CN117866287A - Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer - Google Patents
Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer Download PDFInfo
- Publication number
- CN117866287A CN117866287A CN202311807260.5A CN202311807260A CN117866287A CN 117866287 A CN117866287 A CN 117866287A CN 202311807260 A CN202311807260 A CN 202311807260A CN 117866287 A CN117866287 A CN 117866287A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- solvent
- graphite nano
- water
- resin
- 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.)
- Pending
Links
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 73
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 63
- 239000010439 graphite Substances 0.000 title claims abstract description 63
- 239000002135 nanosheet Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 14
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 32
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 25
- 239000011231 conductive filler Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- -1 amino modified graphite Chemical class 0.000 claims description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960003638 dopamine Drugs 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002064 nanoplatelet Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- YUEDZVRMWQBEPT-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O YUEDZVRMWQBEPT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 229920001973 fluoroelastomer Polymers 0.000 claims description 2
- 229920005560 fluorosilicone rubber Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- XNBSIDRUUSNPGM-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]prop-2-enamide Chemical compound OC1=CC=C(CCNC(=O)C=C)C=C1O XNBSIDRUUSNPGM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920006350 polyacrylonitrile resin Polymers 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920013716 polyethylene resin Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920006380 polyphenylene oxide Polymers 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 14
- 239000004020 conductor Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- 229910021389 graphene Inorganic materials 0.000 description 11
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229920001690 polydopamine Polymers 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019476 oil-water mixture Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphite nano-sheet in-situ growth boron nitride composite material, a preparation method thereof and a heat conducting polymer, and relates to the technical field of heat conducting materials. The invention aims to overcome the defects of poor insulativity and low filling amount of graphite nano sheets in a resin matrix in the prior art; the technical problem of low thermal conductivity of boron nitride is to provide a preparation method of a graphite nano-sheet in-situ growth boron nitride composite material, and the obtained graphite nano-sheet in-situ growth boron nitride composite material is applied to the preparation of a heat conducting polymer, so that the heat conducting property is improved and the insulating property of the polymer is improved.
Description
Technical field:
the invention relates to the technical field of heat conducting materials, in particular to a graphite nano-sheet in-situ growth boron nitride composite material, a preparation method thereof and a heat conducting polymer.
The background technology is as follows:
the key to the development of the modern electronic information industry is the development of new electronic products, and in recent years, people are devoted to miniaturization of electronic equipment and wearable research of electronic devices, and miniaturization of electronic processors is achieved. However, the energy absorbed on the electronic device is not reduced correspondingly, which would lead to an increase in the amount of heat generated per unit area. The increase in heat can raise the temperature of the electronic device, affecting the operating efficiency, reliability and lifetime of the device. Therefore, efficient heat dissipation is particularly urgent in smaller-sized electronic devices. Polymers have attracted considerable attention from researchers because of their light weight, low cost and ease of processing. However, the thermal conductivity of pure polymers is typically only 0.2W/(m.k), which prevents their use in thermal management. In order to improve the heat conductivity, a method is generally used in which a heat conductive filler having high heat conductivity and good insulation is added.
Graphene (Graphene) is a material consisting of carbon atoms in sp 2 The two-dimensional carbon nano material hybridized into hexagonal honeycomb lattice has excellent electrical, optical and mechanical properties, has wide application prospect in the aspects of materials, energy sources, biomedicine, drug delivery, micro-nano processing and the like, and is considered as one of the revolutionary materials in the future of human beings. However, the cost of preparing pure graphene in the current industrial production is higher, the process is complex, and the graphite nano-sheet is used as a low-cost substitute for pure graphene, has excellent thermal, optical and mechanical properties of graphene, and is widely applied to the field of industrial production.
The crystal structure of the hexagonal boron nitride is very similar to that of graphite, and the physical and chemical properties of the hexagonal boron nitride and the graphite are also similar, so the hexagonal boron nitride is also called as white graphite, has important application in the fields of heat conduction, lubrication, hydrogen storage, battery diaphragm materials, high-temperature oxidation resistance coatings, catalysis and the like, has the advantages of low density, high melting point, low hardness, good thermal shock resistance, good mechanical processability and the like, and has excellent performances of high temperature resistance, small thermal expansion coefficient, low dielectric constant, reliable electrical insulation and the like, but the thermal conductivity of the boron nitride is poor.
The thermal conductivity of the polymer matrix composite is also affected by factors such as filler size, shape and structure. Researchers dope fillers of different sizes and shapes in the same matrix, and increase the thermal conductivity of the composite material by increasing the compactness of the filler network. In addition, people also connect different types of fillers with each other by means of covalent bonds or non-covalent bonds to prepare composite fillers containing interaction force, and the heat conduction performance of the material is improved by utilizing the synergistic effect of the composite fillers.
Graphite is widely used in thermally conductive polymeric materials due to its high thermal conductivity and good mechanical properties. However, the single filler has nearly uniform size and shape, and has low filling amount in the polymer matrix, is difficult to disperse uniformly, and is unfavorable for heat transmission. And graphite has poor insulation properties, and is easy to cause short circuit when being directly applied to microelectronic devices.
In order to solve the problems, patent CN202111024525.5 discloses a preparation method of a boron nitride graphene oxide polyimide composite material, which is characterized in that graphene oxide is prepared by a chemical oxidation method, and simultaneously micron boron nitride is prepared into boron nitride nano sheets by a hydrothermal method, and a heat-conducting and insulating composite filler is prepared by utilizing pi-pi interaction between boron nitride and graphene oxide. However, the method needs to treat the graphene by using strong acid, and can damage the lattice structure of the graphene, thereby affecting the heat conduction property. Meanwhile, the acting force between the graphene oxide and the boron nitride is weak, the interface thermal resistance between the two fillers is large, and phase separation is easy to occur.
The invention comprises the following steps:
the invention aims to overcome the defects of poor insulativity and low filling amount of graphite nano sheets in a resin matrix in the prior art; the technical problem of low thermal conductivity of boron nitride is to provide a preparation method of a graphite nano-sheet in-situ growth boron nitride composite material, and the obtained graphite nano-sheet in-situ growth boron nitride composite material is applied to the preparation of a heat conducting polymer, so that the heat conducting property is improved and the insulating property of the polymer is improved.
The inventors of the present invention have unexpectedly found that coupling and sintering a boron nitride precursor with a graphite nanoplatelet can improve the insulating properties of the graphite/boron nitride composite material, and the filling amount of the graphite/boron nitride composite material in the polymer matrix, and form an effective heat conducting network, thereby improving the insulating properties of the polymer while improving the heat conducting properties.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
in order to achieve the above object, one of the objects of the present invention is to provide a method for preparing a graphite nano-sheet in-situ grown boron nitride composite material, comprising the following steps:
(1) Stirring a boron source and a nitrogen source in a solvent for reaction to obtain a boron nitride precursor;
(2) Stirring and reacting the boron nitride precursor and a coupling agent in a solvent to obtain a coupling agent modified boron nitride precursor;
(3) Stirring graphite nano-sheets and an amino-containing modifier in a solvent for reaction to obtain amino-modified graphite nano-sheets;
(4) Mixing a coupling agent modified boron nitride precursor and an amino modified graphite nano-sheet in a solvent, adding isocyanate, stirring for reaction, filtering, washing, drying, and sintering in a protective atmosphere to obtain the graphite nano-sheet in-situ grown boron nitride composite material.
The second object of the present invention is to provide a graphite nano-sheet in-situ grown boron nitride composite material obtained by the above preparation method.
The invention further provides a heat-conducting polymer, which comprises a polymer matrix and a heat-conducting filler, wherein the heat-conducting filler is the graphite nano-sheet in-situ grown boron nitride composite material.
The beneficial effects of the invention are as follows: according to the invention, the bonding force between the graphite nano-sheets and the boron nitride and the insulating property of the in-situ growth boron nitride composite material of the graphite nano-sheets can be improved by compounding the boron nitride precursor and the graphite nano-sheets and then sintering, so that the filling amount of the in-situ growth boron nitride composite material of the graphite nano-sheets in the polymer matrix is further improved, the filling amount in the polymer matrix can be up to 24%, and a heat conduction network can be effectively formed, thereby improving the heat conductivity of the polymer.
Description of the drawings:
FIG. 1 is an infrared spectrum of a boron nitride precursor before and after modification by a silane coupling agent KH750 in example 1 of the present invention;
FIG. 2 is an infrared spectrum of graphite nanoplatelets before and after dopamine hydrochloride modification in example 1 of the present invention;
FIG. 3 is an infrared spectrum of boron nitride precursor/graphite nanoplatelets before and after hexamethylene diisocyanate grafting in example 1 of the present invention;
FIG. 4 is an SEM image of the thermally conductive filler obtained in example 5 of the invention;
fig. 5 is an SEM image of the heat conductive filler prepared in example 6 of the present invention.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The invention provides a preparation method of a graphite nano-sheet in-situ growth boron nitride composite material, which comprises the following steps:
(1) Stirring a boron source and a nitrogen source in a solvent for reaction to obtain a boron nitride precursor;
(2) Stirring and reacting the boron nitride precursor and a coupling agent in a solvent to obtain a coupling agent modified boron nitride precursor;
(3) Stirring graphite nano-sheets and an amino-containing modifier in a solvent for reaction to obtain amino-modified graphite nano-sheets;
(4) Mixing a coupling agent modified boron nitride precursor and an amino modified graphite nano-sheet in a solvent, adding isocyanate, stirring for reaction, filtering, washing, drying, and sintering in a protective atmosphere to obtain the graphite nano-sheet in-situ grown boron nitride composite material.
In the step (1), the boron source is at least one selected from boric acid and borax; the nitrogen source is at least one selected from melamine, amine chloride and urea.
In the step (1), the molar ratio of the boron source to the nitrogen source is (1.5-3.5): 1, wherein the boron source is calculated as boron element, and the nitrogen source is calculated as nitrogen element.
In the step (1), the solvent is an oil-water mixed solution. The oil-water mixed solution is a mixture of water and oil, and comprises 20-80 vol% of water and 20-80 vol% of oily solvent; preferably, the oil-water mixed solution comprises 30-70 Vol% of water and 30-70 Vol% of oily solvent; further preferably, the oil-water mixture comprises 40-60 vol% of water and 40-60 vol% of oily solvent; more preferably, the oil-water mixture contains 45 to 55Vol% of water and 45 to 55Vol% of an oily solvent. Wherein Vol% is the volume percentage.
In a further technical scheme, the oily solvent is at least one selected from liquid paraffin, oleic acid, alkane solvent, silicone oil and petroleum ether.
In some preferred embodiments of the present invention, the oil-water mixture further comprises an emulsifier, wherein the emulsifier can form the oil-water mixture into a water-in-oil structure, and the emulsifier can be span-80.
In the step (1), in order to obtain a precursor with uniform size, the temperature of the stirring reaction is 70-110 ℃, preferably 85-105 ℃, more preferably 90-100 ℃; the stirring reaction time is 4-24 hours, preferably 4-16 hours.
In the step (2), the coupling agent is a silane coupling agent or a titanate coupling agent. Further, the silane coupling agent is at least one selected from KH570, KH560, KH550, KH792, GR-SI351, GR-SI151 and A-151.
In the step (2), the mass ratio of the boron nitride precursor to the coupling agent is 1 (0.1-2), preferably 1 (0.5-1).
In the step (2), the solvent is pure water or a mixed solvent of water and ethanol, wherein the mixed solution of water and ethanol comprises 10-90 Vol% of water and 10-90 Vol% of ethanol; preferably, the water and ethanol mixture comprises 20 to 80Vol% water and 20 to 80Vol% ethanol.
In the step (2), the stirring reaction time is 12-48 hours, preferably 18-24 hours.
In the step (3), the modifier containing amino is at least one selected from dopamine, dopamine hydrochloride, dopamine acrylamide and N-alanyl dopamine; preferably dopamine hydrochloride.
In the step (3), the mass ratio of the graphite nano-sheets to the modifier containing amino groups is 1 (0.5-4), preferably 1 (1-2).
In step (3), the solvent is Tris-Cl buffer or PBS buffer, preferably Tris-Cl buffer.
In the step (3), in order to uniformly adhere the dopamine to the graphite nano-sheets, the temperature of the stirring reaction is 25-70 ℃; the stirring reaction time is 12-24 hours.
In step (4), the isocyanate is a polyisocyanate, and the polyisocyanate may be a diisocyanate and/or a triisocyanate. Further, the diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, tetramethyl isophthalene diisocyanate, 1, 4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1, 4-phenylene diisocyanate, triphenylmethane triisocyanate and dimethyltriphenylmethane tetraisocyanate.
In the step (4), the mass ratio of the coupling agent modified boron nitride precursor to the amino modified graphite nano-sheet is 1 (0.25-6); further preferably 1 (1) to 4); more preferably 1 (2) to (4).
The inventor finds that in the process of compositing the boron nitride precursor and the graphite nano-sheets, the proportion of the graphite nano-sheets is too low, so that a large amount of boron nitride is doped in the prepared filler, and the thermal conductivity of the boron nitride is lower than that of the graphite nano-sheets, so that the thermal conductivity of the composite filler is poor; and too high a proportion of graphite nanoplatelets can lead to deterioration of the insulating properties of the composite filler.
In the step (4), the addition amount of the isocyanate accounts for 1-10% of the total mass of the coupling agent modified boron nitride precursor and the amino modified graphite nano-sheet.
In the step (4), the solvent is at least one selected from N-hexane, N-pentane, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).
In the step (4), the stirring reaction time is 2-24 hours.
In the step (4), the sintering temperature is 900-1600 ℃, preferably 1200-1600 ℃; the sintering time is 1 to 12 hours, preferably 6 to 10 hours. The gradient sintering mode can be adopted, and the temperature is raised to a certain temperature for a period of time, and then raised to a higher temperature for a period of time.
In step (4), the shielding gas may be known to those skilled in the art, including but not limited to nitrogen and/or an inert gas, preferably nitrogen.
The invention provides a graphite nano-sheet in-situ growth boron nitride composite material obtained by the preparation method.
The invention provides a heat-conducting polymer, which comprises a polymer matrix and a heat-conducting filler, wherein the heat-conducting filler is the graphite nano-sheet in-situ grown boron nitride composite material.
In the present invention, the thermally conductive polymer comprises 76 to 99wt% of the polymer matrix and 1 to 24wt% of the thermally conductive filler, based on the total weight of the thermally conductive polymer, and the content of the thermally conductive filler may be 1wt%, 2wt%, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 24wt% or any value in the range of any two of the above values, for example.
In a further technical scheme, the polymer matrix is at least one selected from polypropylene resin, polyethylene resin, polyvinyl acetate, polyvinyl chloride resin, polystyrene resin, polyphenyl ether resin, polyamide resin, polycarbonate, epoxy resin, polyurethane, acrylic resin, polyacrylonitrile resin, polyvinyl alcohol resin, bismaleimide resin, polyimide resin, cyanate resin, natural rubber, polyisoprene rubber, ethylene propylene rubber, styrene butadiene rubber, fluororubber, chloroprene rubber, nitrile butadiene rubber, silicone rubber and fluorosilicone rubber; preferably, the polymer matrix is selected from at least one of epoxy resin, polyurethane and silicone rubber.
The measuring method of the thermal conductivity, the Thermal Conductivity Enhancement (TCE) and the powder resistivity is as follows:
thermal conductivity: the method is obtained by testing a Hot disk thermal constant analyzer, wherein the testing temperature is 20 ℃, the testing depth is 2mm, the thickness of a sample is 3mm, the length and the width are 4cm respectively, each sample is tested 5 times, and the average value is obtained.
The formula of the heat conduction improvement rate is as follows: tce= (K-K) 1 )/K 1 Wherein K is the thermal conductivity of the composite material, K 1 Is the intrinsic thermal conductivity of the matrix.
Powder resistivity: the powder resistivity measuring instrument is used for measuring the resistivity of the powder sample in the die by pressing the upper electrode and the lower electrode, wherein the resistivity of the powder sample in the die can be measured in the measuring process, the measuring sample amount is 0.05g, each sample is measured 5 times, and the average value is obtained.
Example 1
Preparing a boron nitride precursor: boric acid and melamine (the molar ratio is calculated by boron element and nitrogen element) with the molar ratio of 2:1 are dissolved in 200mL of pure water, heated to 95 ℃ and assisted by the rotating speed of 350r/min, and continuously stirred for 20min after the solution is transparent and clear. Then, the solution was dropped into 200mL of liquid paraffin (95 ℃ C.) containing span-80, the amount of span-80 was 0.05wt% based on the weight of the liquid paraffin, and the reaction was stirred for 4 hours. And then placing the reaction vessel in an ice-water bath to enable the boron nitride precursor to be rapidly separated out, filtering, washing and drying to obtain the boron nitride precursor (BM).
Modification of boron nitride precursor: and (3) mixing the prepared BM and a silane coupling agent KH570 with the mass ratio of 1:1 in 200mL of mixed solution of water and ethanol, wherein the volume ratio of the water to the ethanol is 1:3, stirring at room temperature for reaction for 24 hours, washing, and drying to obtain a KH570 modified boron nitride precursor (BM' -KH 570).
FIG. 1 is an infrared spectrum before and after BM modification. As can be seen from FIG. 1, 1085cm was found in the absorption peak after KH570 modification -1 Belonging to-SiO, 2947cm -1 There is a distinct absorption peak, which is-CH 2 and-CH 3 Is guided by telescopic vibrationStarting; 1722cm -1 The absorption peak at is the stretching vibration peak of c=o; the above characteristic peaks indicate that KH570 has been adsorbed to BM surfaces.
Modification of graphite nano-sheets: mixing graphite nano-sheets (GNP) and dopamine hydrochloride with the mass ratio of 1:2 in 200mLTris buffer solution, performing ultrasonic treatment in ice water bath for 10min to disperse the graphite nano-sheets in Tris buffer solution, stirring the solution at 60 ℃ for reaction for 24h to obtain a yellow brown solution, performing suction filtration, and washing to remove free dopamine hydrochloride to obtain polydopamine modified graphite nano-sheets (GNP-PDA).
FIG. 2 is an infrared spectrum of the GNP before and after modification. As can be seen from FIG. 2, 1617cm was found in the absorption peak after dopamine modification -1 、1504cm -1 、1079cm -1 The c=c stretching vibration peak, the N-H bending vibration peak, and the C-N stretching vibration peak were respectively present, and the occurrence of these characteristic peaks indicates that dopamine was successfully adhered to the GNP surface. In addition, since the color of the solution was yellow brown, it was judged that the reaction product was GNP-PDA.
Preparing a boron nitride precursor/graphite nano-sheet: dispersing 0.25. 0.25gBM-KH570 and 1g GNP-PDA into n-hexane, stirring at room temperature, adding 10% Hexamethylene Diisocyanate (HDI) dropwise, stirring for 2 hr, filtering, washing, and oven drying to obtain boron nitride precursor/graphite nano-plate (GNP-BM').
FIG. 3 is an infrared spectrum of BM-GNP before and after HDI grafting. As can be seen from FIG. 3, 2273cm was found in the absorption peak after the addition of HDI -1 The corresponding group is the stretching vibration peak of n=c=o, while the-OH stretching vibration peak disappears, which indicates that the grafting reaction of HDI with GNP and BM takes place.
Preparing a graphite nano-sheet in-situ grown boron nitride composite material: transferring the BM-GNP' prepared in the above to a nitrogen atmosphere tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 1600 ℃ at a heating rate of 3 ℃/min for 6 hours, and cooling with the furnace to obtain graphite nano-sheets (GNP-BN) with boron nitride growing on the surface, which is hereinafter referred to as a heat conducting filler A1.
Preparation of epoxy resin composite material: weighing 10g E-51 type epoxy resin, transferring into a homogenizing cup, adding 3gHK-66 type diluent, homogenizing for 5min at 2000 r/min; adding a heat-conducting filler A1 (the dosage is 9 weight percent of the mass of the epoxy resin), and continuously homogenizing for 5min; 2.5g of T-31 type curing agent is dripped, the homogenization is continued for 5min, then the obtained mixture is poured into a silica gel plate with the depth of 1mm, and the mixture is put into an oven with the temperature of 80 ℃ for curing for 6h after the complete tiling, so as to obtain the epoxy resin composite material. After curing was completed, poured out, cut using a die, and the thermal conductivity of the epoxy composite was tested, and the results are shown in table 1.
Examples 2 to 6
The procedure of example 1 was followed, except that: the weight ratio of GNP-PDA to BM-KH570 was varied to obtain the heat conductive fillers A2-A6, as shown in Table 1.
The powder resistivity of the heat conductive fillers A1 to A6 and the thermal conductivity of the epoxy resin composite material obtained by filling the epoxy resin with the same were tested, and the results are shown in table 1.
Blank examples
Weighing 10g E-51 type epoxy resin, transferring into a homogenizing cup, weighing 3gHK-66 type diluent, pouring, homogenizing at 2000r/min for 5min; 2.5g of T-31 type curing agent is dripped, the mixture is homogenized for 5min at the same rotating speed, then the obtained mixture is poured into a silica gel plate with the depth of 1mm, and the mixture is put into an oven at 80 ℃ for curing for 6h after the complete tiling, so that the epoxy resin composite material is obtained. After curing was completed, poured out, cut using a die, and the thermal conductivity of the epoxy composite was tested, and the results are shown in table 1.
TABLE 1
Fig. 4 is an SEM image of the heat conductive filler prepared in example 5 of the present invention, and fig. 5 is an SEM image of the heat conductive filler prepared in example 6 of the present invention. As can be seen from fig. 4 and 5, the boron nitride can exert a better coating effect on the graphite nano-sheets.
It can be seen from table 1 that the powder resistivity increases with increasing BM-KH570 content, and the thermal conductivity tends to increase and decrease with increasing BM-KH570 content, wherein the thermal conductivity of the epoxy resin composite material prepared in example 5 reaches a maximum value, and at the same time has a higher resistivity, which indicates that the optimal composite ratio of graphite and boron nitride is achieved at this time.
Examples 7 to 9 and comparative example 1
The procedure of example 5 was followed, except that: the amounts of HDI added were varied, as shown in table 2.
The powder resistivity of the heat conductive fillers B1 to B4 and the thermal conductivity of the epoxy resin composite material obtained by filling the epoxy resin with the same were tested, and the results are shown in table 2.
TABLE 2
As can be seen from table 2, the powder resistivity increased with increasing HDI usage, but the thermal conductivity tended to increase and decrease, with the thermal conductivity being maximized at an HDI addition of 10%.
Examples 10 to 11
The procedure of example 5 was followed, except that: the mass ratio of BM to KH570 is different, as shown in table 3.
The powder resistivity of the heat conductive fillers C1, C2 and the thermal conductivity of the epoxy resin composite material obtained by filling the epoxy resin with the same were tested, and the results are shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, as the KH570 content increases, the thermal conductivity tends to increase and then decrease, and reaches a maximum value when the mass ratio of the boron nitride precursor to KH570 is 1:1, and the thermal conductivity decreases instead as the KH570 content continues to increase.
Examples 12 to 13
The procedure of example 5 was followed, except that: the mass ratio of GNP and dopamine hydrochloride was different, as shown in table 4.
The powder resistivity of the heat conductive fillers D1, D2 and the thermal conductivity of the epoxy resin composite material obtained by filling the epoxy resin with the same were tested, and the results are shown in table 4.
TABLE 4 Table 4
As can be seen from table 4, as the proportion of dopamine hydrochloride increases, the thermal conductivity tends to increase and decrease, and when the mass ratio of the graphite nanoplatelets to the dopamine hydrochloride is 1:2, the thermal conductivity reaches the maximum value. This is because when the dopamine content is small, the adhesion of graphite to boron nitride is weak; when the amount of dopamine added is excessive, the interfacial thermal resistance increases, resulting in a decrease in thermal conductivity.
Comparative example 2
BM was prepared as in example 5.
Transferring BM into a nitrogen atmosphere tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min for 4h, heating to 1600 ℃ at a heating rate of 3 ℃/min for 6h, and cooling along with the furnace to obtain Boron Nitride (BN).
Adding BN and KH570 into 200mL of mixed solution of water and ethanol according to the mass ratio of 1:3, wherein the volume ratio of water to ethanol is 1:3, stirring at room temperature for reaction for 24 hours, washing and drying to obtain KH570 modified boron nitride (BN-KH 570).
Preparation of GNP-PDA was the same as in example 5.
And dispersing BN-KH570 and GNP-PDA into n-hexane, stirring at room temperature, dropwise adding 10% of HDI, continuously stirring for 2h, filtering, washing and drying to obtain the heat-conducting filler E1.
Comparative example 3
BN was prepared as in comparative example 2.
0.91g BN and 1g GNP were ground and mixed to obtain a heat conductive filler F1.
The powder resistivity of the heat conductive fillers E1 and F1 and the thermal conductivity of the epoxy resin composite material obtained by filling the epoxy resin with the same were tested, and the results are shown in table 5.
TABLE 5
The estimation method of the ratio of GNP to BN in the heat-conducting filler A5 comprises the following steps: by weight m of the product GNP-BN 1 Minus the amount of GNP fed m 0 Obtaining the mass m of BN 2 Then according to the dosage m of the GNP 0 And the estimated mass m of BN 2 The ratio of GNP to BN was calculated to be 1:0.91.
As can be seen from Table 5, if boron nitride is not grown in situ on the graphite nanoplatelets, the obtained heat conductive filler has the same composition but has very large difference in powder resistivity and heat conductivity, and cannot be endowed with excellent insulating property and heat conductive property. The possible reason is that the bonding force between the boron nitride and the graphite is enhanced in the in-situ growth process, so that the interface thermal resistance is reduced, and the thermal conductivity is improved; meanwhile, in-situ growth of boron nitride on the surface of graphite prevents conduction of electrons between the graphite and improves insulativity of the graphite.
Examples 14 to 19 and comparative examples 6 to 13
The epoxy resin was filled with the heat conductive fillers A5, B1 and E1, respectively, according to the method of example 1, to obtain an epoxy resin composite. The loading of the thermally conductive filler and the thermal conductivity of the epoxy resin composite are shown in table 6.
TABLE 6
As can be seen from table 6, the thermal conductivity of the epoxy resin composite increases with increasing amount of the thermally conductive filler, because as the content of the thermally conductive filler gradually increases, the probability of the thermally conductive fillers coming into contact with each other increases, and a complete thermally conductive network is more easily formed. The filling amount of the heat-conducting filler A5 in the epoxy resin is up to 24 weight percent, and the heat conductivity coefficient of the obtained epoxy resin composite material can be up to 1.04W/(m.K) which is 5.47 times that of the pure epoxy resin; the filling amount of the heat-conducting filler B1 in the epoxy resin can only reach 18wt percent at most, and the heat conductivity coefficient of the obtained epoxy resin composite material can only reach 0.75W/(m.K) at most; the filling amount of the heat-conducting filler E1 in the epoxy resin can only reach 9wt percent at most, and the heat conductivity coefficient of the obtained epoxy resin composite material can only reach 0.46W/(m.K) at most.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the graphite nano-sheet in-situ growth boron nitride composite material is characterized by comprising the following steps of:
(1) Stirring a boron source and a nitrogen source in a solvent for reaction to obtain a boron nitride precursor;
(2) Stirring and reacting the boron nitride precursor and a coupling agent in a solvent to obtain a coupling agent modified boron nitride precursor;
(3) Stirring graphite nano-sheets and an amino-containing modifier in a solvent for reaction to obtain amino-modified graphite nano-sheets;
(4) Mixing a coupling agent modified boron nitride precursor and an amino modified graphite nano-sheet in a solvent, adding isocyanate, stirring for reaction, filtering, washing, drying, and sintering in a protective atmosphere to obtain the graphite nano-sheet in-situ grown boron nitride composite material.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the boron source is at least one selected from boric acid and borax;
preferably, the nitrogen source is selected from at least one of melamine, amine chloride, urea;
preferably, the molar ratio of the boron source to the nitrogen source is (1.5-3.5): 1, wherein the boron source is calculated as boron element and the nitrogen source is calculated as nitrogen element.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the solvent is an oil-water mixed solution; the oil-water mixed solution is a mixture of water and oil, and comprises 20-80 vol% of water and 20-80 vol% of oily solvent; preferably 30 to 70Vol% of water and 30 to 70Vol% of an oily solvent; further preferably 40 to 60Vol% of water and 40 to 60Vol% of an oily solvent; more preferably 45 to 55Vol% of water and 45 to 55Vol% of an oily solvent;
preferably, the oily solvent is at least one selected from liquid paraffin, oleic acid, alkane solvent, silicone oil and petroleum ether;
preferably, the temperature of the stirring reaction is 70-110 ℃; further preferably 85 to 105 ℃; more preferably from 90 to 100 ℃;
preferably, the stirring reaction time is 4-24 hours; more preferably for 4 to 16 hours.
4. The method of manufacturing according to claim 1, characterized in that: in the step (2), the coupling agent is a silane coupling agent or a titanate coupling agent;
preferably, the silane coupling agent is selected from at least one of KH570, KH560, KH550, KH792, GR-SI351, GR-SI151 and A-151;
preferably, the mass ratio of the boron nitride precursor to the coupling agent is 1 (0.1-2); further preferably 1 (0.5 to 1);
preferably, the solvent is pure water or a mixed solvent of water and ethanol, and the mixed solution of water and ethanol comprises 10-90 Vol% of water and 10-90 Vol% of ethanol; preferably 20 to 80Vol% water and 20 to 80Vol% ethanol;
preferably, the stirring reaction time is 12-48 hours; more preferably 18 to 24 hours.
5. The method of manufacturing according to claim 1, characterized in that: in the step (3), the modifier containing amino is at least one selected from dopamine, dopamine hydrochloride, dopamine acrylamide and N-alanyl dopamine; preferably dopamine hydrochloride;
preferably, the mass ratio of the graphite nano-sheets to the modifier containing amino groups is 1 (0.5-4), and more preferably 1 (1-2);
preferably, the solvent is Tris-Cl buffer or PBS buffer, more preferably Tris-Cl buffer;
preferably, the temperature of the stirring reaction is 25-70 ℃ and the time is 12-24 h.
6. The method of manufacturing according to claim 1, characterized in that: in step (4), the isocyanate is a polyisocyanate;
preferably, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, tetramethyl isophthalene diisocyanate, 1, 4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1, 4-phenylene diisocyanate, triphenylmethane triisocyanate and dimethyltriphenylmethane tetraisocyanate;
preferably, the mass ratio of the coupling agent modified boron nitride precursor to the amino modified graphite nano-sheet is 1 (0.25-6); further preferably 1 (1) to 4); more preferably 1, (2-4);
preferably, the addition amount of the isocyanate accounts for 1-10% of the total mass of the boron nitride precursor modified by the coupling agent and the amino modified graphite nano-sheet;
preferably, the solvent is selected from at least one of n-hexane, n-pentane, NMP, DMF, DMSO;
preferably, the stirring reaction time is 2-24 hours.
7. The method of manufacturing according to claim 1, characterized in that: in the step (4), the sintering temperature is 900-1600 ℃, preferably 1200-1600 ℃;
preferably, the sintering time is 1 to 12 hours, more preferably 6 to 10 hours;
preferably, the shielding gas is nitrogen and/or an inert gas, more preferably nitrogen.
8. The graphite nanoplatelets in-situ grown boron nitride composite material obtained by the preparation method of any one of claims 1 to 7.
9. A thermally conductive polymer comprising a polymer matrix and a thermally conductive filler, characterized in that: the heat-conducting filler is the graphite nano-sheet in-situ grown boron nitride composite material as claimed in claim 7.
10. The thermally conductive polymer of claim 9, wherein: based on the total weight of the heat conducting polymer, the heat conducting polymer comprises 76-99 wt% of a polymer matrix and 1-24 wt% of a heat conducting filler;
preferably, the polymer matrix is selected from at least one of polypropylene resin, polyethylene resin, polyvinyl acetate, polyvinyl chloride resin, polystyrene resin, polyphenylene oxide resin, polyamide resin, polycarbonate, epoxy resin, polyurethane, acrylic resin, polyacrylonitrile resin, polyvinyl alcohol resin, bismaleimide resin, polyimide resin, cyanate resin, natural rubber, polyisoprene rubber, ethylene propylene rubber, styrene butadiene rubber, fluororubber, neoprene rubber, nitrile rubber, silicone rubber, fluorosilicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311807260.5A CN117866287A (en) | 2023-12-26 | 2023-12-26 | Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311807260.5A CN117866287A (en) | 2023-12-26 | 2023-12-26 | Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117866287A true CN117866287A (en) | 2024-04-12 |
Family
ID=90585759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311807260.5A Pending CN117866287A (en) | 2023-12-26 | 2023-12-26 | Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117866287A (en) |
-
2023
- 2023-12-26 CN CN202311807260.5A patent/CN117866287A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pan et al. | Vertically aligned silicon carbide nanowires/boron nitride cellulose aerogel networks enhanced thermal conductivity and electromagnetic absorbing of epoxy composites | |
| Zhao et al. | A critical review of the preparation strategies of thermally conductive and electrically insulating polymeric materials and their applications in heat dissipation of electronic devices | |
| Duan et al. | Bioinspired construction of BN@ polydopamine@ Al 2 O 3 fillers for preparation of a polyimide dielectric composite with enhanced thermal conductivity and breakdown strength | |
| CN109825010B (en) | Method for preparing brick-mud structure heat-conducting polymer composite material by utilizing magnetic field orientation | |
| CN107418204B (en) | Preparation method of graphene @ calcium copper titanate-polybenzoxazole three-phase composite film | |
| CN104327515A (en) | Graphene-containing silicon rubber heat-conducting composite material and preparation method thereof | |
| CN108997754B (en) | Polyimide high-temperature dielectric composite film and preparation method thereof | |
| Duan et al. | Improved thermal conductivity and dielectric properties of flexible PMIA composites with modified micro-and nano-sized hexagonal boron nitride | |
| CN111534016B (en) | Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof | |
| CN114854087B (en) | Polyimide composite material with double heat-conducting networks and preparation method thereof | |
| CN112608565A (en) | High-thermal-conductivity graphene heat dissipation film and preparation method thereof | |
| CN111607365B (en) | Flake graphite heat conduction material, preparation method thereof and electronic equipment | |
| Li et al. | Dopamine-mediated bacterial cellulose/hexagonal boron nitride composite films with enhanced thermal and mechanical performance | |
| Xu et al. | A malleable composite dough with well-dispersed and high-content boron nitride nanosheets | |
| CN110894342A (en) | Composite thermal interface material and preparation method thereof | |
| Meng et al. | Investigation on preparation, thermal, and mechanical properties of carbon fiber decorated with hexagonal boron nitride/silicone rubber composites for battery thermal management | |
| Sheng et al. | Enhanced thermal conductivity and stability of boron nitride/phenyl silicone rubber composites via surface modification and grain alignment | |
| Weng et al. | Improved thermal conductivities of epoxy resins containing surface functionalized BN nanosheets | |
| Chi et al. | Simultaneously enhanced in-plane and out-of-plane thermal conductivity of a PI composite film by tetraneedle-like ZnO whiskers and BN nanosheets | |
| Wang et al. | Large flakes of Al–Ti3C2Tx MXene constructing highly ordered layered MXene/ANF films with integrated multifunctionalities | |
| CN117264426A (en) | Insulating heat-conducting gasket and preparation method thereof | |
| CN110684285B (en) | Rubber-based graphene heat conduction material | |
| CN117866287A (en) | Graphite nano-sheet in-situ growth boron nitride composite material, preparation method thereof and heat conducting polymer | |
| Chu et al. | Preparation and properties comparison of ZIF-67/PVDF and SiCNWs/PVDF composites for energy storage | |
| CN115572486B (en) | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |