CN115716991B - Thermal interface material with adjustable orientation direction of two-dimensional lamellar filler and preparation method thereof - Google Patents
Thermal interface material with adjustable orientation direction of two-dimensional lamellar filler and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000000945 filler Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000005060 rubber Substances 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 22
- 238000005520 cutting process Methods 0.000 claims description 21
- 229910052582 BN Inorganic materials 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
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- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
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- 238000004132 cross linking Methods 0.000 description 3
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- 239000011664 nicotinic acid Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- -1 polysiloxanes Polymers 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical group [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 2
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
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- DFWCPLGXFMSUCW-UHFFFAOYSA-N 3-(dimethylamino)propyl carbamimidothioate;hydron;dichloride Chemical compound Cl.Cl.CN(C)CCCSC(N)=N DFWCPLGXFMSUCW-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
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- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
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- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
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- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a thermal interface material with adjustable orientation direction of a two-dimensional lamellar filler and a preparation method thereof. The thermal interface material comprises 100 parts of rubber matrix, 50-1000 parts of two-dimensional lamellar filler and 0.1-50 parts of 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ]. The invention adopts high-temperature mould pressing and tape casting molding, and successfully realizes the vertical orientation of the two-dimensional filler in the thermal interface material.
Description
Technical Field
The invention relates to the field of organic-inorganic composite materials, in particular to the field of thermal management and thermal interface materials, and designs a novel thermal interface material with a shell-like pearl layer bionic structure and a preparation method thereof.
Background
Thermal Interface Materials (TIMs) are indispensable materials to enhance thermal conduction between the heat source and heat sink interfaces, and are about 0.05-2 mm thick. Typically, TIM major products are thermally conductive silicone grease, thermally conductive gel, thermally conductive pads, and the like. Because of the high flexibility of polysiloxanes, most TIMs are composed of polysiloxanes. Only a small proportion of non-silicone elastomer systems, such as acrylate and polyurethane rubbers, do not bleed out relative to silicone rubber systems, but the hardness is higher. The advantages and disadvantages of different TIMs are shown in Table 1.
TABLE 1 merits and demerits, thickness and Heat conductivity of TIM Main product
The problem of heat dissipation in electronic devices is now becoming a bottleneck limiting their development, and the design and fabrication of high performance TIMs is particularly urgent. Inspired by the lamellar shell pearl layer in nature, the submicron-level high-regularity lamellar orientation structure piled by lamellar calcium carbonate and protein has the characteristics of high heat conduction, high toughness and the like.
Therefore, the invention carries out bionic structural design on a series of two-dimensional heat conducting filler and rubber. Because the heat conducting filler with a two-dimensional lamellar structure, such as boron nitride, crystalline flake graphite, graphene, aluminum oxide and zinc oxide, has obvious anisotropy in heat conductivity coefficient and extremely high heat conductivity coefficient in the in-plane direction of the lamellar, the bionic design composite material also has anisotropy in heat conductivity coefficient, and the high heat conductivity direction is the microscopic orientation direction of the heat conducting filler inside the material. It is contemplated that in a practical application of a TIM, the heat flow conduction path is from the heat source to the heat sink interface, this conduction path being perpendicular to the plane of the TIM, parallel to the thickness direction of the TIM. Therefore, the key to utilizing the high thermal conductivity characteristics in the two-dimensional filling plane is to realize the regulation of the vertical orientation of the two-dimensional filling plane, so that the TIM achieves a higher out-of-plane thermal conductivity coefficient (Through-plane kappa).
Currently, the horizontal orientation method of two-dimensional filler is well established (i.e. the two-dimensional filler is parallel to the plane direction of the composite material and perpendicular to the thickness direction), and reports are made in many documents, including high temperature molding, twin roll shearing, stretching orientation, blade coating, extrusion, injection molding, expansion flow field, electrospinning, casting, vacuum assisted suction filtration, ice template method, and electric/magnetic field assisted methods. The suitable scenes of each method are different, and the micro-orientation degree of the finally obtained material is different. Among these methods, the high-temperature molding, twin-roll shearing, extrusion, injection molding, and casting can be performed by means of conventional polymer processing equipment, so that the method has the advantages of simple process and suitability for large-scale preparation. Wherein, high temperature mould pressing, double roller shearing and tape casting can prepare film materials.
Compared with the horizontal orientation of the two-dimensional filler, the difficulty of inducing the vertical arrangement of the flaky filler is higher, the current main stream method is to realize the vertical orientation in a magnetic field after the magnetic nano particles are implanted on the surface of the filler, but the method has higher requirement on the filler and complex process. In recent two years, a new method for preparing vertically oriented TIMs has emerged in the literature: (1) the two-dimensional filler is oriented in parallel to obtain a thin film material with high in-plane heat conductivity coefficient; (2) carrying out stacking welding on the prepared film material to form a block body with higher thickness; (3) the bulk material is slit longitudinally in a specific direction to obtain a vertically oriented TIM.
The implementation of this type of process has two difficulties, (1) a suitable process for the horizontal orientation of the two-dimensional filler; (2) welding performance of the film material. According to the above description, there are many preparation methods of the two-dimensional filler horizontally oriented material, but the process suitable for preparing the two-dimensional filler horizontally oriented film on a large scale only comprises three methods of high-temperature mould pressing, double-roller shearing and tape casting. However, the double-roll shearing has a poor orientation effect on the filler compared with high-temperature die pressing and tape casting, and a highly regular shell-like pearl layer structure cannot be prepared. This is because the twin roll shearing is performed at room temperature and the high temperature molding and casting are performed at high temperature, and the high molecular matrix becomes fluid at high temperature to make the two-dimensional filler in the matrix more easily oriented, so that the prepared film microstructure is similar to a shell nacreous layer structure. However, the polymeric matrix used for TIM is typically thermoset, such as the most commonly used methyl vinyl silicone rubber in TIM, which is not soldered after high temperature molding and cast molding. There is no report on the preparation of filler homeotropically oriented TIMs by high temperature molding and cast molding.
Disclosure of Invention
The preparation method of the TIM with vertical orientation in the prior art is complex and is not beneficial to large-scale preparation, or the prepared TIM has insufficient vertical orientation degree and cannot form a shell-like pearl layer structure. Therefore, aiming at the vertical orientation TIM, the invention designs a novel TIM formula and provides a method for preparing the two-dimensional filler with high orientation degree and suitable for large-scale preparation. This approach utilized high temperature molding and cast molding for the first time and successfully achieved vertical orientation of the two-dimensional filler in the TIM.
The invention aims to provide a thermal interface material with adjustable orientation direction of two-dimensional lamellar filler, which is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
50-1000 parts of two-dimensional lamellar filler;
0.1 to 50 portions of 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ].
Preferably, the thermal interface material is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
50-800 parts of two-dimensional lamellar filler;
1 to 30 parts of 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ].
More preferably, the thermal interface material is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
100-500 parts of two-dimensional lamellar filler;
1-20 parts of 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ].
In the thermal interface material of the present invention, the rubber matrix may be selected from the usual TIM matrix rubbers including, but not limited to: at least one of silicone rubber, acrylate rubber, polyurethane rubber, natural rubber, styrene-butadiene rubber, ethylene propylene rubber, neoprene rubber, nitrile rubber, butyl rubber, isoprene rubber, and styrene block copolymer.
In the thermal interface material of the present invention, the two-dimensional lamellar filler may be selected from commonly used two-dimensional heat conductive fillers, including but not limited to: at least one of boron nitride, crystalline flake graphite, graphene, aluminum oxide, zinc oxide, diamond, flaky silicon carbide, graphite phase carbon nitride, graphene oxide, silver micron flakes, flaky aluminum nitride, flaky silver powder, flaky aluminum powder and Mxene. The two-dimensional lamellar filler may be used in an amount of 50 parts, 100 parts, 200 parts, 300 parts, 400 parts, 500 parts, 600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, etc., based on 100 parts by weight of the rubber matrix.
In the thermal interface material of the present invention, preferably, the two-dimensional lamellar filler has a lamellar diameter of 1nm to 100 μm and a thickness of 0.1nm to 1 μm.
In the thermal interface material, a novel cross-linking agent is introduced: 2,2' - (1, 4-phenylene) -bis [ 4-thiol-1, 3, 2-dioxybenzaldehyde ] (BDB), the specific structural formula is shown in formula (I):
the BDB may be used in an amount of 0.1 part, 0.5 part, 1 part, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, etc., based on 100 parts by weight of the rubber matrix.
The introduction of BDB in the invention can endow the rubber material with the characteristics of Vitramers, ensure the integrity of a network while realizing the 'bond breaking-bond rearrangement', and ensure the gradual change of the viscosity instead of the abrupt viscosity change before and after the glass transition of the thermoplastic polymer or the sol-gel transition in the network with dissociated bonds, thereby having the remarkable advantages of wide processing temperature range and flexible processing technology. The thermal pad obtained after crosslinking with BDB has good shape retention characteristics, similar to TIM crosslinked with common crosslinking agents, and repeatable processability similar to that of thermoplastic elastomer at high temperature. Thus, the formulation of a range of TIMs designed in accordance with the present invention differs from commercially available TIMs in that BDB is used as a cross-linking agent for the TIM, allowing for reproducible processing properties of conventional thermoset TIM matrices.
The thermal interface material of the invention can also comprise common assistants such as silane coupling agents, accelerators and the like.
Silane coupling agents commonly used in the rubber field are used to facilitate filler dispersion. Common silane coupling agents are: bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane.
Accelerators are commonly used in the art as rubber additives for the purpose of promoting crosslinking of the rubber. Common accelerators are: accelerator M (2-mercaptobenzothiazole), accelerator DM (dibenzothiazyl disulfide), accelerator CBS (N-cyclohexyl-2-benzothiazole sulfenamide), accelerator TBBS (N-tert-butyl-2-benzothiazole sulfenamide), accelerator NOBS (N-oxydiethylene-2-benzothiazole sulfenamide), accelerator DZ (N, N' -dicyclohexyl-2-benzothiazole sulfenamide), accelerator TMTD (tetramethylthiuram disulfide), accelerator TMTM (tetramethylthiuram monosulfide), accelerator TETD (tetraethylthiuram disulfide), accelerator DPTT (pentamethylene thiuram hexasulfide), accelerator ZDC (zinc diethyldithiocarbamate), accelerator BZ (zinc dibutyldithiocarbamate), accelerator PZ (zinc dimethyldithiocarbamate), accelerator D (diphenyl guanidine), and the like.
The two-dimensional lamellar fillers of the invention are orderly arranged in any direction relative to the thickness of the thermal interface material.
The second purpose of the invention is to provide a preparation method of the thermal interface material, which comprises the following steps:
(1) Uniformly mixing a rubber matrix, a two-dimensional lamellar filler and 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ] to obtain a premix;
(2) Carrying out hot pressing or extrusion casting on the premix to prepare a film-like material;
(3) Stacking and welding the prepared film-shaped material to form a block;
(4) And cutting the block to obtain the thermal interface material.
In the preparation method of the thermal interface material, based on 100 parts by weight of the rubber matrix, the two-dimensional lamellar filler is 50-1000 parts, and the 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ] is 0.1-50 parts.
In the step (2), the processing temperature of the hot pressing or extrusion casting is 100 to 190 ℃, specifically, 100 ℃, 110 ℃, 120 ℃, 130 ℃,140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and the like.
In the step (2), the thickness of the film-like material is preferably 0.01 to 2mm.
In the step (3), the temperature of the stack welding is 150 to 190 ℃, specifically 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and the like.
In the step (4), the block material can be cut in any direction, and the thermal interface material with the adjustable orientation direction of the two-dimensional lamellar filler is obtained.
The thermal interface material can form a microstructure similar to a shell pearl layer, and the two-dimensional filler is arranged perpendicular to the thickness direction of the thermal interface material.
The invention has the following advantages:
1. after the series of formulas are subjected to hot pressing and tape casting, the compound ceramic has good repeated processing performance, the repairing efficiency can reach 98% after secondary processing, and the mechanical performance is almost the same as that of the compound ceramic during primary processing.
2. Compared with other preparation methods, the preparation method provided by the invention can be beneficial to realizing large-scale preparation of the existing polymer processing equipment, namely, can realize larger productivity.
3. The heat-conducting gasket prepared by the method of the invention has a microstructure with regular longitudinal arrangement of two-dimensional fillers; the macroscopic performance has extremely high heat conductivity coefficient in the vertical direction; in practical applications, the heat dissipation effect is far from that of commercially available TIM.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a vertically oriented thermal interface material according to the present invention.
FIG. 2 is a graph showing stress-strain curves before and after the repetition of the process of preparation example 1.
FIG. 3 is an electron microscopic view of the thermal interface material prepared in comparative example 1.
FIG. 4 is an electron micrograph of the thermal interface material prepared in example 7.
Fig. 5 is XRD data for different parts of two-dimensional boron nitride sheets and thicknesses of thermal interface materials for comparative example 1 and example 7.
Fig. 6 is a comparison of thermal conductivity coefficients of example 7 and comparative example 1.
In fig. 6, the thermal conductivity coefficients of example 7 and comparative example 1 were compared with that based on the thermal conductivity (λ (BR) =0.2W/mK) of the matrix butadiene rubber.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not known to the manufacturer and are available either directly or prepared according to the preparation methods disclosed in the prior art.
BDB was obtained by stirring p-diphenylboric acid (3.0 g,18.1 mmol) and thioglycerol (4.0 g,37.1 mmol) at room temperature for 24 hours.
The invention provides a preparation method of a TIM (TIM) for preparing a two-dimensional filler vertical curve with a shell-like pearl layer structure based on the characteristic that a TIM can be repeatedly processed after BDB crosslinking.
According to a preferred embodiment of the present invention, the preparation method comprises:
(1) the rubber matrix, the two-dimensional lamellar heat conducting filler and BDB are uniformly mixed by a common polymer mixing method, such as: mixing an open mill, an internal mixer, double planetary stirring and the like to obtain a TIM premix;
(2) carrying out high-temperature hot pressing or high-temperature extrusion casting on the premix at 100-190 ℃ to prepare a film-shaped material with the thickness of 0.01-2 mm, wherein the two-dimensional filler can be highly oriented in the film in the step, and the orientation direction is parallel to the surface of the film;
(3) stacking and welding the prepared film material at 150-190 ℃ to form a block with higher thickness;
(4) the bulk material is slit longitudinally in a specific direction to obtain a vertically oriented TIM.
The preparation process is shown in figure 1.
Example 1
100 parts of silicone rubber, 50 parts of two-dimensional boron nitride and 0.1 part of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 100℃to obtain a film having a thickness of 0.01 mm. The films were stacked and welded at 150 c to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 2W/mK.
Example 2
100 parts of acrylate rubber, 1000 parts of two-dimensional graphene and 10 parts of BDB are uniformly mixed in an open mill. Then, extrusion casting was performed at 150℃to obtain a film having a thickness of 0.1 mm. The films were stacked and welded at 170 ℃ to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 50W/mK.
Example 3
100 parts of polyurethane rubber, 200 parts of two-dimensional crystalline flake graphite and 20 parts of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 100℃to obtain a film having a thickness of 2mm. The films were stacked and welded at 160 ℃ to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 15W/mK.
Example 4
100 parts of ethylene propylene rubber, 800 parts of two-dimensional zinc oxide and 1 part of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 100℃to obtain a film having a thickness of 1 mm. The films were stacked and welded at 180 ℃ to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 6W/mK.
Example 5
100 parts of butadiene rubber, 900 parts of two-dimensional alumina and 50 parts of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 120℃to obtain a film of 0.8mm thickness. The films were stacked and welded at 190 ℃ to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 7W/mK.
Example 6
100 parts of natural rubber, 500 parts of two-dimensional boron nitride and 5 parts of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 140℃to obtain a film of 0.2mm thickness. The films were stacked and welded at 150 c to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. The thermal conductivity of the prepared TIM in the vertical direction is 19W/mK.
Example 7
100 parts of butadiene rubber, two-dimensional boron nitride and 10 parts of BDB are uniformly mixed in an open mill. Wherein the actual amount of the two-dimensional boron nitride is 100, 150, 200, 250 and 300 parts. Then, it was hot-pressed at 140℃to obtain a film of 0.1mm thickness. The films were stacked and welded at 150 c to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler. 5 kinds of TIM with different two-dimensional boron nitride dosages are prepared, and the thermal conductivity coefficients in the vertical direction are 5.71W/mK, 6.46W/mK, 10.56W/mK, 13.10W/mK and 15.34W/mK respectively.
According to the formula, hot pressing is carried out at 140 ℃ to respectively obtain films with the thickness of 0.01mm, 0.5mm, 1mm and 2mm, the films are stacked, and welding is carried out at 150 ℃ to form a complete block. And cutting the bulk material into TIM with required thickness, wherein the cutting direction is perpendicular to the orientation direction of the two-dimensional filler.
Preparation example 1
100 parts of butadiene rubber and 10 parts of BDB are uniformly mixed in an open mill. Then, it was hot-pressed at 170℃to obtain a 0.2mm thick one-time formed film. Cutting the once-formed film into 1cm 3 Then hot-pressed at 170 c to give a 0.2mm thick overmoulded film.
Comparative example 1
100 parts of butadiene rubber, two-dimensional boron nitride and 10 parts of BDB are uniformly mixed in an open mill. Wherein the actual amount of the two-dimensional boron nitride is 100, 150, 200, 250 and 300 parts. Vulcanization is carried out at 150 ℃. And cutting the vulcanized bulk material into TIM with the required thickness. The thermal conductivity of the TIM obtained by the preparation method is 1.83W/mK, 3.21W/mK, 3.47W/mK, 3.61W/mK and 3.81W/mK respectively. The thermal conductivity in the vertical and parallel directions is the same.
Claims (6)
1. The thermal interface material with the adjustable orientation direction of the two-dimensional lamellar filler is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
50-1000 parts of two-dimensional lamellar filler;
0.1-50 parts of 2,2' - (1, 4-phenylene) -bis [ 4-thiol-1, 3, 2-dioxybenzaldehyde ];
the rubber matrix is at least one selected from silicon rubber, acrylic rubber, polyurethane rubber, natural rubber, styrene-butadiene rubber, ethylene propylene rubber, chloroprene rubber, nitrile rubber, butyl rubber, isoprene rubber and styrene block copolymer; the two-dimensional lamellar filler is at least one selected from boron nitride, crystalline flake graphite, graphene, aluminum oxide, zinc oxide, diamond, lamellar silicon carbide, graphite-phase carbon nitride, graphene oxide, silver micrometer flakes, lamellar aluminum nitride, lamellar silver powder, lamellar aluminum powder and Mxene;
the thermal interface material is prepared by the following steps:
(1) Uniformly mixing a rubber matrix, a two-dimensional lamellar filler and 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ] to obtain a premix;
(2) Carrying out hot pressing or extrusion casting on the premix to prepare a film-like material;
(3) Stacking and welding the prepared film-shaped material to form a block;
(4) Cutting the block to obtain the thermal interface material;
wherein the processing temperature of the hot-pressing or extrusion casting is 100-190 ℃; the thickness of the film-shaped material is 0.01-2 mm.
2. The thermal interface material of claim 1, wherein the thermal interface material is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
50-800 parts of two-dimensional lamellar filler;
1-30 parts of 2,2' - (1, 4-phenylene) -bis [ 4-thiol-1, 3, 2-dioxybenzaldehyde ].
3. The thermal interface material of claim 2, wherein the thermal interface material is prepared from the following raw materials in parts by weight:
100 parts of a rubber matrix;
100-500 parts of two-dimensional lamellar filler;
1-20 parts of 2,2' - (1, 4-phenylene) -bis [ 4-thiol-1, 3, 2-dioxybenzaldehyde ].
4. A thermal interface material as defined in claim 1, wherein:
the two-dimensional lamellar filler has a lamellar diameter of 1 nm-100 mu m and a thickness of 0.1 nm-1 mu m.
5. A method of preparing a thermal interface material according to any one of claims 1-4, comprising the steps of:
(1) Uniformly mixing a rubber matrix, a two-dimensional lamellar filler and 2,2' - (1, 4-phenylene) -bis [ 4-mercaptan-1, 3, 2-dioxybenzaldehyde ] to obtain a premix;
(2) Carrying out hot pressing or extrusion casting on the premix to prepare a film-like material;
(3) Stacking and welding the prepared film-shaped material to form a block;
(4) Cutting the block to obtain the thermal interface material;
wherein the processing temperature of the hot-pressing or extrusion casting is 100-190 ℃; the thickness of the film-shaped material is 0.01-2 mm.
6. The method according to claim 5, wherein in the step (3):
the temperature of the stack welding is 150-190 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450857A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院青岛生物能源与过程研究所 | Composite graphite heat-conducting membrane material with controllable heat conductivity and preparation process thereof |
| CN108504016A (en) * | 2016-06-14 | 2018-09-07 | 络派模切（北京）有限公司 | A kind of heat-conducting pad and preparation method thereof |
| CN112812331A (en) * | 2021-01-12 | 2021-05-18 | 华南理工大学 | Heterogeneous cross-linked rubber, preparation method and recovery method |
| CN113248900A (en) * | 2021-05-20 | 2021-08-13 | 中山大学 | Dynamic bond crosslinking high-filling heat-conducting composite material and preparation method and application thereof |
| CN114536883A (en) * | 2022-01-26 | 2022-05-27 | 杭州热流新材料有限公司 | Preparation method of high-thermal-conductivity thick film with large-size graphene interface |
-
2022
- 2022-10-13 CN CN202211251308.4A patent/CN115716991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450857A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院青岛生物能源与过程研究所 | Composite graphite heat-conducting membrane material with controllable heat conductivity and preparation process thereof |
| CN108504016A (en) * | 2016-06-14 | 2018-09-07 | 络派模切（北京）有限公司 | A kind of heat-conducting pad and preparation method thereof |
| CN112812331A (en) * | 2021-01-12 | 2021-05-18 | 华南理工大学 | Heterogeneous cross-linked rubber, preparation method and recovery method |
| CN113248900A (en) * | 2021-05-20 | 2021-08-13 | 中山大学 | Dynamic bond crosslinking high-filling heat-conducting composite material and preparation method and application thereof |
| CN114536883A (en) * | 2022-01-26 | 2022-05-27 | 杭州热流新材料有限公司 | Preparation method of high-thermal-conductivity thick film with large-size graphene interface |
Non-Patent Citations (2)
| Title |
|---|
| "Uniaxial Stretching-Induced Alignment of Carbon Nanotubes in Cross-Linked Elastomer Enabled by Dynamic Cross-Link Reshuffling";Zhenghai Tang等;《ACS Macro Letters》(第8期);摘要、第1575、1576页、第1580页左栏、支持信息S1、S2页 * |
| "High thermal conductivity of self-healing polydimethylsiloxane elastomer composites by the orientation of boron nitride nano sheets";Zhihui Shang等;《Polymer Advanced Technologies》;第32卷;第4745-4754页 * |
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