone (Nantong) Co., Ltd., model number Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g)10 parts, a hydrosilylation catalyst platinum ring vinyl methyl siloxane complex 10 parts, a hydrosilylation reaction inhibitor 1-ethynyl-1-cyclohexanol 0.5 part, a silane coupling agent decyl trimethoxy silane 1.0 part, and a large-particle-diameter aluminum powder @ silver hybrid heat-conducting filler (15um)1200 parts. And (3) mixing the materials in a high-speed mixer for 30 minutes at the mixing temperature of 25 ℃ to obtain the heat-conducting gel. And curing the prepared heat-conducting gel at 150 ℃ for 1 hour to obtain the heat-conducting gel layer.
Comparative example 4 Small-particle-size aluminum powder @ silver hybrid heat-conducting filler filling
The preparation of the small-particle-size aluminum powder @ silver hybrid heat-conducting filler is the same as that of example 1.
Vinyl-terminated polydimethylsiloxane (Andius special silicone (Nantong) Co., Ltd., model number Andii VS100, viscosity: 100cst, vinyl content 0.37mmoles/g)100 parts, 2 silicon-bonded hydrogen atom-containing polyorganosiloxanes (Andius special silicone (Nantong) Co., Ltd., model number Andii XL-11, viscosity: 45cst, and silicon hydrogen content 4.35mmoles/g)10 parts, hydrosilylation catalyst platinum ring vinyl methyl siloxane complex 10 parts, hydrosilylation reaction inhibitor 1-ethynyl-1-cyclohexanol 0.5 part, silane coupling agent decyl trimethoxy silane 1.0 part, small-particle-size aluminum powder @ silver hybrid heat-conducting filler (1.0um)1200 parts. And (3) mixing the materials in a high-speed mixer for 30 minutes at the mixing temperature of 25 ℃ to obtain the heat-conducting gel. And curing the prepared heat-conducting gel at 150 ℃ for 1 hour to obtain the heat-conducting gel layer.
The structural schematic diagram of the metal hybrid heat-conducting filler is shown in fig. 1, and small metal fillers exist on the surface of large metal fillers to form strawberry-shaped metal hybrid particles, so that the interface thermal resistance between the fillers is reduced, and the heat-conducting gel has high heat conductivity coefficient and low viscosity.
(1) And (3) testing the heat conductivity coefficient:
a standard test method for measuring heat conduction in a vertical direction by a steady state method is provided, wherein a test instrument is an LW-9389TIM resistance and conductivity measuring instrument, and the method comprises the following specific steps: placing the thermal interface composite material between the instrument bars, and establishing stable heat flow through the assembly; then monitoring the temperature in the strip at two or more points along its length; the temperature difference across the interface is calculated from the temperature readings obtained and used to determine the thermal conductivity of the interface.
(2) Viscosity measurement
The viscosity of the thermally conductive gel was measured using a rheometer.
The thermal conductivity and viscosity of the thermal conductive gels provided in examples 1 to 5 and comparative examples 1 to 4 were tested according to the above methods, and the test results are shown in table 1:
TABLE 1
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. the present invention does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (24)
1. The heat-conducting gel is characterized by being prepared from the following raw materials in parts by mass:
(A) 100 parts of organopolysiloxane containing at least two vinyl groups;
(B) 10-90 parts of polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms;
(C) 0.1-10 parts of a hydrosilylation catalyst;
(D) 0.1-0.5 part of hydrosilylation inhibitor;
(E) 100 portions and 1200 portions of metal hybrid heat-conducting filler;
the metal hybrid heat-conducting filler consists of three metal hybrid heat-conducting fillers with the following limited particle sizes of large, medium and small according to the weight ratio of 8:2:1-5:4:1, wherein the large particle size is 10-30 mu m; the medium particle size is 1-10 μm, and the small particle size is 500nm-1.0 μm;
the metal hybrid heat-conducting filler is defined as a metal filler surface loaded with a nano metal filler; the metal filler is selected from at least one of aluminum powder, silver powder and copper powder; the nano metal filler is selected from at least one of aluminum powder, silver powder and copper powder;
the mass fraction of the metal hybrid heat-conducting filler is 85-91%.
2. The thermally conductive gel of claim 1, wherein the mass ratio of the nano metal filler to the metal filler is 5:95-20: 80.
3. The heat conductive gel according to claim 1, wherein the metal filler has a particle size of 0.5 to 30 μm; the grain diameter of the nano metal filler is 0.05-500 nm.
4. The thermally conductive gel of any one of claims 1-3, wherein the defined metal hybrid thermally conductive filler is formed by depositing nano-metal filler on the surface of a metal filler by chemical reduction.
5. The heat-conducting gel as claimed in claim 4, wherein the preparation method of the metal hybrid heat-conducting filler specifically comprises the following steps: adding a metal filler into absolute ethyl alcohol, then adding a reducing agent, and uniformly stirring to obtain a first solution; adding a precursor of the nano metal filler into absolute ethyl alcohol, and uniformly stirring to obtain a second solution; adding the second solution into the first solution at 25-90 ℃ in a dropwise adding mode under a stirring state, and continuing to react for 1-6 hours after dropwise adding is finished to obtain the metal hybrid heat-conducting filler; the precursor of the nano metal filler is Al (NO)3)3、AgNO3、Cu(NO3)2At least one reducing agent selected from N, N-dimethylformamide, sodium borohydride, ascorbic acid and hydrazine hydrate.
6. The thermally conductive gel of claim 1, wherein said organopolysiloxane containing at least two vinyl groups has a molecular formula of
Wherein R is at least one of methyl, phenyl and ethyl, m =0-100, and n = 1-2000.
7. The thermally conductive gel of claim 6, wherein the organopolysiloxane having at least two vinyl groups has a viscosity of 20 to 1000mPa.s at 25 ℃.
8. The thermally conductive gel of claim 1, wherein said polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms, molecules thereofStructural formula is
Wherein R is hydrogen atom and at least one of methyl, phenyl and ethyl.
9. The thermally conductive gel of claim 8, wherein said polyorganosiloxane having at least 2 silicon-bonded hydrogen atoms has a viscosity of 20 to 100mpa.s at 25 ℃.
10. The thermally conductive gel of claim 1, wherein the hydrosilylation reaction catalyst is a hydrosilylation reaction catalyst capable of initiating a hydrosilylation reaction of components (a) and (B).
11. The thermally conductive gel of claim 10, wherein the hydrosilylation reaction catalyst is selected from platinum-containing catalysts.
12. The thermally conductive gel of claim 11, wherein the platinum-containing catalyst has the general structural formula
。
13. The thermally conductive gel of claim 12, wherein the platinum-containing catalyst comprises at least one of a platinum cyclovinylmethylsiloxane complex, a platinum carbonylcyclovinylmethylsiloxane complex, a platinum divinyltetramethyldisiloxane dimethylfumarate complex, a platinum divinyltetramethyldisiloxane dimethylmaleate complex.
14. The thermally conductive gel of claim 1, wherein the hydrosilylation reaction inhibitor is a hydrosilylation reaction inhibitor capable of inhibiting the hydrosilylation reaction of components (a) and (B).
15. The thermally conductive gel of claim 14, wherein said hydrosilylation reaction inhibitor is selected from the group consisting of acetylenic alcohols.
16. The thermally conductive gel of claim 15, wherein said acetylenic alcohol comprises at least one of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 2-ethynyl-isopropanol, 2-ethynyl-butan-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, and silylated acetylenic alcohol.
17. The thermally conductive gel of claim 1, further comprising a raw material component (F) additive.
18. The thermally conductive gel of claim 17, wherein the additive comprises a silane coupling agent.
19. The thermally conductive gel of claim 18, wherein said additives further comprise plasticizers, flame retardants, and colorants.
20. The thermally conductive gel of claim 18, wherein said additives further comprise 0 to 1.0 parts by mass of a plasticizer, 0.5 to 1.0 parts by mass of a silane coupling agent, 0 to 1.0 parts by mass of a flame retardant, and 0 to 0.5 parts by mass of a colorant.
21. A method of making a thermally conductive gel as claimed in any one of claims 1 to 20, comprising the steps of:
1) compounding of metal hybrid heat-conducting filler
Preparing metal hybrid heat-conducting filler with three particle sizes of large, medium and small, wherein the particle size of the large particle is 10-30 mu m; the medium particle size is 1-10 μm, and the small particle size is 500nm-1.0 μm;
compounding the metal hybrid heat-conducting filler with particle sizes, and weighing and premixing the metal hybrid heat-conducting filler with large, medium and small particle sizes according to the weight ratio of 8:2:1-5:4: 1;
2) solvent-free mixing
Stirring and mixing the compound metal hybrid heat-conducting filler obtained in the step 1) with organopolysiloxane containing at least two alkenyl groups, polyorganosiloxane with at least 2 silicon-bonded hydrogen atoms, a catalyst and an inhibitor for 30-60 minutes to obtain the heat-conducting gel.
22. The method of claim 21, wherein the mixing temperature in step 2) is 25-50 ℃.
23. A thermally conductive gel layer, characterized in that the thermally conductive gel prepared in claim 21 is cured to obtain a thermally conductive gel layer.
24. The thermally conductive gel layer of claim 23, wherein the curing temperature is 100 ℃ and 150 ℃ and the curing time is 1-2 hours.
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| CN115627074B (en) * | 2022-09-22 | 2024-04-19 | 深圳先进电子材料国际创新研究院 | Anti-fatigue heat-conducting gel and preparation method thereof |
| CN115651411A (en) * | 2022-10-26 | 2023-01-31 | 福建臻璟新材料科技有限公司 | High-flexibility low-exudation heat-conducting gel and preparation method thereof |
| CN115521462A (en) * | 2022-10-28 | 2022-12-27 | 北京天山新材料技术有限公司 | Filler treating agent and preparation method thereof, heat-conducting silica gel, packaging material and electronic component |
| CN115627076B (en) * | 2022-10-31 | 2023-10-20 | 长沙先进电子材料工业技术研究院有限公司 | Heat-conducting gel and preparation method and application thereof |
| CN115612300A (en) * | 2022-11-03 | 2023-01-17 | 苏州泰吉诺新材料科技有限公司 | Heat-conducting gasket and preparation method thereof |
| CN115785677A (en) * | 2022-12-09 | 2023-03-14 | 东莞市博恩复合材料有限公司 | Single-component phase-change organic silicon heat-conducting gel and preparation method thereof |
| CN116574383B (en) * | 2023-05-23 | 2024-05-10 | 江西天永诚高分子材料有限公司 | Low-volatility high-heat-conductivity single-component addition type heat-conducting daub and preparation method thereof |
| CN116606608B (en) * | 2023-05-23 | 2024-04-05 | 江西天永诚高分子材料有限公司 | Heat conducting filler, double-component organic silicon pouring sealant containing heat conducting filler and preparation method of double-component organic silicon pouring sealant |
| CN117820866A (en) * | 2023-12-26 | 2024-04-05 | 深圳市锦联科技有限公司 | Organic silicon heat-conducting gel and preparation method thereof |
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