CN103525005A - Preparation method of epoxy composite material with low packing content, high thermal conductivity and ternary nano/micro structure - Google Patents
Preparation method of epoxy composite material with low packing content, high thermal conductivity and ternary nano/micro structure Download PDFInfo
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- CN103525005A CN103525005A CN201310370962.1A CN201310370962A CN103525005A CN 103525005 A CN103525005 A CN 103525005A CN 201310370962 A CN201310370962 A CN 201310370962A CN 103525005 A CN103525005 A CN 103525005A
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000004593 Epoxy Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000012856 packing Methods 0.000 title abstract 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent 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 5
- 239000000945 filler Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Aminopropanesulfonate Chemical compound NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 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 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 239000007822 coupling agent Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000005406 washing 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000703 high-speed centrifugation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- -1 glycidyl ester Chemical class 0.000 claims description 8
- 239000011231 conductive filler Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 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
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000008431 aliphatic amides Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 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
- 239000011159 matrix material Substances 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000004513 sizing Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 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 6
- 238000003917 TEM image Methods 0.000 description 5
- 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
- 238000002955 isolation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 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
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 230000011273 social behavior Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of an epoxy composite material with low packing content, high thermal conductivity and a ternary nano/micro structure. The preparation method comprises the following steps of modifying through a silane coupling agent gamma-APS (Aminopropyltriethoxysilane), and introducing amino groups on the surfaces of Al2O3 and h-BN; grafting hyperbranched aromatic polyamide (HBP) on the surface of initially modified packing by taking grafted amino groups as an active site to obtain modified packing Al2O3-HBP and BN-HBP; sufficiently mixing the two kinds of modified packing and an epoxy resin matrix according to a certain proportion and content; preparing the epoxy composite material with the ternary nano/micro structure by using a two step-by-step heating and curing methods. The heat conducting property of the epoxy composite material provided by the invention has a remarkable synergistic effect, the heat conductivity coefficient of a system can be regulated through changing the proportion of the packing, the epoxy composite material has a high heat conductivity coefficient under low packing content, the favorable mechanical and processing performances of the composite material of a polymer are kept, and the cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy composite material, be specifically related to the preparation method of the high heat conduction ternary of a kind of low sizing content nano-micro structure epoxy composite material.
Background technology
The develop rapidly of and package technique integrated along with microelectronics, the volume of electronic devices and components and logical circuit is more and more less, simultaneously, operating frequency sharply increases, cause semi-conductive envrionment temperature to change to high temperature direction, for guaranteeing the long-time reliable operation of electronic devices and components, heat-sinking capability just becomes the restraining factors of length in its in work-ing life in time.In addition, many production such as electrical equipment and electrical, LED illumination, aerospace, military equipment and high-tech area are also in the urgent need to having the material of excellent heat conductivity performance.Macromolecular material has mechanics, calorifics and the processing characteristics of unique insulating property, excellence, and has certain performance property changed by huge enough control and modification, because have the incomparable advantage of other materials.Yet general macromolecular material is all hot poor conductor, its thermal conductivity is generally lower than 0.5W m
-1k
-1, therefore, it is extensively concerned that preparation has the highly thermally conductive polymeric material of excellent comprehensive performance.
Filled-type thermally conductive polymer composites is by heat conductive filler (carbon system, metal system, pottery are three major types) and polymeric matrix, the heterogeneous composite heat-conducting system compound through disperseing, lamination is compound and form the modes such as surperficial heat conducting film forms after processing.Novel high intrinsic heat conduction carbon class filler, as Graphene, carbon nanotube etc., is difficult to realize industrialization at present because cost is higher, these fillers are electric good conductors simultaneously, has also limited the application of corresponding matrix material in insulation environment.Although tradition heat conductive filler cost is relatively low, due to the intrinsic capacity of heat transmission a little less than, corresponding matrix material filler content is higher, this has not only increased cost, the more important thing is deteriorated mechanics and processing characteristics.Therefore, prepare low sizing content, high thermal conductivity polymer matrix composite 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, the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material is provided.The method is with heat conductivility excellence, electrical isolation, chemically stable micron hexagonal boron nitride (h-BN) and nano aluminium oxide (Al with low cost, over-all properties is good
2o
3) particle is composite heat-conducting filler, and carries out surface modification by the hyperbranched aromatic polyamide of two-step approach grafting; Matrix is selected bonding, mechanics, 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, and the preparation method of a kind of low sizing content, high heat conduction ternary nano-micro structure epoxy composite material, comprises the steps:
Step (1), heat conductive filler Al
2o
3, the silicane coupling agent surface grafted γ-APS of heat conductive filler BN
Take 1～10g Al
2o
3, after fully disperseing in 50～500mL organic solvent, add 1～10wt% silane coupling agent γ-APS and stir, under reflux conditions carry out coupling agent modified reaction 1～10h; After reaction finishes, separation, the precipitated product of acquisition with organic solvent washing 2～3 times and at 50～100 ℃ vacuum-drying 1～10d, obtain coupling agent modified filler Al
2o
3-APS; BN before grafted silane coupling agent through two-step method: first, take 1～10g BN, dispersed with stirring in the hydrochloric acid soln of 50～500mL, 1～30wt%, reacts after 1～10h at 50～100 ℃, filters and uses deionized water wash 2～3 times; Secondly, pre-acidifying BN is added in the hydrogen peroxide of 50～500mL, 1～30wt%, react after 1～10h at 50～75 ℃, continue to be warming up to 75～100 ℃ of reaction 1～10h, then separated, the product of acquisition is vacuum-drying 1～10d at 50～100 ℃; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1～10g Al
2o
3-APS and 3,4-diaminobenzoic acid (DABA) add in 50～500mL organic solvent, are stirred to DABA and fully dissolve; Then add respectively 5～50mL pyridine and triphenyl phosphite (TPP) and react 1～10h under 50～100 ℃ of nitrogen atmospheres; After reaction finishes, separation, organic solvent dissolution washing 2～3 times for the precipitated product of acquisition, at 50～100 ℃, vacuum-drying 1～10d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-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% promotor and epoxy resin and at 50～100 ℃, be fully mixed to get solution A; Take respectively 0～1g Al
2o
3-HBP and BN-HBP, after 1～100mL organic solvent for ultrasonic dispersion, add solution A described in 1～10g under room temperature, and at 50～100 ℃, stir respectively, ultrasonic 1～10h, the solution B that obtains homogeneous, removes organic solvent; Take the solidifying agent that accounts for epoxy resin quality 10～100%, fully mix and vacuum defoamation 1～10h with described solution B; Pour mixed solution into mould, after Procuring 1～10h, be warming up to 125～150 ℃ and continue to solidify 1～10h at 100～125 ℃, cooling and demolding obtains filler content 0～65wt% epoxy composite material, and wherein BN-HBP massfraction in composite filler is 0～100%.
Preferably, described epoxy resin is glycidyl ether based epoxy resin ester, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, line style aliphatic category epoxy resin or alicyclic based epoxy resin.
Preferably, described solidifying agent is aliphatics amine, aromatic amine, amine modified firming agent, polyamide curing agent, anhydride-cured system, polyisocyanate curing agent.
Preferably, described promotor is tertiary amine, tertiary ammonium salt, aliphatic amide, replacement urea promotor, imidazoles, imidazole salts, acetyl acetone salt, triphenylphosphine, three benzene base phosphine Perverse salt, carboxylic metallic salt, carboxylic acid metal's salt complex, boron trifluoride amine complex or phenol accelerant.
Preferably, the temperature of described coupling agent modified reaction is 0～200 ℃.
Preferably, described coupling agent modified filler is by further modify and graft simple linear polymer, branched chain polymer, hyperbranched polymer, comb-shaped polymer or star polymer.
Preferably, step (1) and the separated method that adopts high speed centrifugation, vacuum filtration, normal pressure to filter or topple over described in step (2).
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 is tetrahydrofuran (THF), acetone, dioxan, methylene dichloride, trichloromethane, benzene,toluene,xylene, dimethyl formamide, N-Methyl pyrrolidone or acetonitrile.
In the present invention, heat conductive filler used can be one or more of metal, carbon and pottery, and described metal can be copper, silver, gold, nickel or aluminium; Described carbon can be decolorizing carbon, graphite, diamond, carbon nanotube or Graphene; Described pottery can be boron nitride, aluminium nitride, silicon nitride, magnesium oxide, beryllium oxide, aluminum oxide, zinc oxide, silicon-dioxide or silicon carbide.In addition, described silane coupling agent can replace with titanate coupling agent, aluminate coupling agent or aluminium titanium composite coupler.
Compared with prior art, the present invention has following beneficial effect:
1, hyperbranched aromatic polyamide grafting Al of the present invention
2o
3-HBP and BN-HBP filler disperse homogeneous in matrix, and consistency is outstanding: from modified filler TEM image, learn the polymer layer of filling surface grafting one number of plies nanometer thickness; From matrix material TEM image, learn, reuniting and pi-pi accumulation does not appear in modified filler, and interface does not have open defect (white space is to destroy matrix around in anisotropy distribution BN-HBP slicing processes to cause);
2, ternary nano-micro structure epoxy composite material of the present invention shows obvious cooperative behavior, and from heat conduction, figure learns, its thermal conductivity can regulate by changing compounded mix proportioning, and BN-HBP while accounting for compounded mix 80wt% performance best;
3, ternary nano-micro structure epoxy composite material of the present invention has high thermal conductivity coefficient under low sizing content, from heat conduction, figure learns, add the best proportioning compounded mix of 10wt% and can reach the thermal conductivity that adds the single BN-HBP filler of 30wt%, reduced manufacturing cost, meanwhile, the mechanics and the processing characteristics that have kept polymer composites excellence;
4, ternary nano-micro structure epoxy composite material of the present invention has more complete heat conduction network, learns Al from matrix material TEM image
2o
3-HBP particle plays bridging effect, has connected originally isolation BN-HBP mutually.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is FT-IR spectrogram of the present invention, and wherein (a) represents Al
2o
3, Al
2o
3-APS, Al
2o
3-HBP, (b) represents BN, BN-APS, BN-HBP.
Fig. 2 is the TEM image of modified filler of the present invention, and wherein (a) is Al
2o
3-HBP; (b) be BN-HBP, arrow indication is polymkeric substance.
Fig. 3 is BN-HBP content and the total relation of the amount of filling out in epoxy composite material thermal conductivity 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 matrix thermal conductivity rate of increase in 10wt%, 30wt% system.
Fig. 4 is the TEM figure of the best proportioning epoxy composite material section of 10wt% filler content of the present invention, and wherein figure (b) is the partial enlarged drawing of the boxed area of figure (a).
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These all 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, comprises the steps:
Step (1), Al
2o
3, BN surface grafting γ-aminopropyl triethoxysilane (γ-APS)
Take 2g Al
2o
3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; Reaction finishes rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 ℃ vacuum-drying 1d, obtain Al
2o
3-APS.BN before grafted silane coupling agent through two-step method: first, take 2gBN, dispersed with stirring in 100mL30wt% hydrochloric acid soln, reacts after 1h at 50 ℃, filters and uses deionized water wash 3 times; Secondly, pre-acidifying BN is added in 50mL30wt% hydrogen peroxide, reacts after 1h at 50 ℃, continue to be warming up to 75 ℃ of reaction 1h, product centrifugal and at 50 ℃ vacuum-drying 1d; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1g Al
2o
3-APS and 3,4-diaminobenzoic acid (DABA) add in 50mLN-methyl-2-pyrrolidone (NMP), are stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and react 1h under 50 ℃ of nitrogen atmospheres; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves washing 3 times, and at 50 ℃, vacuum-drying 1d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-APS is identical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 1wt% promotor (DMP-30) Yu Zhihuan family's epoxy resin (DOW6105) and at 50 ℃, be fully mixed to get solution A; Take respectively 0.5gAl
2o
3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion, add 2g solution A and at 50 ℃, stir respectively, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; Take the linking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mix and vacuum defoamation 1h with solution B; Pour mixed solution into mould, after Procuring 1h, be warming up to 125 ℃ and continue to solidify 1h at 100 ℃, cooling and demolding obtains filler content 20wt% epoxy composite material, and wherein BN-HBP massfraction 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, comprises the steps:
Step (1), Al
2o
3, BN surface grafting γ-aminopropyl triethoxysilane (γ-APS)
Take 5g Al
2o
3, after fully disperseing, add 2wt% γ-APS stirring and refluxing 2h in 200mL dimethylbenzene; Reaction finishes rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 ℃ vacuum-drying 1d, obtain Al
2o
3-APS.BN before grafted silane coupling agent through two-step method: first, take 5gBN, dispersed with stirring in 200mL30wt% hydrochloric acid soln, reacts after 1h at 50 ℃, filters and uses deionized water wash 3 times; Secondly, pre-acidifying BN is added in 100mL30wt% hydrogen peroxide, reacts after 1h at 50 ℃, continue to be warming up to 75 ℃ of reaction 1h, product centrifugal and at 50 ℃ vacuum-drying 1d; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1g Al
2o
3-APS and 3,4-diaminobenzoic acid (DABA) add in 50mLN-methyl-2-pyrrolidone (NMP), are stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and react 1h under 50 ℃ of nitrogen atmospheres; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves washing 3 times, and at 50 ℃, vacuum-drying 1d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-APS is identical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 1wt% promotor (DMP-30) Yu Zhihuan family's epoxy resin (DOW6105) and at 50 ℃, be fully mixed to get solution A; Take respectively 0.5gAl
2o
3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion, add 2g solution A and at 50 ℃, stir respectively, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; Take the linking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mix and vacuum defoamation 1h with solution B; Pour mixed solution into mould, after Procuring 1h, be warming up to 125 ℃ and continue to solidify 1h at 100 ℃, cooling and demolding obtains filler content 20wt% epoxy composite material, and wherein BN-HBP massfraction 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, comprises the steps:
Step (1), Al
2o
3, BN surface grafting γ-aminopropyl triethoxysilane (γ-APS)
Take 2g Al
2o
3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; Reaction finishes rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 ℃ vacuum-drying 1d, obtain Al
2o
3-APS.BN before grafted silane coupling agent through two-step method: first, take 2gBN, dispersed with stirring in 100mL30wt% hydrochloric acid soln, reacts after 1h at 50 ℃, filters and uses deionized water wash 3 times; Secondly, pre-acidifying BN is added in 50mL30wt% hydrogen peroxide, reacts after 1h at 50 ℃, continue to be warming up to 75 ℃ of reaction 1h, product centrifugal and at 50 ℃ vacuum-drying 1d; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 2g Al
2o
3-APS and 3,4-diaminobenzoic acid (DABA) add in 100mLN-methyl-2-pyrrolidone (NMP), are stirred to DABA and fully dissolve; Subsequently, add respectively 15mL pyridine and triphenyl phosphite (TPP) and react 2h under 50 ℃ of nitrogen atmospheres; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves washing 3 times, and at 50 ℃, vacuum-drying 1d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-APS is identical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 1wt% promotor (DMP-30) Yu Zhihuan family's epoxy resin (DOW6105) and at 50 ℃, be fully mixed to get solution A; Take respectively 0.5gAl
2o
3-HBP and BN-HBP, under room temperature in 10mL acetone after ultrasonic dispersion, add 2g solution A and at 50 ℃, stir respectively, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; Take the linking agent methyl tetrahydro phthalic anhydride (MTHPA) that DOW6105 quality is equal, fully mix and vacuum defoamation 1h with solution B; Pour mixed solution into mould, after Procuring 1h, be warming up to 125 ℃ and continue to solidify 1h at 100 ℃, cooling and demolding obtains filler content 20wt% epoxy composite material, and wherein BN-HBP massfraction 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, comprises the steps:
Step (1), Al
2o
3, BN surface grafting γ-aminopropyl triethoxysilane (γ-APS)
Take 2g Al
2o
3, after fully disperseing, add 1wt% γ-APS stirring and refluxing 1h in 100mL dimethylbenzene; Reaction finishes rear high speed centrifugation, product with dimethylbenzene washing 3 times and at 50 ℃ vacuum-drying 1d, obtain Al
2o
3-APS.BN before grafted silane coupling agent through two-step method: first, take 2gBN, dispersed with stirring in 100mL30wt% hydrochloric acid soln, reacts after 1h at 50 ℃, filters and uses deionized water wash 3 times; Secondly, pre-acidifying BN is added in 50mL30wt% hydrogen peroxide, reacts after 1h at 50 ℃, continue to be warming up to 75 ℃ of reaction 1h, product centrifugal and at 50 ℃ vacuum-drying 1d; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting (HBP)
Take respectively 1g Al
2o
3-APS and 3,4-diaminobenzoic acid (DABA) add in 50mLN-methyl-2-pyrrolidone (NMP), are stirred to DABA and fully dissolve; Subsequently, add respectively 5mL pyridine and triphenyl phosphite (TPP) and react 1h under 50 ℃ of nitrogen atmospheres; Reaction finishes rear high speed centrifugation, product N, and N`-dimethyl formamide (DMF) dissolves washing 3 times, and at 50 ℃, vacuum-drying 1d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-APS is identical and be designated as BN-HBP;
Step (3), the preparation of ternary nano-micro structure epoxy composite material
Take 1wt% promotor (DMP-30) Yu Zhihuan family's epoxy resin (DOW6105) and at 50 ℃, be fully mixed to get solution A; Take respectively 0.3gAl
2o
3-HBP and 1.2gBN-HBP, under room temperature in 20mL acetone after ultrasonic dispersion, add 2g solution A and at 50 ℃, stir respectively, ultrasonic 1h, the solution B that obtains homogeneous, removes acetone; Take the linking agent methyl tetrahydro phthalic anhydride (MTHPA) of DOW6105 quality 50%, fully mix and vacuum defoamation 1h with solution B; Pour mixed solution into mould, after Procuring 1h, be warming up to 125 ℃ and continue to solidify 1h at 100 ℃, cooling and demolding obtains filler content 33wt% epoxy composite material, and wherein BN-HBP massfraction 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 BN-HBP content and the total mensuration of the relation of the amount of filling out in thermal conductivity and compounded mix.By Fig. 1, Fig. 2 and Fig. 4, shown, ternary nano-micro structure epoxy composite material of the present invention has more complete heat conduction network, learns Al from matrix material TEM image
2o
3-HBP particle plays bridging effect, has connected originally isolation BN-HBP mutually.Heat conductivility test by Fig. 3 shows, adds Al
2o
3the obtained epoxy composite material with nano-micro structure of the composite filler of-HBP and BN-HBP, its heat conductivility shows obvious synergistic effect, and system thermal conductivity can regulate by changing filling mixture ratio, and when BN-HBP accounts for composite filler 80wt%, performance is best; Add the best proportioning compounded mix of 10wt% simultaneously and can reach the thermal conductivity that adds the single BN-HBP filler of 30wt%, illustrate that ternary nano-micro structure epoxy composite material of the present invention has high thermal conductivity coefficient under low sizing content, reduce manufacturing cost, and 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 particular implementation, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. the composite filler filling of modification, a resistance to preparation method who punctures epoxy composite material, is characterized in that, comprises the following steps:
Step (1), heat conductive filler Al
2o
3, the silicane coupling agent surface grafted γ-APS of heat conductive filler BN
Take 1～10gAl
2o
3, after fully disperseing in 50～500mL organic solvent, add 1～10wt% silane coupling agent γ-APS and stir, under reflux conditions carry out coupling agent modified reaction 1～10h; After reaction finishes, separation, the precipitated product of acquisition with organic solvent washing 2～3 times and at 50～100 ℃ vacuum-drying 1～10d, obtain coupling agent modified filler Al
2o
3-APS; BN before grafted silane coupling agent through two-step method: first, take 1～10gBN, dispersed with stirring in the hydrochloric acid soln of 50～500mL, 1～30wt%, reacts after 1～10h at 50～100 ℃, filters and uses deionized water wash 2～3 times; Secondly, pre-acidifying BN is added in the hydrogen peroxide of 50～500mL, 1～30wt%, react after 1～10h at 50～75 ℃, continue to be warming up to 75～100 ℃ of reaction 1～10h, then separated, the product of acquisition is vacuum-drying 1～10d at 50～100 ℃; Pre-treatment BN grafting γ-APS method and Al
2o
3identical and be designated as BN-APS;
Step (2), Al
2o
3, the hyperbranched aromatic polyamide of BN surface grafting
Take respectively 1～10gAl
2o
3-APS and 3,4-diaminobenzoic acid add in 50～500mL organic solvent, are stirred to DABA and fully dissolve; Then add respectively 5～50mL pyridine and triphenyl phosphite and react 1～10h under 50～100 ℃ of nitrogen atmospheres; After reaction finishes, separation, organic solvent dissolution washing 2～3 times for the precipitated product of acquisition, at 50～100 ℃, vacuum-drying 1～10d, obtains Al
2o
3-HBP; BN-APS grafting HBP method and Al
2o
3-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% promotor and epoxy resin and at 50～100 ℃, be fully mixed to get solution A; Take respectively 0～1gAl
2o
3-HBP and BN-HBP, after 1～100mL organic solvent for ultrasonic dispersion, add solution A described in 1～10g under room temperature, and at 50～100 ℃, stir respectively, ultrasonic 1～10h, the solution B that obtains homogeneous, removes organic solvent; Take the solidifying agent that accounts for epoxy resin quality 10～100%, fully mix and vacuum defoamation 1～10h with described solution B; Pour mixed solution into mould, after Procuring 1～10h, be warming up to 125～150 ℃ and continue to solidify 1～10h at 100～125 ℃, cooling and demolding obtains filler content 0～65wt% epoxy composite material, and wherein BN-HBP massfraction in composite filler is 0～100%.
2. preparation method according to claim 1, it is characterized in that, described epoxy resin is glycidyl ether based epoxy resin ester, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, line style aliphatic category epoxy resin or alicyclic based epoxy resin.
3. preparation method according to claim 1, is characterized in that, described solidifying agent is aliphatics amine, aromatic amine, amine modified firming agent, polyamide curing agent, anhydride-cured system, polyisocyanate curing agent.
4. preparation method according to claim 1, it is characterized in that, described promotor is tertiary amine, tertiary ammonium salt, aliphatic amide, replacement urea promotor, imidazoles, imidazole salts, acetyl acetone salt, triphenylphosphine, three benzene base phosphine Perverse salt, carboxylic metallic salt, carboxylic acid metal's salt complex, boron trifluoride amine complex or phenol accelerant.
5. preparation method according to claim 1, is characterized in that, the temperature of described coupling agent modified reaction is 0～200 ℃.
6. preparation method according to claim 1, is characterized in that, described coupling agent modified filler is by further modify and graft simple linear polymer, branched chain polymer, hyperbranched polymer, comb-shaped polymer or star polymer.
7. preparation method according to claim 1, is characterized in that, step (1) and the method that described in step (2), separated employing high speed centrifugation, vacuum filtration, normal pressure filter or topple over.
8. preparation method according to claim 1, is characterized in that, disperse to adopt ultrasonic, stirring or cytoclastic method to carry out described in step (1) and step (3).
9. preparation method according to claim 1, it is characterized in that, in step (1), (2) and (3), described organic solvent is tetrahydrofuran (THF), acetone, dioxan, methylene dichloride, trichloromethane, benzene,toluene,xylene, dimethyl formamide, N-Methyl pyrrolidone or acetonitrile.
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| CN115785864A (en) * | 2022-11-22 | 2023-03-14 | 哈尔滨理工大学 | PI-Al 2 O 3 Preparation method of PI-BN codoped high-thermal-conductivity epoxy resin composite material |
| 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 |
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