CN113105735A - High-molecular polymer composite heat conduction material with high heat conduction and preparation method thereof - Google Patents
High-molecular polymer composite heat conduction material with high heat conduction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-molecular polymer composite heat conduction material with high heat conduction and a preparation method thereof, relates to the technical field of heat conduction materials, and is obtained by adding an Ag/MXene sheet composite material into a high-molecular polymer heat conduction material matrix; the invention also discloses a preparation method of the high-heat-conductivity high-molecular polymer composite heat-conducting material, which comprises the following steps: dispersing the Ag/MXene sheet composite material into an organic solvent, then adding the organic solvent into a polyurethane prepolymer, and heating, stirring and dispersing under a protective atmosphere; adding polyisocyanate and catalyst into the reaction system, heating, stirring for reaction, removing bubbles from the mixed material, pouring into a mould, and curing to obtain the product. The Ag nano particles and the two-dimensional MXene sheet material have synergistic effect in heat conduction performance, and the Ag/MXene sheet composite material is added into a high-molecular polymer heat conduction material matrix such as polyurethane and the like, so that the heat conduction performance of the material can be remarkably improved, and the Ag/MXene sheet composite material can be applied to electronic packaging materials; and the preparation method is effective and controllable, economic and environment-friendly.
Description
Technical Field
The invention relates to the technical field of heat conduction materials, in particular to a high-molecular polymer composite heat conduction material with high heat conduction and a preparation method thereof.
Background
With the rapid development of electronic integration technology, electronic components and electronic equipment are developing in the directions of smaller size, lighter weight, thinner thickness and the like, however, with the continuous increase of operating frequency, the electronic components inevitably generate a large amount of heat due to electric power loss, so that the operating temperature of the circuit of the electronic component is continuously increased, which leads to the failure of some components sensitive to temperature. Therefore, a problem to be solved is to develop a heat dissipation material with high thermal conductivity.
The traditional polymer material has the advantages of light weight, good processing performance, good electrical insulation performance, low cost and large-scale production, and is a good choice for preparing heat conduction materials. However, the polymer is a poor thermal conductor, and the conditions for constructing the structural heat-conducting polymer are very harsh, so that the industrial production is difficult to realize. In order to improve the thermal conductivity of polymers, the conventional researches mostly adopt that high-content (30-50 wt%) traditional thermal conductive fillers (such as graphene, carbon fiber, SiC and Al) are added into a polymer matrix2O3BN, etc.). The high-content heat-conducting filler can lead the modified composite high molecular material to be heavy in weight, and also reduce the excellent mechanical property of the polymer, and the high-content heat-conducting filler has poor compatibility with the polymer in the curing process, so that the high-content heat-conducting filler is difficult to uniformly disperse in a polymer matrix, and the heat-conducting property is not obviously improved. The polymer material has the problem of poor heat dissipation performance, and further application of the polymer material in electronic devices is hindered. Therefore, research on preparation of high-thermal-conductivity and ultralow-filler-load thermal conductive filler and polymer composite thereofThe material has important significance.
MXene, a novel two-dimensional transition metal carbide or nitride, has a graphene-like two-dimensional layered structure and is synthesized by selectively etching an Al atomic layer of MAX phase with HF. The chemical formula can be Mn+1XnTxWherein M is a transition metal, X is C or/and N, N is generally 1 to 3, and T isxRefers to surface groups (e.g., -OH, -F, -O, etc.). The graphene composite material has the characteristics of high specific surface area and high conductivity of graphene, has the advantages of flexible and adjustable components, controllable minimum nano-layer thickness and the like, and has great potential in the fields of energy storage, adsorption, sensors, conductive fillers and the like. Nowadays, MXene has less application in the field of heat conduction, and due to the excellent heat conduction performance of MXene and the existence of more functional groups on the surface of MXene, such as-F, -OH, -O and the like, MXene can have better compatibility with a high-molecular polymer matrix, can be used as an ideal filler of a high-heat-conduction polymer composite material, and the heat conduction performance of pure MXene is not ideal.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-heat-conductivity high-molecular polymer composite heat-conducting material and a preparation method thereof.
The invention provides a high-molecular polymer composite heat conduction material with high heat conduction, which is obtained by adding an Ag/MXene sheet composite material into a high-molecular polymer heat conduction material matrix.
Preferably, the addition amount of the Ag/MXene flake composite material is 0.1-2.2 wt% of the mass of the high polymer heat conduction material matrix; preferably, the mass percentage of Ag in the Ag/MXene flake composite material is 0.2-2.0 wt%.
Preferably, the preparation of the Ag/MXene flake composite material comprises the following steps:
s11, etching MAX phase Ti by HF solution3AlC2Powdering, washing and drying to obtain multilayer Ti3C2TxPowder;
s12, forming a multilayer Ti3C2TxAdding the powder into the intercalation solvent, stirring for reaction, washing to remove the intercalation solvent, and precipitatingDispersing the precipitate in deoxidized deionized water, ultrasonically dispersing under protective atmosphere, filtering, and drying to obtain Ti3C2TxA sheet;
s13, mixing Ti3C2TxFlake addition AgNO3Stirring the solution for reaction, centrifugally washing and drying to obtain the Ag/MXene flake composite material.
In step S13, the intercalation solvent may be removed by centrifugal washing with deionized water and ethanol.
Preferably, in S12, the intercalation solvent is any one of DMSO, DMF, TPAOH, NMP, preferably DMSO; preferably, in S12, the protective atmosphere is an argon atmosphere; preferably, in S13, the reaction is stirred at room temperature for 3-9 h.
In the invention, the intercalation solvent plays a role in stripping and layering, and can separate multiple layers of Ti3C2TxTi exfoliated in few layers3C2TxA sheet; DMSO is most effective in terms of intercalation efficiency and economy.
Preferably, the high molecular polymer heat conduction material matrix comprises one or more of polyurethane resin, epoxy resin, polyaniline, polyvinylidene fluoride, polystyrene and polypropylene; preferably, a polyurethane resin.
The invention also provides a preparation method of the high-heat-conductivity high-molecular polymer composite heat-conducting material, which comprises the following steps:
s21, dispersing the Ag/MXene flake composite material into an organic solvent, then adding the dispersed Ag/MXene flake composite material into hydroxyl-terminated polyester for a polyurethane prepolymer, and heating, stirring and dispersing under a protective atmosphere to obtain a material A;
s22, adding an isocyanate curing agent and a catalyst into the material A, heating, and stirring for reaction to obtain a material B;
and S23, vacuumizing the material B, removing bubbles, pouring into a mold, and curing to obtain the material B.
Preferably, in S21, under a protective atmosphere, the temperature is firstly increased to 55-65 ℃, stirring is carried out for 2.5-3.5 h, ultrasonic dispersion is carried out for 20-40 min, and then the temperature is increased to 75-85 ℃, and stirring is carried out for 22-26 h; preferably, in S22, the temperature is raised to 70-75 ℃, and the stirring reaction is carried out for 3-4 hours.
Preferably, the organic solvent is one or more of DMF, TOL, MEK; preferably, the catalyst is one of dibutyltin laurate and tin octylate; preferably, the hydroxyl-terminated polyester is one of hydroxyl-terminated polybutadiene and hydroxyl-terminated polypropylene; preferably, the isocyanate curing agent is one or more of toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, and tetramethylxylylene diisocyanate.
Preferably, the isocyanate curing agent is used in an amount of 0.8 to 1.2 wt% based on the weight of the hydroxyl-terminated polyester.
The invention also provides the application of the Ag/MXene sheet composite material in the high polymer composite heat conduction material, and the Ag/MXene sheet composite material is added into the high polymer heat conduction material matrix.
As MXene has weak reducibility, MXene can in-situ react with Ag in the stirring process+Reducing to Ag to obtain highly dispersed Ag nanoparticles tightly adhered to Ti3C2TxOn the sheet, highly dispersed Ag nanoparticles and Ti3C2TxThe thin sheets exert a synergistic heat-conducting effect, and on the other hand, Ag/Ti3C2TxThe abundant functional groups on the surface of the thin sheet enhance the compatibility with the high molecular polymer matrix precursor, so that the thin sheet and the high molecular polymer matrix precursor are combined more tightly, the thermal interface impedance between the thin sheet and the high molecular polymer matrix precursor is reduced, and the improvement of the thermal conductivity of the composite high molecular polymer matrix material is further promoted. It was found by experiment that Ag/MXene flakes achieve better thermal conductivity at lower levels (0.2-2.0 wt%). The Ag/MXene flake has a relatively great prospect in enhancing the heat conduction of the polymer and is expected to become a good nano heat-conducting filler in the future.
Has the advantages that: the invention provides a novel polymer heat conduction material with good heat conductivity, which is prepared by adding an Ag/MXene sheet composite material into a high polymer heat conduction material matrix such as polyurethane and the like to prepare a high heat conduction polymer heat conduction material. In the preparation of the Ag/MXene sheet composite material, the self-reduction and uniform dispersion of Ag nanoparticles at the edge of the MXene two-dimensional material can be realized by utilizing the self-reduction property of the MXene and the unique chemical structure of the edge of the MXene, and the MXene is more easily and uniformly dispersed in a matrix material and can form a stable interface structure with a polymer matrix due to the existence of rich functional groups such as OH, O, F and the like on the surface of the MXene material, so that the heat conductivity of the polymer material can be improved. The method is simple and convenient to operate, effective and controllable, economical, environment-friendly and excellent in heat-conducting property, and can be applied to electronic packaging materials.
Drawings
FIG. 1 shows Ti prepared in example 1 of the present invention3C2TxSEM images of the flakes;
fig. 2 is a graph of the thermal conductivity of Ag/MXene flakes/polyurethane composites prepared in examples 4-14 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparation of Ag/MXene sheet composite material
S1, weighing a certain amount of Ti3AlC2(MAX) powder is slowly added into a polytetrafluoroethylene beaker filled with 50ml of HF solution with the mass fraction of 40%, the polytetrafluoroethylene beaker is heated, stirred and etched for 24 hours at the water bath temperature of 60 ℃, deionized water is used for centrifugal washing after etching is finished until the PH of the solution is 6, the centrifugal powder is dried for 24 hours in vacuum at the temperature of 60 ℃, and multilayer Ti is obtained3C2Tx(MXene) powder;
s2, taking 2g of multilayer Ti3C2TxAdding the powder into 30ml dimethyl sulfoxide (DMSO) solution, stirring at room temperature for 24 hr, repeatedly centrifuging with deionized water and ethanol to remove DMSO solvent to obtain pasty precipitate, dispersing the precipitate in deoxidized deionized water, protecting with flowing argon gas, and ultrasonic cleaningUltrasonic dispersing in a container, performing suction filtration on the ultrasonic suspension by using a Polytetrafluoroethylene (PVDF) membrane, and performing suction filtration to obtain Ti3C2TxDrying the colloid at 60 deg.C for 12h to obtain Ti3C2TxA sheet;
s3, weighing a certain amount of AgNO3Dissolving in 50ml deionized water to obtain AgNO3Solution of 1g of Ti3C2TxFlakes were slowly added to the AgNO3Stirring the solution at room temperature for 6h, and centrifuging and washing to remove excessive Ag+Finally, the washed product is dried in a vacuum drying oven at 60 ℃ for 24 hours to obtain Ag/Ti with the Ag content of 1.0wt percent3C2TxA sheet composite.
Example 2
Preparation of Ag/MXene sheet composite material
Compared with the embodiment 1, the difference is only that S3 is different, and the rest are the same, specifically: s3, weighing a certain amount of AgNO3Dissolving in 50ml deionized water to obtain AgNO3Solution of 1g of Ti3C2TxFlakes were slowly added to the AgNO3Stirring the solution at room temperature for 3h, and centrifuging and washing to remove excessive Ag+Finally, the washed product is dried in a vacuum drying oven at 60 ℃ for 24 hours to obtain Ag/Ti with the Ag content of 0.2wt percent3C2TxA sheet composite.
Example 3
Preparation of Ag/MXene sheet composite material
Compared with the embodiment 1, the difference is only that S3 is different, and the rest are the same, specifically: s3, weighing a certain amount of AgNO3Dissolving in 50ml deionized water to obtain AgNO3Solution of 1g of Ti3C2TxFlakes were slowly added to the AgNO3Stirring the solution at room temperature for 9h, and centrifuging and washing to remove excessive Ag+Finally, the washed product is dried in a vacuum drying oven at 60 ℃ for 24 hours to obtain Ag/Ti with the Ag content of 2.0wt percent3C2TxA sheet composite.
Example 4
Preparation of Ag/MXene sheet/polyurethane composite material
S1, weighing a certain amount of the Ag/MXene sheet composite material prepared in the example 1 (the addition amount is 0.2 wt% of the hydroxyl-terminated polyester for the HTPB prepolymer), dispersing the Ag/MXene sheet composite material in 10ml of N, N-Dimethylformamide (DMF), adding the mixture into 20g of hydroxyl-terminated polybutadiene (HTPB prepolymer), and mechanically stirring for 3 hours at 60 ℃, ultrasonically dispersing for 30 minutes and stirring for 24 hours at 80 ℃ in a nitrogen atmosphere to obtain an Ag/MXene/HTPB prepolymer mixed system;
s2, adding a curing agent TDI accounting for 1.0% of hydroxyl-terminated polybutadiene HTPB into the mixed system of S1, heating and stirring for 3 hours at 75 ℃, uniformly mixing, removing bubbles in vacuum, pouring the mixture into a mold, and curing for 36 hours at 70 ℃ to obtain the high-performance polyester adhesive.
Example 5
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 0.4 wt%.
Example 6
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 0.6 wt%.
Example 7
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 0.8 wt%.
Example 8
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 1.0 wt%.
Example 9
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 1.2 wt%.
Example 10
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 1.4 wt%.
Example 11
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 1.6 wt%.
Example 12
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 1.8 wt%.
Example 13
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 2.0 wt%.
Example 14
Preparation of Ag/MXene sheet/polyurethane composite material with high thermal conductivity
Compared with the embodiment 4, the difference is only that S1 is different, and the rest are the same, specifically: the amount of Ag/MXene flake composite added in S1 was 2.2 wt%.
Example 15
Preparation of high-thermal-conductivity Ag/MXene sheet/polyvinylidene fluoride composite material
Preparing the composite material by a solvent method: an appropriate amount of polyvinylidene fluoride (PVDF) powder was weighed and placed in a beaker. Adding a proper amount of DMF into a test tube, and stirring at 60 ℃ to dissolve PVDF to obtain a solution A. The appropriate amount of Ag/Ti prepared in example 1 was taken3C2TxPutting the sheet composite material into a beaker, adding DMF, ultrasonically stirring at room temperature for 24 hours, and mixing the obtained suspension B with the solution A. Continuously stirring for 30min at 60 ℃, heating to 120 ℃, stirring to volatilize most of solvent, taking out the composite material at the bottom of the beaker, putting the composite material into a blast oven to dry for 24h at 60 ℃, and then drying in a vacuum oven for about 24h at 120 ℃ in vacuum to obtain Ag/Ti3C2TxAg// Ti with flake content of 1.0 wt%3C2TxA sheet/polyvinylidene fluoride composite.
Example 16
Preparation of high-thermal-conductivity Ag/MXene sheet/epoxy resin composite material
S1, adding neodymium acetylacetonate Nd (III) acac into epoxy resin, wherein the weight ratio is 1: 1000(Nd (III) acac: epoxy resin), to give a solution A, stirred at 80 ℃ for 3 hours and subsequently cooled to room temperature.
S2 taking a proper amount of Ag/Ti prepared in example 13C2TxThe flake composite material was added to a certain amount of ethanol and sonicated for 1h to form a uniformly dispersed suspension B. Solution A was added to suspension B and stirred at 80 ℃ for 6 h. Subsequently, curing agent 3, 4-dimethoxyaniline was added to the mixture in a weight ratio of 95: 100 (curing agent: mixture), stirring for 30 min. Vacuum drying at 50 deg.C for 2 hr, pouring the mixture onto a mold, pre-curing in a 135 deg.C oven for 2 hr, heating to 165 deg.C, maintaining for 14 hr to obtain Ag/Ti3C2TxAg/Ti with flake composite material content of 1.0 wt%3C2TxA sheet/epoxy composite.
Comparative example 1
Preparation of polyurethane composite material
S1, weighing 20g of hydroxyl-terminated polybutadiene, adding the hydroxyl-terminated polybutadiene into 10ml of N, N-Dimethylformamide (DMF), mechanically stirring for 3h at 60 ℃ in a nitrogen atmosphere, ultrasonically dispersing for 30min, and stirring for 24h at 80 ℃ to obtain an HTPB prepolymer solution;
s2, adding a curing agent TDI accounting for 1.0% of hydroxyl-terminated polybutadiene HTPB into the mixed system of S1, heating and stirring for 3 hours at 75 ℃, uniformly mixing, removing bubbles in vacuum, pouring the mixture into a mold, and curing for 36 hours at 70 ℃ to obtain the high-performance polyester adhesive.
Comparative example 2
Preparation of Ag/polyurethane composite material
Compared with the embodiment 8, the difference is only that S1 is different, and the rest are the same, specifically:
s1, weighing a certain amount of Ag powder (the adding amount is 1.0 wt% of the hydroxyl-terminated polyester for the HTPB prepolymer), dispersing the Ag powder in 10ml of N, N-Dimethylformamide (DMF), adding the mixture into 20g of hydroxyl-terminated polybutadiene, mechanically stirring for 3h at 60 ℃ under a nitrogen atmosphere, ultrasonically dispersing for 30min, and stirring for 24h at 80 ℃ to obtain an Ag/HTPB prepolymer mixed system.
Comparative example 3
Preparation of Ag/MXene composite material
Compared with the embodiment 1, the difference is that S2-S3 are different, and the rest are the same, specifically:
s2, weighing a certain amount of AgNO3Dissolving in 50ml deionized water to obtain AgNO3Solution of 1g of a multi-layer Ti3C2TxPowder slowly added to the AgNO3Stirring the solution at room temperature for 3h, and centrifuging and washing to remove excessive Ag+Finally, the washed product is dried in a vacuum drying oven at 60 ℃ for 24 hours to obtain Ag/Ti with the Ag content of 1.0wt percent3C2TxA composite material.
Comparative example 4
Preparation of Ag/MXene/polyurethane composite material
Compared with the embodiment 8, the difference is only that S1 is different, and the rest are the same, specifically:
s1, weighing a certain amount of the Ag/MXene composite material prepared in the comparative example 3 (the addition amount is 1.0 wt% of the hydroxyl-terminated polyester for the HTPB prepolymer), dispersing the Ag/MXene composite material in 10ml of N, N-Dimethylformamide (DMF), adding the mixture into 20g of hydroxyl-terminated polybutadiene (HTPB), and mechanically stirring for 3 hours at 60 ℃, ultrasonically dispersing for 30 minutes and stirring for 24 hours at 80 ℃ in a nitrogen atmosphere to obtain an Ag/MXene/HTPB prepolymer mixed system.
For Ti prepared in the invention of example 13C2TxThe flakes were characterized and the results are shown in FIG. 1. As can be seen from fig. 1, the interlayer spacing of the multiple layers of MXene is obviously increased by adding DMSO intercalator into the multiple layers of MXene, and finally the MXene flakes are obtained by ultrasonic stripping.
The results of examining the thermal conductivity of examples 4 to 16 of the present invention and comparative examples 1, 2 and 4 are shown in FIG. 2 and Table 1.
As can be seen from FIG. 2 and Table 1, the intrinsic thermal conductivity in the x-y direction of the MXene sheets is in the range of tens to hundreds of W/(m.K), while the intrinsic thermal conductivity in the z direction between the MXene sheets is less than 3X 10-6W/(m.K), so the heat conductivity of the Ag/MXene sheet to the polymer matrix is obviously improved more than that of the Ag/MXene sheet. Due to the synergistic effect of the Ag nano particles and the MXene flakes, the heat conduction effect of the Ag/MXene serving as a filler on a high polymer matrix is enhanced most obviously. And with the increase of the addition amount of the Ag/MXene flake filler, the thermal conductivity, namely the thermal conductivity of the Ag/MXene flake/polyurethane composite material shows a tendency of gradually increasing, but when the addition amount of the filler is more than 1.0 wt%, the increase amplitude of the thermal conductivity gradually decreases, and when the addition amount reaches 2.2%, the thermal conductivity reaches the best value, but because the cost of the filler is generally higher, the addition amount of 1.0 wt% is taken as the best value.
The Ag/MXene flake surface functional groups have good compatibility with matrix polyurethane, thereby reducing the thermal interface impedance between the Ag/MXene flake surface functional groups and the matrix polyurethane.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The high-heat-conductivity high-molecular polymer composite heat conduction material is characterized in that the high-heat-conductivity high-molecular polymer composite heat conduction material is obtained by adding an Ag/MXene sheet composite material into a high-molecular polymer heat conduction material matrix.
2. The high-heat-conductivity high-molecular polymer composite heat-conducting material according to claim 1, wherein the addition amount of the Ag/MXene sheet composite material is 0.1-2.2 wt% of the mass of the high-molecular polymer heat-conducting material matrix; preferably, the mass percentage of Ag in the Ag/MXene flake composite material is 0.2-2.0 wt%.
3. The high-thermal-conductivity high-molecular polymer composite thermal conductive material according to claim 2, wherein the preparation of the Ag/MXene flake composite material comprises the following steps:
s11, etching MAX phase Ti by HF solution3AlC2Powdering, washing and drying to obtain multilayer Ti3C2TxPowder;
s12, forming a multilayer Ti3C2TxAdding the powder into an intercalation solvent, stirring for reaction, washing to remove the intercalation solvent, dispersing the precipitate in deoxidized deionized water, ultrasonically dispersing under a protective atmosphere, filtering, and drying to obtain Ti3C2TxA sheet;
s13, mixing Ti3C2TxFlake addition AgNO3Stirring the solution for reaction, centrifugally washing and drying to obtain the Ag/MXene flake composite material.
4. The high-molecular polymer composite heat conduction material with high heat conductivity of claim 3, wherein in S12, the intercalation solvent is any one of DMSO, DMF, TPAOH and NMP, preferably DMSO; preferably, in S12, the protective atmosphere is an argon atmosphere; preferably, in S13, the reaction is stirred at room temperature for 3-9 h.
5. The high-molecular-polymer composite heat conduction material with high heat conductivity of any one of claims 1 to 4, wherein the high-molecular-polymer heat conduction material matrix comprises one or more of polyurethane resin, epoxy resin, polyaniline, polyvinylidene fluoride, polystyrene and polypropylene; preferably, a polyurethane resin.
6. The preparation method of the high-thermal-conductivity high-molecular polymer composite thermal conductive material according to claim 5 is characterized by comprising the following steps:
s21, dispersing the Ag/MXene flake composite material into an organic solvent, then adding the dispersed Ag/MXene flake composite material into hydroxyl-terminated polyester for a polyurethane prepolymer, and heating, stirring and dispersing under a protective atmosphere to obtain a material A;
s22, adding an isocyanate curing agent and a catalyst into the material A, heating, and stirring for reaction to obtain a material B;
and S23, vacuumizing the material B, removing bubbles, pouring into a mold, and curing to obtain the material B.
7. The preparation method of the high-heat-conductivity high-molecular polymer composite heat-conducting material according to claim 6, wherein in S21, under a protective atmosphere, the temperature is raised to 55-65 ℃ and stirred for 2.5-3.5 h, ultrasonic dispersion is carried out for 20-40 min, and then the temperature is raised to 75-85 ℃ and stirred for 22-26 h; preferably, in S22, the temperature is raised to 70-75 ℃, and the stirring reaction is carried out for 3-4 hours.
8. The method for preparing high-molecular polymer composite heat-conductive material with high heat conductivity according to claim 6, wherein the organic solvent is one or more of DMF, TOL and MEK; preferably, the catalyst is one of dibutyltin laurate and tin octylate; preferably, the hydroxyl-terminated polyester is one of hydroxyl-terminated polybutadiene and hydroxyl-terminated polypropylene; preferably, the isocyanate curing agent is one or more of toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, and tetramethylxylylene diisocyanate.
9. The preparation method of the high-heat-conductivity high-molecular polymer composite heat-conducting material according to claim 6, wherein the amount of the isocyanate curing agent is 0.8-1.2 wt% of the weight of the hydroxyl-terminated polyester.
10. The application of the Ag/MXene sheet composite material in the high polymer composite heat conducting material is characterized in that the Ag/MXene sheet composite material is added into a high polymer heat conducting material matrix.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276513A (en) * | 2022-01-10 | 2022-04-05 | 北京理工大学 | Lightweight electromagnetic cloud damage airborne object and preparation method and application thereof |
| CN114573872A (en) * | 2022-03-02 | 2022-06-03 | 安徽大学 | Preparation method of thiophene ionic liquid modified MXene heat-conducting filler and heat-conducting composite material |
| CN114689218A (en) * | 2022-03-29 | 2022-07-01 | 合肥工业大学 | MXene/Ag composite structure material-based ionic mechanical sensor, and preparation method and application thereof |
| CN116063793A (en) * | 2023-02-28 | 2023-05-05 | 武汉金发科技有限公司 | Polyolefin composite material and preparation method and application thereof |
| CN116446177A (en) * | 2023-03-15 | 2023-07-18 | 天津工业大学 | Preparation method of MXene/metal nanoparticle multifunctional coating composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107058851A (en) * | 2016-12-29 | 2017-08-18 | 上海大学 | A kind of metal-base composites of two-dimensional slice Material reinforcement |
| CN109827945A (en) * | 2019-02-28 | 2019-05-31 | 合肥工业大学 | A kind of preparation method of high SERS activity Ag/MXene-Ti3C2 composite material |
| CN110628155A (en) * | 2019-09-27 | 2019-12-31 | 中国科学院深圳先进技术研究院 | MXene/metal composite aerogel, preparation method and application thereof, and thermal interface material comprising MXene/metal composite aerogel |
| CN110699568A (en) * | 2019-09-12 | 2020-01-17 | 安徽工业大学 | Shell-core structure MXene @ MAX composite contact reinforcing phase material and preparation method thereof |
| CN111250122A (en) * | 2020-01-23 | 2020-06-09 | 福建工程学院 | Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof |
| CN111809439A (en) * | 2020-06-30 | 2020-10-23 | 陕西科技大学 | Flexible high-strength MXene-based electromagnetic shielding composite film and preparation method thereof |
-
2021
- 2021-02-22 CN CN202110196519.1A patent/CN113105735B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107058851A (en) * | 2016-12-29 | 2017-08-18 | 上海大学 | A kind of metal-base composites of two-dimensional slice Material reinforcement |
| CN109827945A (en) * | 2019-02-28 | 2019-05-31 | 合肥工业大学 | A kind of preparation method of high SERS activity Ag/MXene-Ti3C2 composite material |
| CN110699568A (en) * | 2019-09-12 | 2020-01-17 | 安徽工业大学 | Shell-core structure MXene @ MAX composite contact reinforcing phase material and preparation method thereof |
| CN110628155A (en) * | 2019-09-27 | 2019-12-31 | 中国科学院深圳先进技术研究院 | MXene/metal composite aerogel, preparation method and application thereof, and thermal interface material comprising MXene/metal composite aerogel |
| CN111250122A (en) * | 2020-01-23 | 2020-06-09 | 福建工程学院 | Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof |
| CN111809439A (en) * | 2020-06-30 | 2020-10-23 | 陕西科技大学 | Flexible high-strength MXene-based electromagnetic shielding composite film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHANGZENG YAN ETC.: "Interconnecting the Promising MXenes via Ag Nanowire in Epoxy Nanocomposites for High-Performance Thermal Management Applications", 《2018 19TH INTERNATIONAL CONFERENCE ON ELECTRONIC PACKAGING TECHNOLOGY》 * |
| ELUMALAI SATHEESHKUMAR ETC.: "One-step Solution Processing of", 《SCIENTIFIC REPORTS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276513A (en) * | 2022-01-10 | 2022-04-05 | 北京理工大学 | Lightweight electromagnetic cloud damage airborne object and preparation method and application thereof |
| CN114276513B (en) * | 2022-01-10 | 2022-12-27 | 北京理工大学 | Lightweight electromagnetic cloud damage airborne object and preparation method and application thereof |
| CN114573872A (en) * | 2022-03-02 | 2022-06-03 | 安徽大学 | Preparation method of thiophene ionic liquid modified MXene heat-conducting filler and heat-conducting composite material |
| CN114573872B (en) * | 2022-03-02 | 2024-05-14 | 安徽大学 | Preparation method of thiophene ionic liquid modified MXene heat-conducting filler and heat-conducting composite material |
| CN114689218A (en) * | 2022-03-29 | 2022-07-01 | 合肥工业大学 | MXene/Ag composite structure material-based ionic mechanical sensor, and preparation method and application thereof |
| CN116063793A (en) * | 2023-02-28 | 2023-05-05 | 武汉金发科技有限公司 | Polyolefin composite material and preparation method and application thereof |
| CN116063793B (en) * | 2023-02-28 | 2024-03-12 | 武汉金发科技有限公司 | Polyolefin composite material and preparation method and application thereof |
| CN116446177A (en) * | 2023-03-15 | 2023-07-18 | 天津工业大学 | Preparation method of MXene/metal nanoparticle multifunctional coating composite material |
| CN116446177B (en) * | 2023-03-15 | 2024-05-28 | 天津工业大学 | Preparation method of MXene/metal nanoparticle multifunctional coating composite material |
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