CN103525005B - The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material - Google Patents
The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material Download PDFInfo
- Publication number
- CN103525005B CN103525005B CN201310370962.1A CN201310370962A CN103525005B CN 103525005 B CN103525005 B CN 103525005B CN 201310370962 A CN201310370962 A CN 201310370962A CN 103525005 B CN103525005 B CN 103525005B
- Authority
- CN
- China
- Prior art keywords
- hbp
- aps
- composite material
- preparation
- epoxy composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000004593 Epoxy Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004513 sizing Methods 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 238000011049 filling Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000004760 aramid Substances 0.000 claims abstract description 9
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000703 high-speed centrifugation Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 7
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002012 dioxanes Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- 150000003866 tertiary ammonium salts Chemical class 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- -1 carrene Chemical compound 0.000 claims 3
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000011085 pressure filtration Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000002079 cooperative effect Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The preparation method who the present invention relates to the high heat conduction ternary of a kind of low sizing content nano-micro structure epoxy composite material, comprises the following steps: by silane coupler γ-APS modification, at Al2O3And h-BN surface is introduced amino; Taking the amino of grafting as avtive spot, at the preliminary hyperbranched aromatic polyamide of modified filler surface grafting (HBP), obtain modified filler Al2O3-HBP and BN-HBP; Two kinds of modified fillers are fully mixed with epoxy resin-base with certain proportioning and content; By the two steps substeps curing method that heats up, make ternary nano-micro structure epoxy composite material. The heat conductivility of epoxy composite material provided by the invention shows obvious cooperative effect, system thermal conductivity factor can regulate by changing filling mixture ratio, under low sizing content, there is high thermal conductivity coefficient, kept the good mechanics of polymer composites and processing characteristics, and significantly reduced costs.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy composite material, be specifically related to the high heat conduction ternary of a kind of low sizing content and receiveThe preparation method of micro-structural epoxy composite material.
Background technology
The develop rapidly of and package technique integrated along with microelectronics, the volume of electronic devices and components and logic circuit is more and more less,Meanwhile, operating frequency sharply increases, and causes semi-conductive environment temperature to change to high temperature direction, for ensureing electronic devices and componentsLong-time reliably working, heat-sinking capability just becomes the restraining factors of length in its in service life in time. In addition, electrical equipment and electrical,Many manufacturing industry such as LED illumination, Aero-Space, military equipment and high-tech area are also in the urgent need to having excellent heat conductivityThe material of energy. Macromolecular material has mechanics, calorifics and the processing characteristics of unique insulating properties, excellence, and by hugeVolume is enough controlled with modification has certain performance property changed, because have the incomparable advantage of other materials. But, oneAs macromolecular material be all hot non-conductor, its thermal conductivity factor is generally lower than 0.5Wm-1K-1, therefore, prepare toolThere is the highly thermally conductive polymeric material of excellent comprehensive performance extensively concerned.
Filled-type thermally conductive polymer composites is by heat filling (carbon system, metal system, pottery are three major types) and polymerizationThing matrix, compound through disperseing, lamination is compound and form the modes such as surperficial heat conducting film process after form heterogeneous composite guideHot system. Novel high intrinsic heat conduction carbon class filler, as Graphene, CNT etc., is difficult to reality at present because cost is higherExisting industrialization, these fillers are electric good conductors simultaneously, have also limited the application of corresponding composite in insulation environment.Although tradition heat filling cost is relatively low, due to the intrinsic capacity of heat transmission a little less than, corresponding composite filler content isHeight, this has not only increased cost, the more important thing is deteriorated mechanics and processing characteristics. Therefore, prepare low sizing content, heightThermally conductive polymer based composites becomes current study hotspot, also has great application prospect.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of low sizing content, high heat conduction are providedThe preparation method of ternary nano-micro structure epoxy composite material. The method is with heat conductivility excellence, electric insulation, chemically stableMicron hexagonal boron nitride (h-BN) and nano aluminium oxide (Al with low cost, combination property is good2O3) particle is compoundHeat filling, and carry out surface modification by the hyperbranched aromatic polyamide of two-step method grafting; Matrix is selected bonding, power, excellent insulation performance, and the Zhi Huan family epoxy resin that industry-wideization is applied.
Object of the present invention is achieved through the following technical solutions, a kind of low sizing content, high heat conduction ternary nano-micro structure epoxyThe preparation method of composite, comprises the steps:
Step (1), heat filling Al2O3, the silicane coupling agent surface grafted γ-APS of heat filling BN
Take 1～10gAl2O3, after fully disperseing, add 1～10wt% silane coupler in 50～500mL organic solventγ-APS also stirs, and under reflux conditions carries out coupling agent modified reaction 1～10h; After reaction finishes, separate, obtainPrecipitated product with organic solvent washing 2～3 times and at 50～100 DEG C vacuum drying 1～10d, obtain coupling agent and changeProperty filler Al2O3-APS; BN is process two-step method before grafted silane coupling agent: first, take 1～10gBN,Dispersed with stirring in the hydrochloric acid solution of 50～500mL, 1～30wt%, reacts after 1～10h at 50～100 DEG C, filters and usesDeionized water washing 2～3 times; Secondly, pre-acidifying BN is added in the hydrogen peroxide of 50～500mL, 1～30wt%, 50～At 75 DEG C, react after 1～10h, continue to be warming up to 75～100 DEG C of reaction 1～10h, then separate, the product of acquisition existsVacuum drying 1～10d at 50～100 DEG C; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1～10gAl2O3-APS and 3,4-diaminobenzoic acid (DABA) add 50～500mL organic solventIn, be stirred to DABA and fully dissolve; Then add respectively 5～50mL pyridine and triphenyl phosphite (TPP) and 50～Under 100 DEG C of nitrogen atmospheres, react 1～10h; After reaction finishes, separate, the precipitated product of acquisition is washed with organic solvent dissolutionWash 2～3 times, at 50～100 DEG C, vacuum drying 1～10d, obtains Al2O3-HBP; BN-APS grafting HBP method withAl2O3-APS is identical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 0.1～10wt% promoter and epoxy resin and at 50～100 DEG C, be fully mixed to get solution A; Take respectively0～1gAl2O3-HBP and BN-HBP, after 1～100mL organic solvent for ultrasonic dispersion, add 1～10g under room temperatureDescribed solution A, and at 50～100 DEG C respectively stir, ultrasonic 1～10h, obtain homogeneous, remove the molten of organic solventLiquid B; Take the curing agent that accounts for epoxy resin quality 10～100%, fully mix and vacuum defoamation 1 with described solution B～10h; Pour mixed liquor into mould, after precuring 1～10h, be warming up to 125～150 DEG C and continue to solidify at 100～125 DEG C1～10h, cooling and demolding obtains filer content 0～65wt% epoxy composite material, wherein BN-HBP matter in composite fillerAmount mark is 0～100%.
Preferably, described epoxy resin is glycidol ether based epoxy resin ester, ethylene oxidic ester based epoxy resin, shrinkGlyceramine based epoxy resin, line style aliphatic category epoxy resin or alicyclic based epoxy resin.
Preferably, described curing agent be aliphatic amine, aromatic amine, amine modified firming agent, polyamide curing agent,Anhydride-cured system, polyisocyanate curing agent.
Preferably, described promoter is tertiary amine, tertiary ammonium salt, fatty amine, replacement urea promoter, imidazoles, imidazole salts, secondAcyl acetone slaine, triphenylphosphine, three benzene base phosphine Perverse salt, carboxylic metallic salt, carboxylic acid metal's salt complex, boron trifluorideAmine complex or phenol accelerant.
Preferably, the temperature of described coupling agent modified reaction is 0～200 DEG C.
Preferably, described coupling agent modified filler is by further modify and graft linear polymer, branch polymer, over-expenseFluidized polymer, comb-shaped polymer or star polymer.
Preferably, step (1) with described in step (2), separate adopt high speed centrifugation, vacuum filtration, normal pressure to filter orThe method of toppling over.
Preferably, described in step (1) and step (3), disperse to adopt ultrasonic, stirring or cytoclastic method to carry out.
Preferably, in step (1), (2) and (3), described organic solvent be oxolane, acetone, dioxanes,Carrene, chloroform, benzene,toluene,xylene, dimethyl formamide, 1-METHYLPYRROLIDONE or acetonitrile.
In the present invention, heat filling used can be one or more of metal, carbon and pottery, and described metal can beCopper, silver, gold, nickel or aluminium; Described carbon can be amorphous carbon, graphite, diamond, CNT or Graphene; InstituteStating pottery can be boron nitride, aluminium nitride, silicon nitride, magnesia, beryllium oxide, aluminium oxide, zinc oxide, silicaOr carborundum. In addition, described silane coupler can use titanate coupling agent, aluminate coupling agent or the compound idol of aluminium titaniumConnection agent replaces.
Compared with prior art, the present invention has following beneficial effect:
1, hyperbranched aromatic polyamide grafting Al of the present invention2O3-HBP and BN-HBP filler disperse homogeneous in matrix,Compatibility is outstanding: learn the polymeric layer of filling surface grafting one number of plies nanometer thickness from modified filler TEM image; From multipleCondensation material TEM image learns, reuniting and pi-pi accumulation does not appear in modified filler, and interface does not have open defect (blankRegion is in anisotropy distribution BN-HBP slicing processes, to destroy matrix around to cause);
2, ternary nano-micro structure epoxy composite material of the present invention shows obvious agreement, and from heat conduction, figure learns, itsThermal conductivity factor can regulate by changing compounded mix proportioning, and BN-HBP performance the best while accounting for compounded mix 80wt%;
3, ternary nano-micro structure epoxy composite material of the present invention has high thermal conductivity coefficient under low sizing content, from heat conductionFigure learns, adds the best proportioning compounded mix of 10wt% and can reach the thermal conductivity factor that adds the single BN-HBP filler of 30wt%,Reduce manufacturing cost, meanwhile, kept mechanics and the processing characteristics of polymer composites excellence;
4, ternary nano-micro structure epoxy composite material of the present invention has more complete heat conduction network, from composite TEMImage is learnt, Al2O3-HBP particle plays bridging effect, has connected originally isolation BN-HBP mutually.
Brief description of the drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, further feature of the present invention,It is more obvious that object and advantage will become:
Fig. 1 is FT-IR spectrogram of the present invention, and wherein (a) represents Al2O3、Al2O3-APS、Al2O3-HBP, (b) generationTable BN, BN-APS, BN-HBP.
Fig. 2 is the TEM image of modified filler of the present invention, and wherein (a) is Al2O3-HBP; (b) be BN-HBP, arrowIndication is polymer.
Fig. 3 is BN-HBP content and the total relation of the amount of filling out in epoxy composite material thermal conductivity factor of the present invention and compounded mix;Wherein built-in: the single filler material of the relative BN-HBP of optimal proportion epoxy composite material and base in 10wt%, 30wt% systemBody thermal conductivity factor growth rate.
Fig. 4 is the TEM figure of the best proportioning epoxy composite material section of 10wt% filer content of the present invention, wherein figure (b)For the partial enlarged drawing of boxed area of figure (a).
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail. Following examples will contribute to this areaTechnical staff further understands the present invention, but does not limit in any form the present invention. It should be pointed out that this areaThose of ordinary skill, without departing from the inventive concept of the premise, can also make certain adjustments and improvements. TheseAll belong to protection scope of the present invention.
Embodiment 1
The present embodiment relates to the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material, bagDraw together following steps:
Step (1), Al2O3, BN surface grafting gamma-aminopropyl-triethoxy-silane (γ-APS)
Take 2gAl2O3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; InsteadShould finish rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 DEG C vacuum drying 1d, obtain Al2O3-APS。BN is process two-step method before grafted silane coupling agent: first, take 2gBN, at 100mL30wt% hydrochloric acid solutionMiddle dispersed with stirring, reacts after 1h at 50 DEG C, filters and with deionized water washing 3 times; Secondly, pre-acidifying BN is addedEnter in 50mL30wt% hydrogen peroxide, react after 1h at 50 DEG C, continue to be warming up to 75 DEG C of reaction 1h, product is centrifugalAnd at 50 DEG C vacuum drying 1d; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1gAl2O3-APS and 3,4-diaminobenzoic acid (DABA) add 50mLN-methyl pyrrolidone (NMP)In, be stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and at 50 DEG CUnder nitrogen atmosphere, react 1h; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves to be washedWash 3 times, at 50 DEG C, vacuum drying 1d, obtains Al2O3-HBP; BN-APS grafting HBP method and Al2O3-APSIdentical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Taking 1wt% promoter (DMP-30) fully mixes at 50 DEG C with Zhi Huan family epoxy resin (DOW6105)Obtain solution A; Take respectively 0.5gAl2O3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion,Add 2g solution A and at 50 DEG C respectively stir, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; TakeThe crosslinking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mixes and vacuum defoamation 1h with solution B;Pour mixed liquor into mould, after precuring 1h, be warming up to 125 DEG C and continue to solidify 1h at 100 DEG C, cooling and demoldingObtain filer content 20wt% epoxy composite material, wherein BN-HBP mass fraction in composite filler is 50%.
Embodiment 2
The present embodiment relates to the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material, bagDraw together following steps:
Step (1), Al2O3, BN surface grafting gamma-aminopropyl-triethoxy-silane (γ-APS)
Take 5gAl2O3, after fully disperseing, add 2wt% γ-APS stirring and refluxing 2h in 200mL dimethylbenzene; InsteadShould finish rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 DEG C vacuum drying 1d, obtain Al2O3-APS。BN is process two-step method before grafted silane coupling agent: first, take 5gBN, at 200mL30wt% hydrochloric acid solutionMiddle dispersed with stirring, reacts after 1h at 50 DEG C, filters and with deionized water washing 3 times; Secondly, pre-acidifying BN is addedEnter in 100mL30wt% hydrogen peroxide, react after 1h at 50 DEG C, continue to be warming up to 75 DEG C of reaction 1h, product fromThe heart and at 50 DEG C vacuum drying 1d; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1gAl2O3-APS and 3,4-diaminobenzoic acid (DABA) add 50mLN-methyl pyrrolidone (NMP)In, be stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and at 50 DEG CUnder nitrogen atmosphere, react 1h; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves to be washedWash 3 times, at 50 DEG C, vacuum drying 1d, obtains Al2O3-HBP; BN-APS grafting HBP method and Al2O3-APSIdentical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Taking 1wt% promoter (DMP-30) fully mixes at 50 DEG C with Zhi Huan family epoxy resin (DOW6105)Obtain solution A; Take respectively 0.5gAl2O3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion,Add 2g solution A and at 50 DEG C respectively stir, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; TakeThe crosslinking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mixes and vacuum defoamation 1h with solution B;Pour mixed liquor into mould, after precuring 1h, be warming up to 125 DEG C and continue to solidify 1h at 100 DEG C, cooling and demoldingObtain filer content 20wt% epoxy composite material, wherein BN-HBP mass fraction in composite filler is 50%.
Embodiment 3
The present embodiment relates to the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material, bagDraw together following steps:
Step (1), Al2O3, BN surface grafting gamma-aminopropyl-triethoxy-silane (γ-APS)
Take 2gAl2O3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; InsteadShould finish rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 DEG C vacuum drying 1d, obtain Al2O3-APS。BN is process two-step method before grafted silane coupling agent: first, take 2gBN, at 100mL30wt% hydrochloric acid solutionMiddle dispersed with stirring, reacts after 1h at 50 DEG C, filters and with deionized water washing 3 times; Secondly, pre-acidifying BN is addedEnter in 50mL30wt% hydrogen peroxide, react after 1h at 50 DEG C, continue to be warming up to 75 DEG C of reaction 1h, product is centrifugalAnd at 50 DEG C vacuum drying 1d; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 2gAl2O3-APS and 3,4-diaminobenzoic acid (DABA) add 100mLN-methyl pyrrolidone(NMP), in, be stirred to DABA and fully dissolve; Subsequently, add respectively 15mL pyridine and triphenyl phosphite (TPP)And react 2h under 50 DEG C of nitrogen atmospheres; Reaction finishes rear high speed centrifugation, product N, N`-dimethyl formamide (DMF)Dissolve washing 3 times, at 50 DEG C, vacuum drying 1d, obtains Al2O3-HBP; BN-APS grafting HBP method and Al2O3-APSIdentical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Taking 1wt% promoter (DMP-30) fully mixes at 50 DEG C with Zhi Huan family epoxy resin (DOW6105)Obtain solution A; Take respectively 0.5gAl2O3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion,Add 2g solution A and at 50 DEG C respectively stir, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; TakeThe crosslinking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mixes and vacuum defoamation 1h with solution B;Pour mixed liquor into mould, after precuring 1h, be warming up to 125 DEG C and continue to solidify 1h at 100 DEG C, cooling and demoldingObtain filer content 20wt% epoxy composite material, wherein BN-HBP mass fraction in composite filler is 50%.
Embodiment 4
The present embodiment relates to the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material, bagDraw together following steps:
Step (1), Al2O3, BN surface grafting gamma-aminopropyl-triethoxy-silane (γ-APS)
Take 2gAl2O3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; InsteadShould finish rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 DEG C vacuum drying 1d, obtain Al2O3-APS。BN is process two-step method before grafted silane coupling agent: first, take 2gBN, at 100mL30wt% hydrochloric acid solutionMiddle dispersed with stirring, reacts after 1h at 50 DEG C, filters and with deionized water washing 3 times; Secondly, pre-acidifying BN is addedEnter in 50mL30wt% hydrogen peroxide, react after 1h at 50 DEG C, continue to be warming up to 75 DEG C of reaction 1h, product is centrifugalAnd at 50 DEG C vacuum drying 1d; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1gAl2O3-APS and 3,4-diaminobenzoic acid (DABA) add 50mLN-methyl pyrrolidone (NMP)In, be stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and at 50 DEG CUnder nitrogen atmosphere, react 1h; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves to be washedWash 3 times, at 50 DEG C, vacuum drying 1d, obtains Al2O3-HBP; BN-APS grafting HBP method and Al2O3-APSIdentical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Taking 1wt% promoter (DMP-30) fully mixes at 50 DEG C with Zhi Huan family epoxy resin (DOW6105)Obtain solution A; Take respectively 0.3gAl2O3-HBP and 1.2gBN-HBP, under room temperature in 20mL acetone ultrasonic pointAfter loose, add 2g solution A and at 50 DEG C, stir respectively, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone;Take the crosslinking agent methyl tetrahydro phthalic anhydride (MTHPA) of DOW6105 quality 50%, fully mix and vacuum defoamation with solution B1h; Pour mixed liquor into mould, after precuring 1h, be warming up to 125 DEG C and continue to solidify 1h at 100 DEG C, coolingThe demoulding obtains filer content 33wt% epoxy composite material, and wherein BN-HBP mass fraction in composite filler is 80%.
Implementation result
The ternary nano-micro structure epoxy composite material that above-described embodiment is obtained carries out TEM mensuration, and thermal conductivity factor and multipleClose in filler BN-HBP content and the total mensuration of the relation of the amount of filling out. Shown ternary of the present invention by Fig. 1, Fig. 2 and Fig. 4Nano-micro structure epoxy composite material has more complete heat conduction network, learns Al from composite TEM image2O3-HBPParticle plays bridging effect, has connected originally isolation BN-HBP mutually. Heat conductivility test by Fig. 3 shows, addsAl2O3The obtained epoxy composite material with nano-micro structure of the composite filler of-HBP and BN-HBP, its heat conductivility showsObviously cooperative effect, system thermal conductivity factor can regulate by changing filling mixture ratio, when BN-HBP accounts for composite filler 80wt%Time, performance the best; Adding the best proportioning compounded mix of 10wt% can reach and add the single BN-HBP of 30wt% and fill out simultaneouslyThe thermal conductivity factor of material, illustrates that ternary nano-micro structure epoxy composite material of the present invention has high heat conduction and is under low sizing contentNumber, has reduced manufacturing cost, and has kept mechanics and the processing characteristics of polymer composites excellence.
Above specific embodiments of the invention are described. It will be appreciated that, the present invention is not limited to above-mentioned spyDetermine embodiment, those skilled in the art can make various distortion or amendment within the scope of the claims, and this is shadow notRing flesh and blood of the present invention.
Claims (4)
1. a preparation method for the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material, is characterized in that,Formed by following steps:
Step (1), heat filling Al2O3, the silicane coupling agent surface grafted γ-APS of heat filling BN
Take 1～10gAl2O3, after fully disperseing, add 1～10wt% silane coupler in 50～500mL organic solventγ-APS also stirs, and under reflux conditions carries out coupling agent modified reaction 1 or 2h; After reaction finishes, separate, obtainPrecipitated product with organic solvent washing 2～3 times and at 50～100 DEG C vacuum drying 1～10d, obtain coupling agent and changeProperty filler Al2O3-APS; BN is process two-step method before grafted silane coupling agent: first, take 1～10gBN,Dispersed with stirring in the hydrochloric acid solution of 50～500mL, 1～30wt%, reacts after 1～10h at 50～100 DEG C, filters and usesDeionized water washing 2～3 times; Secondly, pre-acidifying BN is added in the hydrogen peroxide of 50～500mL, 1～30wt%, 50～At 75 DEG C, react after 1～10h, continue to be warming up to 75～100 DEG C of reaction 1～10h, then separate, the product of acquisition existsVacuum drying 1～10d at 50～100 DEG C; Pretreatment BN grafting γ-APS method and Al2O3Identical and be designated as BN-APS;
Step (2), Al2O3, the hyperbranched aromatic polyamide of BN surface grafting
Take respectively 1～10gAl2O3-APS and 3,4-diaminobenzoic acid add in 50～500mL organic solvent, stirFully dissolve to DABA; Then add respectively 5～50mL pyridine and triphenyl phosphite and at 50～100 DEG C of nitrogen atmospheresLower reaction 1～10h; After reaction finishes, separate, organic solvent dissolution washing 2～3 times for the precipitated product of acquisition,At 50～100 DEG C, vacuum drying 1～10d, obtains Al2O3-HBP; BN-APS grafting HBP method and Al2O3-APS is identicalAnd be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 0.1～10wt% promoter and epoxy resin and at 50～100 DEG C, be fully mixed to get solution A; Take respectively0～1gAl2O3-HBP and BN-HBP, after 1～100mL organic solvent for ultrasonic dispersion, add 1～10g under room temperatureDescribed solution A, and at 50～100 DEG C respectively stir, ultrasonic 1～10h, obtain homogeneous, remove the molten of organic solventLiquid B; Take the curing agent that accounts for epoxy resin quality 10～100%, fully mix and vacuum defoamation 1 with described solution B～10h; Pour mixed liquor into mould, after precuring 1～10h, be warming up to 125～150 DEG C and continue to solidify at 100～125 DEG C1～10h, cooling and demolding obtains filer content 20 or 33wt% epoxy composite material, and wherein BN-HBP is in composite fillerMass fraction is 50%, 80% or 90%;
The temperature of described coupling agent modified reaction is 0～200 DEG C;
Step (1) and the side that separates employing high speed centrifugation, vacuum filtration, normal pressure filtration described in step (2) or topple overMethod;
In step (1), (2) and (3), described organic solvent be oxolane, acetone, dioxanes, carrene,Chloroform, benzene,toluene,xylene, dimethyl formamide, 1-METHYLPYRROLIDONE or acetonitrile.
2. preparation method according to claim 1, is characterized in that, described epoxy resin is glycidol ethersEpoxy resin ester, ethylene oxidic ester based epoxy resin, glycidol amine epoxy resin, line style aliphatic category epoxy resinOr alicyclic based epoxy resin.
3. preparation method according to claim 1, is characterized in that, described curing agent is aliphatic amine, fragranceFamily's amine, amine modified firming agent, polyamide curing agent, anhydride-cured system, polyisocyanate curing agent.
4. preparation method according to claim 1, is characterized in that, described promoter is tertiary amine, tertiary ammonium salt, fatFat amine, replacement urea promoter, imidazoles, imidazole salts, acetyl acetone salt, triphenylphosphine, carboxylic metallic salt, carboxylic acidMetal salt complex, boron trifluoride amine complex or phenol accelerant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310370962.1A CN103525005B (en) | 2013-08-22 | 2013-08-22 | The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310370962.1A CN103525005B (en) | 2013-08-22 | 2013-08-22 | The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103525005A CN103525005A (en) | 2014-01-22 |
| CN103525005B true CN103525005B (en) | 2016-05-04 |
Family
ID=49927377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310370962.1A Expired - Fee Related CN103525005B (en) | 2013-08-22 | 2013-08-22 | The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103525005B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461963B (en) * | 2014-09-11 | 2018-07-20 | 佛山市三水金戈新型材料有限公司 | A kind of boron nitride powder of surface organic modification and its preparation method and application |
| CN106633641A (en) * | 2016-11-29 | 2017-05-10 | 太湖县金辉煌电子科技有限公司 | Silane-modified epoxy heat conduction material and preparation method thereof |
| CN106633644A (en) * | 2016-11-29 | 2017-05-10 | 太湖县金辉煌电子科技有限公司 | Antistatic epoxy heat-conducting material and preparation method thereof |
| CN106633642A (en) * | 2016-11-29 | 2017-05-10 | 太湖县金辉煌电子科技有限公司 | Octadecylamine graft epoxy heat-conducting material and preparation method thereof |
| CN106633643A (en) * | 2016-11-29 | 2017-05-10 | 太湖县金辉煌电子科技有限公司 | A nanometer epoxy heat-conducting material and a preparing method thereof |
| CN106751477A (en) * | 2016-11-29 | 2017-05-31 | 太湖县金辉煌电子科技有限公司 | A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof |
| CN106753129A (en) * | 2016-12-16 | 2017-05-31 | 安徽中威光电材料有限公司 | A kind of LED tack coats are modified enhanced high heat conduction type epoxy resin composite material and preparation method thereof with hyperbranched surface |
| CN106674611A (en) * | 2016-12-27 | 2017-05-17 | 铜陵市铜峰光电科技有限公司 | AlN-cellulose-CdTe high-thermal-conductivity type composite for LED and preparation method of AlN-cellulose-CdTe high-thermal-conductivity type composite |
| CN106674927A (en) * | 2016-12-27 | 2017-05-17 | 铜陵市铜峰光电科技有限公司 | Carbon fiber-graphene filled flame retardant type plastic with high thermal conductivity for LED and preparation method of carbon fiber-graphene filled flame retardant type plastic |
| CN107189348B (en) * | 2017-05-11 | 2020-01-21 | 华中科技大学 | Epoxy resin heat-conducting composite material and preparation and application thereof |
| WO2021035383A1 (en) * | 2019-08-23 | 2021-03-04 | Evonik Specialty Chemicals (Shanghai) Co., Ltd. | Thermal conductive filler and preparation method thereof |
| CN110718659A (en) * | 2019-10-21 | 2020-01-21 | 重庆云天化纽米科技股份有限公司 | Boron nitride coated battery separator and method of making same |
| CN111892753B (en) * | 2020-08-18 | 2022-08-23 | 华东理工大学 | Preparation method of modified hexagonal boron nitride heat-conducting film |
| CN114055881A (en) * | 2021-12-31 | 2022-02-18 | 苏州凯姆勒绝缘材料有限公司 | Composite polyimide film and preparation method thereof |
| CN115785864B (en) * | 2022-11-22 | 2024-08-06 | 哈尔滨理工大学 | PI-Al2O3Preparation method of PI-BN co-doped high-heat-conductivity epoxy resin composite material |
| CN117736549A (en) * | 2024-02-02 | 2024-03-22 | 广东博汇新材料科技有限公司 | Preparation method of high-heat-conductivity epoxy resin compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
| CN103224692A (en) * | 2013-05-09 | 2013-07-31 | 江门市道生工程塑料有限公司 | Filled polymer based heat conductive plastic and preparation method thereof |
-
2013
- 2013-08-22 CN CN201310370962.1A patent/CN103525005B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
| CN103224692A (en) * | 2013-05-09 | 2013-07-31 | 江门市道生工程塑料有限公司 | Filled polymer based heat conductive plastic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "超支化聚芳酰胺接枝氮化硼/环氧复合材料的制备与性能研究";彭鹏等;《绝缘材料》;20121231;第45卷(第3期);第1-5页 * |
| Influence of Interface Structure on Dielectric Properties of Epoxy/Alumina Nanocomposites;Jinhong Yu,et al.;《Macromolecular Research》;20120831;第20卷(第8期);第816-826页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103525005A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103525005B (en) | The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material | |
| CN103467917B (en) | The composite filler of modification is filled the resistance to preparation method who punctures epoxy composite material | |
| CN109913185B (en) | Multilayer structure heat-conducting composite material containing heat-conducting film and preparation method thereof | |
| CN101831264B (en) | Isotropic high-performance thermal conductive adhesive for filling carbon nano tube | |
| CN112210120B (en) | Heat-conducting filler and preparation method thereof, and polyarylethersulfone heat-conducting composite material and preparation method thereof | |
| CN104861910A (en) | Graphene-coated inorganic filler and epoxy resin composite adhesive and preparation method thereof | |
| CN109825010B (en) | Method for preparing brick-mud structure heat-conducting polymer composite material by utilizing magnetic field orientation | |
| CN104830031B (en) | A kind of epoxy resin composite material and preparation method thereof having both heat conduction and antistatic property | |
| CN113105735B (en) | High-molecular polymer composite heat conduction material with high heat conduction and preparation method thereof | |
| CN102191003A (en) | Silver-plated carbon nanotube heat-conducting adhesive and preparation method thereof | |
| CN109972398B (en) | High-thermal-conductivity flexible epoxy resin insulating material and preparation method and application thereof | |
| CN111909645A (en) | Epoxy resin composition for motor rotor encapsulation | |
| CN106751477A (en) | A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof | |
| CN112961461B (en) | Organic resin composite material with 3D polyimide as heat conducting framework and preparation method thereof | |
| CN111777776B (en) | Fabric-reinforced heat-conducting filler-soluble polymer heat-conducting composite material and preparation method thereof | |
| CN117659621A (en) | Epoxy resin-based composite material and preparation method and application thereof | |
| CN106633642A (en) | Octadecylamine graft epoxy heat-conducting material and preparation method thereof | |
| Chen et al. | Synthesis of PVA@ S-BNNSs flexible fiber backbone by electrostatic spinning assisting the construction of excellent ductile epoxy thermal interface materials | |
| CN105802488A (en) | Coating containing composite silicone rubber and preparation method of coating | |
| CN102079958B (en) | Diamond-filled isotropical high-performance heat-conductive adhesive and preparation method thereof | |
| CN102746489B (en) | Composition and preparation technology of hydroxyl-terminated liquid butadiene styrene rubber modified epoxy resin | |
| CN106633644A (en) | Antistatic epoxy heat-conducting material and preparation method thereof | |
| CN102617982B (en) | Carbon nanotube/nylon fiber modified epoxy resin composite material | |
| CN106633641A (en) | Silane-modified epoxy heat conduction material and preparation method thereof | |
| CN111040380A (en) | Heat-conducting modified epoxy resin-based composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 |