CN114573872A - Preparation method of thiophene ionic liquid modified MXene heat-conducting filler and heat-conducting composite material - Google Patents
Preparation method of thiophene ionic liquid modified MXene heat-conducting filler and heat-conducting composite material Download PDFInfo
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- CN114573872A CN114573872A CN202210218696.XA CN202210218696A CN114573872A CN 114573872 A CN114573872 A CN 114573872A CN 202210218696 A CN202210218696 A CN 202210218696A CN 114573872 A CN114573872 A CN 114573872A
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 76
- 229930192474 thiophene Natural products 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000945 filler Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002033 PVDF binder Substances 0.000 claims abstract description 38
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- RFSKGCVUDQRZSD-UHFFFAOYSA-N 3-methoxythiophene Chemical compound COC=1C=CSC=1 RFSKGCVUDQRZSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 6
- ALSSUPAAWXPLMJ-UHFFFAOYSA-N 3-(2-bromoethoxy)thiophene Chemical compound BrCCOC=1C=CSC=1 ALSSUPAAWXPLMJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005893 bromination reaction Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 8
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- VYDVLDNLTSOBLM-UHFFFAOYSA-N 2-ethoxythiophene Chemical compound CCOC1=CC=CS1 VYDVLDNLTSOBLM-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011231 conductive filler Substances 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
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- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000017525 heat dissipation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
A preparation method of thiophene ionic liquid modified MXene heat-conducting filler and a heat-conducting composite material are disclosed, wherein the preparation method comprises the following steps: s100, taking 3-methoxythiophene as a raw material, carrying out bromination reaction to obtain 3- (2-bromo) ethoxythiophene, and carrying out charge reaction to obtain thiophene ionic liquid, which is marked as IL; s200, etching MAX by an in-situ hydrofluoric acid generation method, and then obtaining MXene nanosheets after centrifuging, washing and ultrasonic multiple circulating treatment; s300, blending and modifying the IL and the MXene nanosheets to obtain the thiophene ionic liquid modified MXene heat-conducting filler. According to the preparation method of the thiophene ionic liquid modified MXene heat-conducting filler and the heat-conducting composite material, the heat-conducting capacity is enhanced through hydrogen bonds formed between MXene and PVDF and between MXene and IL, and meanwhile, due to the addition of the thiophene ionic liquid, the compatibility between the filler and the base material of the heat-conducting composite material is improved, and the improvement of the heat-conducting performance of the heat-conducting composite material is further promoted.
Description
Technical Field
The invention relates to the field of heat-conducting polymer composite materials, in particular to a preparation method of a thiophene ionic liquid modified MXene heat-conducting filler and a heat-conducting composite material.
Background
At present, with the rapid development of various technologies, especially in the field of electronic products, the heat dissipation problem is closely related to the energy consumption and the service life of devices. Therefore, it is important to develop a lightweight heat conductive composite material. In precise electronic equipment, the research on the high-thermal-conductivity composite material is an effective method for helping to solve the problem of accuracy of an equipment operation result and service life of the electronic equipment caused by heat accumulation of the electronic equipment, and the composite material can improve the thermal conductivity by constructing a thermal conduction path and reducing interface thermal resistance. The polymer-based composite material has relatively strong mechanical properties and can become a good choice for a thermal management material in an electronic device. The interfacial thermal resistance between the filler and the substrate or between the filler and the filler can be controlled by modifications to the substrate and the filler. The modification can be divided into covalent modification and non-covalent modification, the covalent modification can damage the self structure of the material, the modifier can be connected to the material by the formation of chemical bonds, but the heat conductivity can be influenced to a certain extent; the non-covalent modification can achieve the effect similar to the covalent modification on the premise of ensuring that the structure of the material is not damaged, such as the formation of non-covalent bonds through hydrogen bond interaction, pi-pi interaction and the like. The non-covalent modification can modify the material itself or reduce the interface thermal resistance. Therefore, in the field of heat-conducting polymer composite materials, the problem of controlling the thermal interface resistance between the filler and the base material or between the filler and the filler through the modification of the base material and the filler is an important subject of current research, and further research is urgently needed.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a thiophene ionic liquid modified MXene heat-conducting filler and a heat-conducting composite material.
In order to achieve the purpose, the invention provides a preparation method of a thiophene ionic liquid modified MXene heat-conducting filler, which comprises the following steps:
s100, taking 3-methoxythiophene as a raw material, carrying out bromination reaction to obtain 3- (2-bromo) ethoxythiophene, and carrying out charge reaction to obtain thiophene ionic liquid, which is marked as IL;
s200, etching titanium aluminum carbide by an in-situ hydrofluoric acid generation method, and performing centrifugation, washing and ultrasonic multiple cycle treatment to obtain MXene nanosheets;
s300, blending and modifying the thiophene ionic liquid and the MXene nanosheets to obtain the thiophene ionic liquid modified MXene heat-conducting filler, which is marked as MXene @ IL.
As a further preferable technical solution of the present invention, the step S100 specifically includes the steps of:
s101, under the condition of nitrogen purging, taking 3-methoxythiophene, toluene, bromoethanol and sodium bisulfate, mixing and adding into a reaction container, then placing into an oil bath pot, and magnetically stirring at the temperature of 100-115 ℃ for 10-15h for reaction, wherein the dosage of the corresponding toluene is 20-30ml, the dosage of the bromoethanol is 20-30mmol, and the dosage of the sodium bisulfate is 200-300mg on the basis of the dosage of each 10mmol 3-methoxythiophene;
s102, after the reaction in the step S101 is finished, cooling the reactant to room temperature, washing with deionized water, separating with a separating funnel, collecting the water phase, circulating for at least three times, extracting the water phase with diethyl ether, and separating the extracted water phase with the separating funnel to finally obtain an organic phase;
s103, adding anhydrous magnesium sulfate into the organic phase for dewatering, standing for 8-12h, pouring out the organic phase, distilling under reduced pressure by using a rotary evaporator to remove a solvent and unreacted bromoethanol, separating and purifying by using a silica gel chromatographic column by using petroleum ether as an eluent, and finally performing rotary evaporation to obtain a colorless transparent solid which is 3- (2-bromo) ethoxythiophene;
s104, under the protection of nitrogen, adding 3- (2-bromine) ethoxy thiophene, N-methylimidazole and acetonitrile into a reaction container, and stirring and reacting for 2-5 days at the temperature of 60-80 ℃ in an oil bath kettle, wherein the dosage of each 1mmol of 3- (2-bromine) ethoxy thiophene is 1.5-2.5mmol, and the dosage of acetonitrile is 10-15 ml;
and S105, after the stirring reaction in the step S104 is finished, reducing the temperature of the product to room temperature, performing reduced pressure distillation through a rotary evaporator, removing the solvent, repeatedly washing the product subjected to reduced pressure distillation in a detergent prepared by mixing petroleum ether and ethyl acetate, and finally obtaining the washed product which is the thiophene ionic liquid.
In a further preferred embodiment of the present invention, in step S102, the amount of deionized water is 20 to 40ml and the amount of diethyl ether is 20 to 40ml based on the amount of 3-methoxythiophene per 10mmol in step S101 in each washing and extraction.
In a further preferred embodiment of the present invention, the detergent in step S105 is prepared by mixing petroleum ether and ethyl acetate at a ratio of 2:1 to 6: 1.
As a further preferable technical solution of the present invention, the step S200 specifically includes the steps of:
s201, slowly adding titanium aluminum carbide into an etching agent, continuing stirring for 8-15 minutes after the titanium aluminum carbide is completely added, then placing the mixture into an oil bath kettle, magnetically stirring and reacting for 18-24 hours at 35-45 ℃, wherein the stirring speed is 600-750 revolutions per minute, the etching agent is prepared by mixing a hydrochloric acid solution and lithium fluoride, and the amount of the titanium aluminum carbide in each 1g corresponds to 1-1.6g of the lithium fluoride in the etching agent;
s202, after the reaction in the step S201 is finished, extracting reactants, and centrifugally washing the reactants twice by using hydrochloric acid at a centrifugal rotation speed of 3200-3600 revolutions per minute to wash away unreacted lithium fluoride and salts generated in the etching process;
s203, performing ultrasonic treatment on the product after the acid washing in the step S202 for 6-12 minutes in an ice bath, performing centrifugal washing by using deionized water, circulating for multiple times until the pH value of the centrifuged supernatant is greater than 6, continuing centrifuging at the rotating speed of 300 revolutions per minute, taking the supernatant, continuing centrifuging the obtained supernatant at the rotating speed of 8000 revolutions per minute, and then taking the precipitate for freeze drying for 15-24 hours to obtain the MXene nanosheet.
As a further preferable technical scheme of the invention, the concentration of the hydrochloric acid solution for preparing the etching agent in the step S201 is 9 mol/L.
As a further preferable technical solution of the present invention, the step S300 specifically includes the steps of:
s301, adding thiophene ionic liquid into deionized water, and stirring to obtain an IL aqueous solution, wherein the amount of thiophene ionic liquid per 0.5g corresponds to 50-100ml of deionized water;
s302, slowly adding MXene nano-sheets into the aqueous solution of all IL obtained in the step S301, carrying out ice bath ultrasonic treatment for 8-10 minutes, and then carrying out magnetic stirring at room temperature for 15-24 hours, wherein the mass ratio of the MXene nano-amount to the thiophene ionic liquid in the step S301 is 1:1-1: 2;
and S303, after the magnetic stirring is finished, washing with deionized water for at least two times to remove redundant thiophene ionic liquid, then carrying out suction filtration and separation, and finally carrying out freeze drying for 12-24 hours to obtain the thiophene ionic liquid modified MXene heat-conducting filler.
According to another aspect of the present invention, the present invention further provides a thermal conductive composite material, wherein the thermal conductive composite material is prepared by adding the thiophene ionic liquid modified MXene thermal conductive filler prepared by the thiophene ionic liquid modified MXene thermal conductive filler preparation method according to any one of claims 1 to 6 to a PVDF solution to compound the thiophene ionic liquid modified MXene thermal conductive filler.
As a further preferable technical scheme of the invention, the thiophene ionic liquid modified MXene heat-conducting filler is added into a PVDF solution to be compounded to obtain the heat-conducting composite material, and the method specifically comprises the following steps:
adding the thiophene ionic liquid modified MXene heat-conducting filler into the PVDF solution, wherein the mass ratio of the thiophene ionic liquid modified MXene heat-conducting filler to the PVDF in the PVDF solution is 0.001:1-0.25:1, uniformly stirring and dispersing, then carrying out vacuum drying at 60-80 ℃, and finally carrying out hot pressing at 185 ℃ to obtain the heat-conducting composite material.
As a further preferable technical scheme of the invention, the PVDF solution is obtained by adding PVDF particles into a DMF solvent and stirring at 50-60 ℃.
The preparation method of the thiophene ionic liquid modified MXene heat-conducting filler and the heat-conducting composite material can achieve the following beneficial effects by adopting the technical scheme:
1) the heat-conducting composite material has the advantages that the heat-conducting capacity is enhanced through hydrogen bonds formed between MXene and PVDF and between MXene and IL, and meanwhile, due to the addition of the thiophene ionic liquid, the compatibility between the filler (MXene @ IL) and the base material (PVDF) of the heat-conducting composite material is improved, so that the improvement of the heat-conducting performance of the heat-conducting composite material is promoted;
2) according to the invention, the thiophene ionic liquid and MXene nanosheet are blended and modified, and the MXene is subjected to non-covalent modification, so that compared with covalent modification, the operation is convenient and fast, one-step organic reaction is not required to be carried out, and the solvent used in the step of modifying the MXene by the thiophene ionic liquid is deionized water, so that the use of the organic solvent is reduced, and meanwhile, the non-covalent modification does not need to damage the structure of the MXene.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic diagram of the synthesis scheme of thiophene Ionic Liquid (IL) in example 1 of the present invention;
FIG. 2 is a TEM image and mapping image of S, N of MXene @ IL of example 1, wherein (a) is MXene @ IL, (b) is a mapping image of N, and (c) is a mapping image of S;
FIG. 3 is a local infrared spectrum of MXene @ IL of example 1 of the present invention;
fig. 4 is a graph comparing thermal conductivities of the products of examples 1-3 of the present invention and comparative examples 1-3.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
The invention provides a preparation method of a thiophene ionic liquid modified MXene heat-conducting filler and a heat-conducting composite material, and aims to use thiophene ionic liquid obtained after thiophene is subjected to charge as a micromolecular modifier to modify MXene, uniformly mix PVDF (also called polyvinylidene fluoride) and MXene @ IL by a solution blending method, and prepare the heat-conducting composite material by a hot pressing method. A heat conduction path is constructed in the composite material by utilizing a hot pressing method, so that the heat conduction capability is enhanced due to the hydrogen bond effect formed between MXene and PVDF and between MXene and IL, and meanwhile, the compatibility between the filler and the base material is improved due to the formation of the hydrogen bond, so that the heat conduction performance of the polymer composite material is improved.
In order to further understand the technical scheme of the invention, the invention is further explained in detail by the specific implementation method.
Comparative example 1
This comparative example 5 wt% MXene/PVDF composite was prepared as follows
Step 1, preparing MXene nano-sheets.
Step 1.1, adding 5ml of deionized water and 15ml of 12M hydrochloric acid into a polytetrafluoroethylene lining to prepare 9M hydrochloric acid solution, then weighing 1.6g of lithium fluoride, slowly adding the lithium fluoride into the polytetrafluoroethylene lining, and stirring for 30 minutes to obtain an etching agent;
step 1.2, weighing 1g of MAX, slowly adding the MAX into the polytetrafluoroethylene lining, adding the MAX a little at a time when no bubbles exist in the lining, continuously stirring for 10 minutes after the MAX is completely added, placing the MAX into an oil bath pot, reacting for 24 hours at 40 ℃, and reacting at a magnetic stirring speed of about 700 revolutions per minute;
step 1.3, after the reaction is finished, preparing 1M hydrochloric acid solution, centrifugally washing the product for 3 times at a rotating speed of 3500 revolutions per minute, and washing away unreacted lithium fluoride and salt generated in the etching process by acid;
and 1.4, after acid washing, carrying out ice bath ultrasonic treatment for 10 minutes, firstly washing with deionized water and centrifuging, carrying out ice bath ultrasonic treatment again, circulating for multiple times until the pH value of the centrifuged supernatant is greater than 6, finally centrifuging at the rotating speed of 300 revolutions per minute, taking the supernatant, centrifuging the obtained supernatant at the rotating speed of 8000 revolutions per minute, and taking the precipitate to freeze and dry for 24 hours to obtain the MXene nanosheet.
And 2, preparing the MXene/PVDF composite material.
Step 2.1, adding 10ml of DMF (also called N, N-dimethylformamide) into a 25ml glass bottle, weighing 1g of PVDF, adding the PVDF, heating and stirring at 60 ℃ to obtain a uniform PVDF solution;
and 2.2, adding 0.05g of MXene nanosheets into the PVDF solution, stirring and uniformly dispersing at room temperature to obtain a mixed solution, and finally, carrying out vacuum drying and hot pressing on the mixed solution at 70 ℃ to obtain the MXene/PVDF composite material.
Comparative example 2
This comparative example 15 wt% MXene/PVDF composite was prepared according to the same procedure as comparative example 1, except that in step 2: the amount of MXene nanosheet was 0.15 g.
Comparative example 3
This comparative example a 25 wt% MXene/PVDF composite was prepared following the same procedure as comparative example 1, except that in step 2: the amount of MXene nanosheets used was 0.25 g.
Example 1
This example prepares a 5 wt% MXene @ IL/PVDF composite as follows:
step 1, preparing 3- (2-bromine) ethoxy thiophene.
Step 1.1, under the condition of nitrogen purging, adding 25ml of toluene, 12.62mmol of 3-methoxythiophene, 27.74mmol of bromoethanol and 288.3mg of sodium bisulfate into a 50ml three-neck flask in sequence, then placing the three-neck flask into an oil bath kettle, magnetically stirring the three-neck flask at 105 ℃ for 10 hours to perform reaction, and observing the color of the system to change from light color to reddish brown and finally to be blackish brown along with the reaction;
step 1.2, after the reaction is finished, cooling the reactant to room temperature, washing with deionized water, separating by using a separating funnel, collecting the water phase, circulating for three times, extracting the water phase by using diethyl ether, extracting 30ml of diethyl ether each time, and separating by using the separating funnel to obtain an organic phase;
and step 1.3, adding anhydrous magnesium sulfate into the organic phase for dewatering, standing for 12 hours, pouring out the organic phase, removing the solvent and unreacted bromoethanol through reduced pressure distillation by a rotary evaporator, then realizing separation and purification of a silica gel chromatographic column by using petroleum ether as an eluent, judging the product point through a point plate, and finally performing rotary evaporation again to obtain a colorless transparent solid, namely 3- (2-bromine) ethoxythiophene.
And 2, synthesizing the thiophene ionic liquid.
Step 2.1, under the protection of nitrogen, adding 50ml of acetonitrile into a 100ml flask, sequentially adding 4.8mmol of 3- (2-bromine) ethoxy thiophene and 9.6mmol of N-methylimidazole, placing the mixture into an oil bath kettle, stirring the mixture for 3 days at 70 ℃ for reaction, wherein in the reaction process, the color can be seen to change, and the reaction system changes from colorless to orange;
after 2.2 days and 3 days, stopping the reaction, and after the temperature of the reactant is reduced to room temperature, carrying out reduced pressure distillation by a rotary evaporator to remove the solvent to obtain a product;
and 2.3, preparing a detergent from petroleum ether and ethyl acetate according to the ratio of 3:1, and repeatedly washing the product obtained in the step 2.2 by using the detergent to finally obtain thiophene ionic liquid, namely IL.
And 3, preparing the MXene nanosheet.
Step 3.1, adding 5ml of deionized water and 15ml of 12M hydrochloric acid into the polytetrafluoroethylene lining to prepare 9M hydrochloric acid solution, then weighing 1.6g of lithium fluoride, slowly adding the lithium fluoride into the polytetrafluoroethylene lining, and stirring for 30 minutes to obtain an etching agent;
step 3.2, weighing 1g of MAX (titanium carbide self-sown), slowly adding the weighed MAX into the polytetrafluoroethylene lining, adding the weighed MAX into the polytetrafluoroethylene lining a little at a time when no bubbles exist in the lining, continuously stirring for 10 minutes after the MAX is completely added, placing the obtained product into an oil bath pot, and carrying out magnetic stirring reaction for 24 hours at the temperature of 40 ℃, wherein the magnetic stirring speed is about 700 revolutions per minute;
step 3.2, after the reaction is finished, centrifugally washing the product for 3 times by 1M hydrochloric acid solution, wherein the centrifugal rotating speed is 3500 revolutions per minute, and washing out unreacted lithium fluoride and salt generated in the etching process by acid washing;
and 3.3, after acid washing, carrying out ultrasonic treatment on the mixed solution in an ice bath for 10 minutes, firstly carrying out centrifugal washing on the mixed solution by using deionized water, carrying out ultrasonic treatment on the mixed solution in an ice bath again, circulating the steps for multiple times until the pH value of the centrifuged supernatant is greater than 6, finally, centrifuging the centrifuged supernatant at a rotating speed of 300 revolutions per minute, taking the supernatant, centrifuging the obtained supernatant at a rotating speed of 8000 revolutions per minute, and then taking the precipitate for freeze drying for 24 hours to obtain the MXene nanosheet.
And 4, preparing the modified MXene nanosheets from the thiophene Ionic Liquid (IL).
Step 4.1, adding 0.5gIL into 100ml of deionized water, and stirring and dissolving to obtain an IL water solution;
step 4.2, slowly adding 0.5g of MXene nanosheets into an IL aqueous solution, carrying out ice bath ultrasonic treatment for 10 minutes to promote dispersion, and finally carrying out magnetic stirring reaction at room temperature for 24 hours;
and 4.3, washing the product of the stirring reaction with deionized water for three times to remove redundant IL, performing suction filtration separation, and freeze-drying for 24 hours to obtain the thiophene ionic liquid modified MXene heat-conducting filler, namely MXene @ IL.
And step 5, preparing the MXene @ IL/PVDF composite material.
Step 5.1, adding 10ml of DMF into a 25ml glass bottle, weighing 1g of PVDF, adding the PVDF, heating and stirring at 60 ℃ to obtain a uniform PVDF solution;
and step 5.2, adding 0.05g of MXene @ IL prepared in the step 4 into the PVDF solution, stirring and uniformly dispersing at room temperature to obtain a mixed solution, and finally carrying out vacuum drying on the mixed solution at 70 ℃ and then carrying out hot pressing to obtain the MXene @ IL/PVDF composite material.
The reaction mechanism of the thiophene ionic liquid in example 1 is shown in FIG. 1.
FIG. 2 is a TEM image of MXene modified by IL, wherein the flaky structure of MXene can be seen, and a mapping image of S, N elements can prove that IL is successfully grafted on the MXene surface. FIG. 3 is an infrared spectrum of IL modified MXene, and the red shift of-OH peak position can illustrate that hydrogen bonds are formed between the electrochemical-charged thiophene ionic liquid and MXene, and further proves that IL is connected on the MXene surface. Thus, the successful modification of MXene nanosheets by the thiophene ionic liquid disclosed by the invention can be proved.
Example 2
This example prepared 15 wt% MXene @ IL/PVDF composite in the same manner as in example 1, except that in step 5: MXene @ IL was used in an amount of 0.15 g.
Example 3
This example prepares a 25 wt% MXene @ IL/PVDF composite in the same manner as in example 1, except that in step 5: MXene @ IL was used in an amount of 0.25 g.
The thermal conductivity of the final products of comparative examples 1 to 3 and examples 1 to 3 was measured, and the results are shown in fig. 4, from which it can be seen that the thermal conductivity shows an increasing trend as the amount of the filler increases, because the heat conduction path is relatively dense as the amount of the filler increases; meanwhile, under the same filler amount, the thermal conductivity of the composite material prepared from the modified filler is obviously higher than that of the composite material prepared from the unmodified filler, which shows that the thiophene ionic liquid plays a good role in MXene interlayer and helps to form a heat conduction path.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. The preparation method of the thiophene ionic liquid modified MXene heat-conducting filler is characterized by comprising the following steps of:
s100, taking 3-methoxythiophene as a raw material, carrying out bromination reaction to obtain 3- (2-bromo) ethoxythiophene, and carrying out charge reaction to obtain thiophene ionic liquid;
s200, etching titanium aluminum carbide by an in-situ hydrofluoric acid generation method, and performing centrifugation, washing and ultrasonic multiple cycle treatment to obtain MXene nanosheets;
s300, blending and modifying the thiophene ionic liquid and the MXene nanosheets to obtain the thiophene ionic liquid modified MXene heat-conducting filler.
2. The method for preparing the thiophene ionic liquid modified MXene heat-conducting filler according to claim 1, wherein the step S100 specifically comprises the following steps:
s101, under the condition of nitrogen purging, taking 3-methoxythiophene, toluene, bromoethanol and sodium bisulfate, mixing and adding into a reaction container, then placing into an oil bath pot, and magnetically stirring at the temperature of 100-115 ℃ for 10-15h for reaction, wherein the dosage of the corresponding toluene is 20-30ml, the dosage of the bromoethanol is 20-30mmol, and the dosage of the sodium bisulfate is 200-300mg, based on the dosage of each 10mmol of 3-methoxythiophene;
s102, after the reaction in the step S101 is finished, cooling the reactant to room temperature, washing with deionized water, separating with a separating funnel, collecting the water phase, circulating for at least three times, extracting the water phase with diethyl ether, and separating the extracted water phase with the separating funnel to finally obtain an organic phase;
s103, adding anhydrous magnesium sulfate into the organic phase for dewatering, standing for 8-12h, pouring out the organic phase, distilling under reduced pressure by using a rotary evaporator to remove the solvent and unreacted bromoethanol, separating and purifying the silica gel chromatographic column by using petroleum ether as an eluent, and finally performing rotary evaporation to obtain a colorless transparent solid which is 3- (2-bromo) ethoxythiophene;
s104, under the protection of nitrogen, adding 3- (2-bromine) ethoxy thiophene, N-methylimidazole and acetonitrile into a reaction container, and stirring and reacting for 2-5 days at the temperature of 60-80 ℃ in an oil bath kettle, wherein the dosage of each 1mmol of 3- (2-bromine) ethoxy thiophene is 1.5-2.5mmol, and the dosage of acetonitrile is 10-15 ml;
and S105, after the stirring reaction in the step S104 is finished, reducing the temperature of the product to room temperature, performing reduced pressure distillation through a rotary evaporator, removing the solvent, repeatedly washing the product subjected to reduced pressure distillation in a detergent prepared by mixing petroleum ether and ethyl acetate, and finally obtaining the washed product which is the thiophene ionic liquid.
3. The method for preparing the thiophene ionic liquid modified MXene thermal conductive filler according to claim 2, wherein in step S102, the amount of deionized water is 20-40ml and the amount of diethyl ether is 20-40ml based on the amount of 3-methoxythiophene per 10mmol in step S101 in each washing and extraction.
4. The preparation method of the thiophene ionic liquid modified MXene heat-conducting filler according to claim 2, wherein the detergent in step S105 is prepared by mixing petroleum ether and ethyl acetate according to a ratio of 2: 1-6: 1.
5. The method for preparing the thiophene ionic liquid modified MXene thermally conductive filler according to claim 1, wherein the step S200 specifically comprises the following steps:
s201, slowly adding titanium aluminum carbide into an etching agent, continuing stirring for 8-15 minutes after the titanium aluminum carbide is completely added, then placing the mixture into an oil bath kettle, magnetically stirring and reacting for 18-24 hours at 35-45 ℃, wherein the stirring speed is 600-750 revolutions per minute, the etching agent is prepared by mixing a hydrochloric acid solution and lithium fluoride, and the amount of the titanium aluminum carbide in each 1g corresponds to 1-1.6g of the lithium fluoride in the etching agent;
s202, after the reaction in the step S201 is finished, extracting a reactant, and centrifugally washing the reactant at least twice by using hydrochloric acid at a centrifugal rotation speed of 3200-;
s203, performing ultrasonic treatment on the product after the acid washing in the step S202 for 6-12 minutes in an ice bath, performing centrifugal washing by using deionized water, circulating for multiple times until the pH value of the centrifuged supernatant is greater than 6, continuing centrifuging at the rotating speed of 300 revolutions per minute, taking the supernatant, continuing centrifuging the obtained supernatant at the rotating speed of 8000 revolutions per minute, and then taking the precipitate for freeze drying for 15-24 hours to obtain the MXene nanosheet.
6. The method for preparing the thiophene ionic liquid modified MXene thermal conductive filler according to claim 5, wherein the hydrochloric acid solution used for preparing the etchant in step S201 has a concentration of 9 mol/L.
7. The method for preparing the thiophene ionic liquid modified MXene heat-conducting filler according to claim 1, wherein the step S300 specifically comprises the following steps:
s301, adding thiophene ionic liquid into deionized water, and stirring to obtain an IL aqueous solution, wherein the amount of each 0.5g of thiophene ionic liquid corresponds to 50-100ml of deionized water;
s302, slowly adding MXene nano-sheets into the aqueous solution of all IL obtained in the step S301, carrying out ice bath ultrasonic treatment for 8-10 minutes, and then carrying out magnetic stirring at room temperature for 15-24 hours, wherein the mass ratio of the MXene nano-amount to the thiophene ionic liquid in the step S301 is 1:1-1: 2;
and S303, after the magnetic stirring is finished, washing with deionized water for at least two times to remove redundant thiophene ionic liquid, then carrying out suction filtration and separation, and finally carrying out freeze drying for 12-24 hours to obtain the thiophene ionic liquid modified MXene heat-conducting filler.
8. A heat-conducting composite material, characterized in that the heat-conducting composite material is prepared by adding the thiophene ionic liquid modified MXene heat-conducting filler prepared by the preparation method of the thiophene ionic liquid modified MXene heat-conducting filler according to any one of claims 1-7 into a PVDF solution for compounding.
9. The heat-conducting composite material as claimed in claim 8, wherein the thiophene ionic liquid modified MXene heat-conducting filler is added into the PVDF solution to obtain the heat-conducting composite material, and the method specifically comprises the following steps:
adding the thiophene ionic liquid modified MXene heat-conducting filler into the PVDF solution, wherein the mass ratio of the thiophene ionic liquid modified MXene heat-conducting filler to the PVDF in the PVDF solution is 0.001:1-0.25:1, uniformly stirring and dispersing, then carrying out vacuum drying at 60-80 ℃, and finally carrying out hot pressing at 185 ℃ to obtain the heat-conducting composite material.
10. The thermally conductive composite material as claimed in claim 9, wherein the PVDF solution is obtained by adding PVDF particles into DMF solvent and stirring at 50-60 ℃.
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