CN116178618A - High-heat-conductivity polyion liquid/boron nitride composite insulating material and preparation method thereof - Google Patents
High-heat-conductivity polyion liquid/boron nitride composite insulating material and preparation method thereof Download PDFInfo
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- CN116178618A CN116178618A CN202310243542.0A CN202310243542A CN116178618A CN 116178618 A CN116178618 A CN 116178618A CN 202310243542 A CN202310243542 A CN 202310243542A CN 116178618 A CN116178618 A CN 116178618A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007788 liquid Substances 0.000 title claims abstract description 104
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 103
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000011810 insulating material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 27
- 150000001450 anions Chemical class 0.000 claims abstract description 25
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
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- 230000002829 reductive effect Effects 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 32
- -1 trimethylammonium salt cation Chemical class 0.000 claims description 28
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 8
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- 238000006116 polymerization reaction Methods 0.000 claims description 7
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- 238000000605 extraction Methods 0.000 claims description 6
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 150000001768 cations Chemical class 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 210000003097 mucus Anatomy 0.000 claims description 2
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- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000017525 heat dissipation Effects 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08K3/38—Boron-containing compounds
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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Abstract
The invention discloses a high-heat-conductivity polyionic liquid/boron nitride composite insulating material and a preparation method thereof. The composite material is prepared by uniformly mixing a polyionic liquid monomer, boron nitride powder, a cross-linking agent and an initiator, and polymerizing in situ, and has high mechanical strength, insulativity and flame retardance while obtaining high heat conductivity, wherein anions of the polyionic liquid are adjustable, the intrinsic heat conductivity of a polyionic liquid matrix is improved by changing the magnitude of intermolecular hydrogen bonding acting force, the heat conductivity of the polyionic liquid is far higher than that of a traditional polymer, and meanwhile, anions in the polyionic liquid have flame retardance, so that the polyionic liquid has excellent flame retardance; and secondly, the functional groups in the polyionic liquid can also form hydrogen bonds with the inorganic boron nitride filler material, so that the filler is tightly combined, the interface thermal resistance is effectively reduced, and the thermal conductivity of the composite material is further improved.
Description
Technical Field
The invention belongs to the field of preparation of heat-conducting insulating materials, and relates to a high-heat-conducting polyion liquid/boron nitride composite insulating material and a preparation method thereof.
Background
Smaller and higher power densities are a development direction of modern electronic devices, however, this causes serious problems of heating of the electronic devices, and if heat cannot be dissipated in time, normal operation of electronic components is seriously compromised, and even the devices are damaged. The problem of heat dissipation of electronic components is becoming a major issue in the current industry and academia. At present, heat dissipation of electronic components generally adopts natural, forced, refrigeration, heat conduction, liquid, heat isolation and the like. The conduction technology has the advantages of excellent heat conduction property and isothermal property, excellent heat flux density in application, excellent constant temperature property, rapid environment adaptation and the like, and is widely applied to the aspects of cooling of electric equipment and electronic components and heat dissipation of semiconductor elements.
In order to achieve rapid heat conduction in electronic devices, materials excellent in heat dissipation performance are required. The ideal heat dissipation material needs to have not only high thermal conductivity but also good electrical insulation, mechanical properties, heat resistance, and even flame retardance. Metal or ceramic materials have high thermal conductivity, but their electrical conductivity or brittleness are not suitable for heat dissipation of electronic devices. Polymeric materials have significant advantages over metals or ceramics, including insulation, flexibility, light weight, ease of processing, and the like. However, the thermal conductivity of polymeric materials is low (typically in the range of 0.1-0.3 wm -1 K -1 ) Limiting its application. The preparation of filled heat conducting material from composite polymer and high heat conducting stuffing is the most common method for developing heat dissipating material. The prior art still faces two challenges: firstly, the thermal conductivity of the polymer is low; secondly, the compatibility between the polymer and the ceramic filler is poor, the interface thermal resistance is large, and the improvement of the thermal conductivity of the composite material is hindered. Therefore, development of novel high thermal conductive polymers is urgently required. The polyionic liquid (polymer ionic liquid, PIL) is polymerized by the ionic liquid, and has various characteristics (flame retardance, high stability and the like) of the ionic liquid and polymer processability. Boron Nitride (BN) is a novel two-dimensional material composed of Boron element and nitrogen element, and has high intrinsic thermal conductivity, excellent chemical stability and insulation. The polyionic liquid structural unit contains a large number of functional groups, can form hydrogen bonds with BN filler, and is helpful for eliminationRemoving interface thermal resistance. In addition, the ion units of the polyionic liquid can exchange ions under the heated condition, thereby facilitating the heat transmission. The polyionic liquid developed by the patent has thermal conductivity far higher than that of the traditional polymer. The polyion liquid and BN filler are combined, so that the advantages and disadvantages can be overcome, and the high-heat-conductivity polyion liquid/boron nitride composite insulating material can be prepared.
Disclosure of Invention
The invention aims to solve the problems in the existing filled heat-conducting composite material and provides a composite material with the characteristics of high heat conduction, good insulativity, high stability, easiness in preparation and the like and a preparation method thereof. The key point is that a novel quaternary ammonium salt type ionic liquid monomer is synthesized, the ionic liquid monomer, BN heat-conducting filler, cross-linking agent and initiator are uniformly mixed, and in-situ polymerization is carried out to form the composite heat-conducting material. The prepared composite heat conduction material has the following characteristics: (1) The structure unit of the polyionic liquid contains a large number of functional groups, and hydrogen bonds are easy to form among molecules, so that the intrinsic heat conductivity of the polyionic liquid is improved; (2) The polyionic liquid side group contains ionic groups, and under the action of heat, exchange reaction occurs between ions to transfer energy, so that the heat transfer is facilitated; (3) The quaternary ammonium salt ionic group and N atoms in BN form hydrogen bonds, so that the polymer and BN particles are tightly combined, interface thermal resistance is eliminated, and the thermal conductivity of the composite material is improved; (4) The BN particles have wide band gap and good insulativity, thus blocking the movement of electrons in the composite material and improving the electrical insulation property; (5) Both the polyionic liquid and the BN particles have flame retardance, and excellent flame retardance is imparted to the composite material. The method is suitable for mass production, does not involve the use of corrosive chemical reagents, and is easy to operate.
The invention aims at realizing the following technical scheme:
the invention provides a high-heat-conductivity polyion liquid/boron nitride composite insulating material, which comprises the following substances in percentage by mass, 0-70% of boron nitride powder, 0.5-1% of cross-linking agent, 0.5-1% of initiator and the balance polyion liquid monomer; the polyion liquid insulating composite material takes polyion liquid as a matrix and Boron Nitride (BN) powder as a filler; the preparation method comprises the steps of uniformly mixing a polyion liquid monomer, BN powder, a cross-linking agent and an initiator, and carrying out in-situ polymerization to obtain a master batch, wherein the master batch is subjected to hot press molding in a flat vulcanizing machine, the processing condition is that the temperature is 100 ℃, the pressure is 12MPa, and the hot press is carried out for 12 hours, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-2 is obtained.
The polyionic liquid monomer is self-made 2- (trimethylammonium salt cation) ethyl methacrylate ionic liquid and comprises cations and anions, wherein the cations are trimethylammonium salt cations (N) + ) The anions include iodide anions (I) - ) Tetrafluoroborate anion (BF) 4 - ) Hexafluorophosphate anion (PF) 6 - ) Bis-fluorosulfonyl imide anions (FSI) - ) Lithium bis (trifluoromethylsulfonyl) imide (TFSI) - ) The method comprises the steps of carrying out a first treatment on the surface of the The cross-linking agent is Ethylene Glycol Dimethacrylate (EGDMA), and the initiator is Azobisisobutyronitrile (AIBN).
Preferably, the high thermal conductivity BN filler has a diameter of one or more of 10 microns, 20 microns and 30 microns.
Preferably, the preparation of the polyionic liquid monomer comprises the following steps:
A. ionization of ethyl 2- (dimethylamino) methacrylate: reaction of ethyl 2- (dimethylamino) methacrylate with methyl iodide to produce iodinated ethyl 2- (trimethylammonium salt) methacrylate] + [I] - ；
B. [2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving, adding lithium salt with corresponding mass to carry out anion displacement reaction, extracting, decompressing and distilling to obtain a polymerized monomer;
preferably, in the step A, the molar ratio of the ethyl 2- (dimethylamino) methacrylate to the methyl iodide is 3:4, the solvent is chloroform, the solution concentration is 0.25 g/mL, the nitrogen atmosphere and the reaction temperature is 60 o C, the reaction time is 12 hours, and the solvent is removed by reduced pressure distillation after the reaction is finished, so that white powdery iodine is obtainedIonization of ethyl [2- (trimethylamino salt) methacrylate] + [I] - 。
Preferably, in step B, ethyl [2- (trimethylamino salt) methacrylate is used] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt (LiBF 4 、LiPF 6 LiSSI or LiTFSI ethyl [2- (trimethylaminosalt) methacrylate] + [I] - The molar ratio of (2) is 1.5:1, and the polymer monomer is white mucus, and the anion of the polymer monomer is BF after the anion replacement reaction, the extraction and the reduced pressure distillation are carried out 4 - 、PF 6 - 、FSI - And TFSI - One of them.
The mass ratio of the polymerized monomer, BN powder, initiator and cross-linking agent is 89:10:0.5:0.5, 78:20:1:1, 69:30:0.5:0.5, 58:40:1:1, 49:49:1:1, 40:59:0.5:0.5 and 30:68:1:1.
The polymer monomer is firstly mixed with BN powder, a cross-linking agent and an initiator, and a mixing mode adopts a planetary mixer to prepare a precursor; subsequently, the composite insulation material is prepared by in-situ polymerization.
Preferably, the conditions for planetary mixing are 2000 revolutions for 20 minutes.
The conditions of the in-situ polymerization are 100 o C. And (3) obtaining the high-heat-conductivity polyion liquid/boron nitride composite insulating material after 12 hours.
According to the invention, the polyion liquid is used as a polymer substrate, BN powder with outstanding electrical insulation performance and heat conduction performance is used as a filler, and the high-heat-conductivity polyion liquid/boron nitride composite insulating material is prepared in an in-situ polymerization mode, so that the prepared composite material has high heat conductivity, excellent electrical insulation performance and flame retardance. The method for preparing the heat-conducting and insulating composite material by taking the polyion liquid as the heat-conducting substrate has not been reported yet.
Compared with the prior art, the invention has the following beneficial effects:
1. polyionic liquids are chosen as polymer substrates, which have a higher thermal conductivity than existing polymers because: firstly, the structural unit of the polyionic liquid contains a large number of functional groups, and hydrogen bonds are easy to form among molecules, so that the intrinsic heat conductivity of the polyionic liquid is improved; secondly, the polyionic liquid side group contains ionic groups, and under the action of heat, exchange reaction occurs between ions to transfer energy, so that the heat transfer is facilitated; finally, the quaternary ammonium salt ionic group in the polyion liquid and N atoms in BN form hydrogen bonds, so that the polymer and BN particles are tightly combined, interface thermal resistance is eliminated, and the thermal conductivity of the composite material is improved;
2. the BN particles added by the invention are used as heat conduction filler, firstly BN has excellent heat conductivity> 1000 W m -1 K -1 ) Is a novel heat-conducting filler; secondly, BN particles have wide band gap and good insulativity, thus blocking the movement of electrons in the composite material and improving the electrical insulation of the composite material;
3. the polyion liquid and BN particles related to the invention have flame retardance, and endow the composite material with excellent flame retardance. The method is suitable for mass production, does not involve the use of corrosive chemical reagents, and is easy to operate.
4. Through many years of research, the inventors have obtained expected inventive results from composite insulating materials prepared by using polyionic liquid as a matrix and BN particles as fillers. The prepared heat-conducting and insulating composite material has the performances of high heat conductivity, high direct-current breakdown strength and high flame retardance, and is suitable for the fields of advanced electronic packaging, 5G base stations, heat dissipation of chips and new energy batteries, and the like.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram of a process for preparing a polyionic liquid monomer according to the present invention;
thermal conductivity (a) of the polyionic liquid prepared in the example of fig. 2; thermal conductivity (b) maps for polyionic liquid/BN insulating composites and comparative composites;
FIG. 3 is a graph showing the DC breakdown strength Weibull distribution of the polyionic liquid/BN insulation composite material prepared in the example;
FIG. 4 is a graph of thermal weight loss of the polyionic liquid/BN insulation composite material prepared in example 4;
fig. 5 is a scanning electron micrograph of a frozen section of the polyionic liquid/BN insulating composite material prepared in example 4.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The following examples used a planetary mixer (hinky ARE-250, japan) to solution blend BN filler and a polyionic liquid matrix; and (3) performing hot press molding on the polyion liquid/BN composite material by adopting a flat vulcanizing machine (Shanghai rubber mechanical factory, QLB-D).
The DC breakdown strength of the polyionic liquid/BN insulating composite material prepared in the following examples was tested by using a DC high voltage generator (AHDZ-10/100 type, shanghai blue wave Co., ltd.).
The thermal conductivity of the polyionic liquid/BN insulation composite prepared in the following examples was tested using the laser pulse method (Netzsch LFA 467, germany).
The dispersibility of the filler in the polyionic liquid/BN insulation composite prepared in the following examples was observed using a transmission electron microscope (SEM) (FEI Nova NanoSEM 450, usa).
The thermal stability of the samples prepared in the examples below was determined using a thermogravimetric analyzer (type TG 209 F3, netzsch company, germany).
In FIG. 1, X - Is an anion, the anion is BF 4 - 、PF 6 - 、FSI - And TFSI - One of them.
Example 1
The embodiment relates to a high-heat-conductivity polyionic liquid/boron nitride composite insulating material and a preparation method thereof. The preparation process of the polyionic liquid monomer (IL-1) is shown in figure 1, and the polyionic liquid monomer (IL-1) is prepared by the following steps:
iodination of ethyl 2- (dimethylamino) methacrylate: the ethyl 2- (dimethylamino) methacrylate and methyl iodide are dissolved in chloroform according to the mol ratio of 3:4, the concentration of the solution is 0.25 g/mL, the reaction temperature is 60 in nitrogen atmosphere o C, the reaction time is 12 hours, and after the reaction is finished, the solvent is distilled off under reduced pressure to obtain white powder iodinated [2- (trimethylammonium salt) ethyl methacrylate] + [I] - 。
[2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt LiBF 4 With [2- (trimethylaminosalt) ethyl methacrylate] + [I] - The reaction, the mole ratio of the two is 1.5:1, the anion replacement reaction is carried out, the white mucilage is obtained after the extraction and the reduced pressure distillation, and the anion of the polymerized monomer is BF 4 - And is designated IL-1.
The embodiment also relates to a preparation method of the high-heat-conductivity polyionic liquid/boron nitride composite insulating material, which comprises the following steps:
And 2, carrying out hot press molding on the master batch in a plate vulcanizing machine, wherein the processing conditions are that the temperature is 100 ℃, the pressure is 12MPa, and the hot pressing is carried out for 12 hours, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-1 is obtained.
Example two
The embodiment relates to a high-heat-conductivity polyionic liquid/boron nitride composite insulating material and a preparation method thereof. The preparation process of the polyionic liquid monomer (IL-2) is shown in figure 1, and the polyionic liquid monomer (IL-2) is prepared by the following steps:
iodination of ethyl 2- (dimethylamino) methacrylate: the ethyl 2- (dimethylamino) methacrylate and methyl iodide are dissolved in chloroform according to the mol ratio of 3:4, the concentration of the solution is 0.25 g/mL, the reaction temperature is 60 in nitrogen atmosphere o C, the reaction time is 12 hours, and after the reaction is finished, the solvent is distilled off under reduced pressure to obtain white powder iodinated [2- (trimethylammonium salt) ethyl methacrylate] + [I] - 。
[2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt LiPF 6 With [2- (trimethylaminosalt) ethyl methacrylate] + [I] - The reaction, the mole ratio of the two is 1.5:1, the anion replacement reaction is carried out, the white mucilage is obtained after the extraction and the reduced pressure distillation, and the anion of the polymerized monomer is BF 4 - And is designated IL-2.
The embodiment also relates to a preparation method of the high-heat-conductivity polyionic liquid/boron nitride composite insulating material, which comprises the following steps:
And 2, carrying out hot press molding on the master batch in a plate vulcanizing machine, wherein the processing conditions are that the temperature is 100 ℃, the pressure is 12MPa, and the hot pressing is carried out for 12 hours, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-2 is obtained.
Example III
The embodiment relates to a high-heat-conductivity polyionic liquid/boron nitride composite insulating material and a preparation method thereof. The preparation process of the polyionic liquid monomer (IL-3) is shown in figure 1, and the polyionic liquid monomer (IL-3) is prepared by the following steps:
iodination of ethyl 2- (dimethylamino) methacrylate: the ethyl 2- (dimethylamino) methacrylate and methyl iodide are dissolved in chloroform according to the mol ratio of 3:4, the concentration of the solution is 0.25 g/mL, the reaction temperature is 60 in nitrogen atmosphere o C, the reaction time is 12 hours, and after the reaction is finished, the solvent is distilled off under reduced pressure to obtain white powder iodinated [2- (trimethylammonium salt) ethyl methacrylate] + [I] - 。
[2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt LiFSI and ethyl [2- (trimethylaminosalt) methacrylate] + [I] - The reaction, the mole ratio of the two is 1.5:1, the anion replacement reaction is carried out, the white mucilage is obtained after the extraction and the reduced pressure distillation, and the anion of the polymerized monomer is BF 4 - And is designated IL-3.
The embodiment also relates to a preparation method of the high-heat-conductivity polyionic liquid/boron nitride composite insulating material, which comprises the following steps:
And 2, carrying out hot press molding on the master batch in a plate vulcanizing machine, wherein the processing conditions are that the temperature is 100 ℃, the pressure is 12MPa, and the hot pressing is carried out for 12 hours, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-3 is obtained.
Example IV
The embodiment relates to a high-heat-conductivity polyionic liquid/boron nitride composite insulating material and a preparation method thereof. The preparation process of the polyionic liquid monomer (IL-4) is shown in figure 1, and the polyionic liquid monomer (IL-4) is prepared by the following steps:
iodination of ethyl 2- (dimethylamino) methacrylate: the ethyl 2- (dimethylamino) methacrylate and methyl iodide are dissolved in chloroform according to the mol ratio of 3:4, the concentration of the solution is 0.25 g/mL, the reaction temperature is 60 in nitrogen atmosphere o C, the reaction time is 12 hours, and after the reaction is finished, the solvent is distilled off under reduced pressure to obtain white powder iodinated [2- (trimethylammonium salt) ethyl methacrylate] + [I] - 。
[2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt LiTFSI and ethyl [2- (trimethylaminosalt) methacrylate] + [I] - The reaction, the mole ratio of the two is 1.5:1, the anion replacement reaction is carried out, the white mucilage is obtained after the extraction and the reduced pressure distillation, and the anion of the polymerized monomer is BF 4 - And is designated IL-4.
The embodiment also relates to a preparation method of the high-heat-conductivity polyionic liquid/boron nitride composite insulating material, which comprises the following steps:
And 2, carrying out hot press molding on the master batch in a plate vulcanizing machine, wherein the processing conditions are that the temperature is 100 ℃, the pressure is 12MPa, and the hot pressing is carried out for 12 hours, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-4 is obtained.
Example five
The embodiment relates to a high-heat-conductivity polyion liquid/boron nitride composite insulating material and a preparation method thereof. The preparation of the monomers (IL-1, IL-2, IL-3 and IL-4) of the hybrid polyionic liquid is described in example 1, example 2, example 3 and example 4.
The embodiment also relates to a preparation method of the high-heat-conductivity polyionic liquid/boron nitride composite insulating material, which comprises the following steps:
And 2, carrying out hot press molding on the master batch in a plate vulcanizing machine, wherein the processing conditions are that the temperature is 100 ℃, the pressure is 12MPa, and the hot pressing is carried out for 12 hours, so that the high heat conduction polyion liquid/boron nitride composite insulating material HPIL/BN is obtained.
Comparative example 1
The comparative example relates to a preparation of a heat-conducting polydimethylsiloxane/boron nitride composite insulating material, which consists of Polydimethylsiloxane (PDMS) serving as a matrix and BN powder serving as a filler, wherein the mass ratio of PDMS to BN filler is 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60 and 30:70, and the processing method adopts the steps 1 and 2 of the embodiment, so that the high heat-conducting polydimethylsiloxane/boron nitride composite insulating material PDMS/BN is obtained.
Comparative example 2
The comparative example relates to a preparation of a heat-conducting polyurethane/boron nitride composite insulating material, wherein the composite material is prepared by taking Polyurethane (PU) as a matrix and BN powder as a filler, wherein the mass ratio of the PU to the BN filler is 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60 and 30:70, and the processing method adopts the steps 1 and 2 in the embodiment, so that the heat-conducting polyurethane/boron nitride composite insulating material PU/BN is obtained.
Comparative example 3
The comparative example relates to a heat-conducting polymethyl methacrylate/boron nitride composite insulating material, which is prepared by taking polymethyl methacrylate (PMMA) as a matrix and BN powder as a filler, wherein the mass ratio of PMMA to BN filler is 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60 and 30:70, and the processing method adopts the steps 1 and 2 of the embodiment, so that the heat-conducting polymethyl methacrylate/boron nitride composite insulating material PMMA/BN is obtained.
The implementation effect is as follows: FIG. 2 (a) shows the thermal conductivity of the four polyionic liquids prepared in examples 1 to 4, the thermal conductivity of PIL-4 is highest because the intermolecular forces and the ion exchange rate can be adjusted by changing the kind of anions, TFSI - With the largest dimensions, ion exchange is more likely to occur to promote heat transfer.
FIG. 2 (b) is the thermal conductivity of the composites prepared in example 4 and comparative examples 1-3, with PIL/BN-4 having the highest thermal conductivity, at the same filler content, the thermal conductivity is 2-3 times that of the conventional polymers, demonstrating that the polyionic liquid can effectively build a thermal conduction path, reducing the interfacial thermal resistance, and thus increasing the thermal conductivity of the composites.
Fig. 3 is a graph showing the Weibull distribution of the dc breakdown strength of the polyionic liquid/boron nitride composite insulating material and the polymer/boron nitride composite material prepared in example 4 and comparative examples 1-3, and the graph shows that the polyionic liquid/boron nitride composite insulating material has a breakdown voltage higher than 200kV/mm and excellent electrical insulation.
Fig. 4 is a graph of thermal weight loss of the polyionic liquid/boron nitride composite insulation material prepared in example 4, and the initial decomposition temperature of the composite material is about 345 ℃, so that the composite material has higher thermal stability.
Fig. 5 is a scanning electron micrograph of the high thermal conductivity polyionic liquid/boron nitride composite insulating material prepared in example 4, and it is known from the figure that the boron nitride particles have good compatibility with the polyionic liquid matrix, and the polyionic liquid serves as an adhesive to tightly connect the boron nitride particles, so that the thermal conductivity and the electrical insulation property are improved.
In summary, the polyionic liquid/boron nitride composite insulating material is prepared through in-situ free radical polymerization, and the composite material has high mechanical strength, insulativity and flame retardance while obtaining high thermal conductivity. The anions of the polyion liquid are adjustable, the intrinsic heat conductivity of a polyion liquid matrix is improved by changing the magnitude of intermolecular hydrogen bond acting force, the heat conductivity of the polyion liquid is far higher than that of a traditional polymer, and meanwhile, the anions in the polyion liquid have flame retardant capability, so that the polyion liquid has excellent flame retardance; secondly, the functional groups in the polyionic liquid can also form hydrogen bonds with inorganic boron nitride filler materials, so that the fillers are tightly combined, the interface thermal resistance is effectively reduced, and the thermal conductivity of the composite material is further improved; finally, the two-dimensional boron nitride filler not only has excellent heat conductivity, but also has excellent electrical insulation, and the effects of inhibiting space charge accumulation and injection improve the electrical insulation of the composite material. The prepared composite material has high heat conductivity, electrical insulation and flame retardance, and is suitable for the fields of advanced electronic packaging, 5G base stations, chips, heat dissipation of new energy batteries and the like.
There are many ways in which the invention may be practiced, and the foregoing is merely a preferred embodiment of the invention. It should be noted that the above-mentioned embodiments are only for illustrating the present invention, but not for limiting the scope of the present invention. It will be apparent to those skilled in the art that several variations may be made without departing from the mechanism of the invention, and such variations are considered to be within the scope of the invention.
Claims (8)
1. A high heat conduction polyion liquid/boron nitride composite insulating material is characterized in that: comprises the following substances in percentage by mass, 0-70% of boron nitride powder, 0.5-1% of cross-linking agent, 0.5-1% of initiator and the balance of polyionic liquid monomer;
the polyionic liquid monomer is self-made 2- (trimethylammonium salt cation) ethyl methacrylate ionic liquid and comprises cations and anions, wherein the cations are trimethylammonium salt cations (N) + ) The anions include iodide anions (I) - ) Tetrafluoroborate anion (BF) 4 - ) Hexafluorophosphate anion (PF) 6 - ) Bis-fluorosulfonyl imide anions (FSI) - ) Lithium bis (trifluoromethylsulfonyl) imide (TFSI) - ) One or more of the above combinations;
the cross-linking agent is Ethylene Glycol Dimethacrylate (EGDMA), and the initiator is Azobisisobutyronitrile (AIBN).
2. A preparation method of a high-heat-conductivity polyionic liquid/boron nitride composite insulating material is characterized by comprising the following steps of: firstly, mixing a polymer monomer with boron nitride powder, a cross-linking agent and an initiator, wherein a mixing mode adopts a planetary mixer to prepare a precursor; and then, carrying out in-situ polymerization to obtain a master batch, and carrying out hot press molding on the master batch in a plate vulcanizing machine under the processing conditions of 100 ℃ and 12MPa and hot pressing for 12 hours to obtain the high-heat-conductivity polyion liquid/boron nitride composite insulating material PIL/BN-2.
3. The high thermal conductivity polyionic liquid/boron nitride composite insulating material according to claim 1, wherein: the boron nitride diameter is one or more of 10 microns, 20 microns and 30 microns.
4. The high thermal conductivity polyionic liquid/boron nitride composite insulating material according to claim 1, wherein: the preparation of the polyionic liquid monomer comprises the following steps:
ionization of ethyl 2- (dimethylamino) methacrylate: reacting ethyl 2- (dimethylamino) methacrylate with methyl iodide,preparation of iodinated [2- (trimethylamino salt) ethyl methacrylate] + [I] - ；
[2- (trimethylamino salt) ethyl methacrylate] + [I] - Is an anion exchange reaction of: will [2- (trimethylamino salt) methacrylic acid ethyl ester] + [I] - Dissolving, adding lithium salt with corresponding mass to carry out anion replacement reaction, extracting, decompressing and distilling to obtain a polymerized monomer.
5. The high thermal conductivity polyionic liquid/boron nitride composite insulating material according to claim 4, wherein: in the step A, the mol ratio of the 2- (dimethylamino) ethyl methacrylate to the methyl iodide is 3:4, the solvent is chloroform, the solution concentration is 0.25 g/mL, the nitrogen atmosphere is adopted, and the reaction temperature is 60 o C, the reaction time is 12 hours, and after the reaction is finished, the solvent is distilled off under reduced pressure to obtain white powder iodinated [2- (trimethylammonium salt) ethyl methacrylate] + [I] - 。
6. The high thermal conductivity polyionic liquid/boron nitride composite insulating material according to claim 4, wherein: in step B, [2- (trimethylamino salt) ethyl methacrylate] + [I] - Dissolving in deionized water at a concentration of 0.25 g/mL, adding lithium salt (LiBF 4 、LiPF 6 LiSSI or LiTFSI ethyl [2- (trimethylaminosalt) methacrylate] + [I] - The molar ratio of (2) is 1.5:1, and the polymer monomer is white mucus, and the anion of the polymer monomer is BF after the anion replacement reaction, the extraction and the reduced pressure distillation are carried out 4 - 、PF 6 - 、FSI - And TFSI - One of them.
7. The high thermal conductivity polyionic liquid/boron nitride composite insulating material according to claim 2, wherein the condition of adopting planetary mixing is 2000 revolutions for 20 minutes.
8. According to claim 2The high heat conduction polyionic liquid/boron nitride composite insulating material is characterized in that the condition of in-situ polymerization is 100 o C. And (3) 12 hours and the pressure is 12MPa, so that the high-heat-conductivity polyion liquid/boron nitride composite insulating material is obtained.
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| US20070241303A1 (en) * | 1999-08-31 | 2007-10-18 | General Electric Company | Thermally conductive composition and method for preparing the same |
| WO2016141301A1 (en) * | 2015-03-04 | 2016-09-09 | William Marsh Rice University | Boron nitride-ionic liquid composites and their use for energy storage devices |
| US11050082B1 (en) * | 2016-09-29 | 2021-06-29 | United States Of America As Represented By The Secretary Of The Air Force | Colloidal ionic-liquid electrolytes |
| KR20220067767A (en) * | 2020-11-18 | 2022-05-25 | 단국대학교 천안캠퍼스 산학협력단 | Solid electrolyte impregnated with polymeric ionic compound and manufacturing method thereof |
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|---|---|---|---|---|
| US20070241303A1 (en) * | 1999-08-31 | 2007-10-18 | General Electric Company | Thermally conductive composition and method for preparing the same |
| WO2016141301A1 (en) * | 2015-03-04 | 2016-09-09 | William Marsh Rice University | Boron nitride-ionic liquid composites and their use for energy storage devices |
| US11050082B1 (en) * | 2016-09-29 | 2021-06-29 | United States Of America As Represented By The Secretary Of The Air Force | Colloidal ionic-liquid electrolytes |
| KR20220067767A (en) * | 2020-11-18 | 2022-05-25 | 단국대학교 천안캠퍼스 산학협력단 | Solid electrolyte impregnated with polymeric ionic compound and manufacturing method thereof |
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