CN105368046B - Cyanate ester resin/heat conduction filler composition, prepreg and its application - Google Patents
Cyanate ester resin/heat conduction filler composition, prepreg and its application Download PDFInfo
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- CN105368046B CN105368046B CN201510850002.4A CN201510850002A CN105368046B CN 105368046 B CN105368046 B CN 105368046B CN 201510850002 A CN201510850002 A CN 201510850002A CN 105368046 B CN105368046 B CN 105368046B
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- Prior art keywords
- resin
- cyanate ester
- heat conduction
- ester resin
- filler composition
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- 229920005989 resin Polymers 0.000 title claims abstract description 139
- 239000011347 resin Substances 0.000 title claims abstract description 139
- 239000004643 cyanate ester Substances 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000000945 filler Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 24
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 60
- 239000003822 epoxy resin Substances 0.000 claims description 51
- 229920000647 polyepoxide Polymers 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 22
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 19
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 17
- -1 glycidol ethers Chemical class 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 2
- 150000002924 oxiranes Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 32
- 238000001291 vacuum drying Methods 0.000 description 29
- 239000000178 monomer Substances 0.000 description 28
- 150000001913 cyanates Chemical class 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 229930185605 Bisphenol Natural products 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003760 hair shine Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 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
- 150000001336 alkenes Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- PTIXGJYNJPLSCB-PGDPNYEUSA-N CCC(C[C@@H](C)[C@@H](C)[C@H]1C)C1(C)C=C Chemical compound CCC(C[C@@H](C)[C@@H](C)[C@H]1C)C1(C)C=C PTIXGJYNJPLSCB-PGDPNYEUSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007786 learning performance Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to cyanate ester resin/heat conduction filler compositions, prepreg and its application, said composition includes heat filling and cyanate ester resin, wherein the mass percentage content of heat filling is 0.5~10%, the mass percentage content of cyanate ester resin is 90~99.5%, the heat filling is the multi-walled carbon nanotube handled using monofunctional isocyanates or one kind in the graphene for using monofunctional isocyanates processing or combination, if heat filling is the combination of the multi-walled carbon nanotube handled using monofunctional isocyanates and the graphene using monofunctional isocyanates processing, then the mass ratio of the two is 20~80：80~20, said composition can be mixed with prepreg with continuous fiber or fabric, the present composition and its prepreg excellent thermal conductivity, matrix resin as high-performance composite materials, or as High-performance adhesive and coating, available for all conglomeraties such as electronics industry, Aeronautics and Astronautics, defence and military.
Description
Technical field
The present invention relates to cyanate ester resin/heat conduction filler composition, prepreg and its application, which is used for
Prepare high-performance composite materials, High-performance adhesive and coating.
Background technology
Cyanate ester resin refers to the amphyl containing two or more-OCN functional groups, is a kind of novel high-performance
Polymer material.
There are many method, industrialized the most frequently used and realization is in condition existing for alkali for the synthesis of cyanate resin alicyclic monomer
Under, cyanogen halides prepares cyanate ester monomer with phenolic compound reaction.Tricyclic occurs for cyanate ester resin under heat or catalyst action
Change reaction, generate the macromolecular of the high crosslink density network structure containing triazine ring.The cyanate ester resin of this structure has low
Dielectric coefficient and minimum dielectric loss tangent value, high glass-transition temperature, low hydroscopicity, low-shrinkage and excellent power
The features such as learning performance and adhesive property.Cyanate ester resin has the processing performance similar to epoxy resin, can consolidate at 177 DEG C
Change, and generated in the curing process without volatile small molecule.And it has and the comparable resistance to height of bimaleimide resin
Warm nature energy has dielectric properties more superior than polyamide-imide, has and the comparable flame resistance energy of phenolic resin.
Background technology in relation to cyanate and its primary synthetic methods may be referred to Chen Xiangbao and exist《High-performance resin matrix》
([J] engineering plastics should in " synthesis of bisphenol A cyanate ester resin " for (Chemical Industry Press, version in 1999), Yan Fusheng etc.
With 1999,27 (8)), SNOW A W are in " The synthesis manufacture and characterization of
Cyanate ester monomers " ([J] .SAMPE J, 2000 (36)), Hamerton etc. are in " Recent
developments in the chemistry of cyanate ester”([J].Polym Int,1998,47(4))、
Chaplin A etc. are in " Development of novel functionalized arylcyanate ester oligomers
1.Synthesis and thermal characterization of the monomers”([J].Macromolecules,
1994,27 (18)) etc. the method that is previously mentioned in works and article and research background.
Although cyanate ester resin has excellent performance, the thermal conductivity factor of cured product is still relatively low, this limitation
It is in the application of Heat Conduction Material field.To improve the thermal conductivity factor of ethylene rhodanate resin curing product, it has been reported that part cyanogen
Acid ester resin composite system.Such as close sub- man, 2013- University Of Suzhou, high heat conduction aluminium nitride-carbon nano-tube/polymer base
The research [academic dissertation] of composite material, has mainly inquired into aluminium nitride-carbon nanotubes/cyanate ester resin composite material, has been prepared for
Aluminium nitride-content of carbon nanotubes is respectively 40~47.5% and 1.5~2.5%, and thermal conductivity factor can reach 2.28~5W
m-1·K-1, but wherein heat filling content is very high, is not suitable for prepreg resin.
Such as (1) Su Lei, 2012- Institutes Of Technology Of Nanjing, the preparation of cyanate resin base heat conductive insulating composite material is with grinding
Study carefully [academic dissertation]；(2) Zhao Chunbao, Su Lei etc., the preparation of cyanate ester resin/ZnOw composite material and performance study,
New Chemical Materials, 2013,41 (11), 62-64；(3) Zhao Chunbao, Su Lei etc., cyanate ester resin/oxidized graphite flake composite material
Preparation and performance study, functional material, 2013,44 (16) silane coupling agent is mainly used in the above-mentioned reports of 2301-2304.
(KH550) four acicular type zinc oxide crystal whisker (T-ZnOw), hexagonal boron nitride (h-BN) are surface-treated, select lauryl amine
(DDA) organic modification of surface is carried out to graphite oxide (GO)；And it is prepared for T-ZnOw/CE, BN/CE, BN-ZnOw/CE, GO-
When a series of cyanate resin base heat conductive insulating composite materials such as DDA/CE, wherein ZnOw contents are 12%, composite material is led
Hot coefficient reaches 0.79Wm-1·K-1；When BN volume parts are 24%, the thermal conductivity factor of composite material reaches 1.33Wm-1·
K-1；It adds in (BN-ZnOw) after the mixed fillers of 20% volume fraction, the thermal conductivity of composite material reaches 1.19Wm-1·K-1；
During GO-DDA contents 1%, thermal conductivity factor reaches 0.43Wm-1·K-1.Above-mentioned work can prepare a variety of heat-conductive composite materials,
But be not suitable for preparing prepreg heat-conducting resin, it is specially that packing density mentioned above is big, causes composite weight
It increases, is not suitable for the spacecraft for having strict demand to construction weight；Silane coupling agent is low-molecular material, may under space environment
It can be precipitated, it is impossible to meet under composite space environment the requirement pair volatile matter can be coagulated；In addition the amount added in above all exists
More than 10%, the viscosity of gained resin is too big, poor fluidity can not prepare prepreg.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, cyanate ester resin/heat conduction filler composition is provided,
Said composition is suitable for the prepreg resin of fibrous composite, and cured product has higher thermal conductivity factor and excellent
Performance.
Another object of the present invention is to provide cyanate ester resin/heat conduction filler composition prepreg and its application.
What the above-mentioned purpose of the present invention was mainly achieved by following technical solution：
Cyanate ester resin/heat conduction filler composition includes the quality of heat filling and cyanate ester resin, wherein heat filling
Degree is 0.5~10%, and the mass percentage content of cyanate ester resin is 90~99.5%, and the heat filling is to adopt
With monofunctional isocyanates handle multi-walled carbon nanotube or using monofunctional isocyanates handle graphene in one kind or
Combination, if heat filling is the multi-walled carbon nanotube handled using monofunctional isocyanates and is handled using monofunctional isocyanates
Graphene combination, then mass ratio both is 20~80：80~20.
In above-mentioned cyanate ester resin/heat conduction filler composition, monofunctional isocyanates are octadecylisocyanate, ten
Six alkyl isocyanates or dodecyl isocyanate.
In above-mentioned cyanate ester resin/heat conduction filler composition, multi-walled carbon nanotube is handled using monofunctional isocyanates
Or the specific method of graphene is as follows：
Using toluene as solvent, multi-walled carbon nanotube or graphene, monofunctional isocyanates, di lauric dibutyl are added in
Tin is stirred and heated to 65~75 DEG C, when isothermal reaction 10~13 is small；After completion of the reaction, product is filtered, third is added in filter residue
It more than when ketone agitator treating 2 is small, 3~4 times repeatedly, is subsequently isolated, and is dried in vacuo 22~25h, it is isocyanic acid to obtain product
Ester modified multi-walled carbon nanotube or isocyanate-modified graphene.
In above-mentioned cyanate ester resin/heat conduction filler composition, multi-walled carbon nanotube or graphene, the simple function of addition are different
Cyanate, the mass ratio of dibutyl tin laurate are 1:0.9~1.1:0.3~0.6.
In above-mentioned cyanate ester resin/heat conduction filler composition, the general formula of cyanate ester resin is as follows：
N≡C-O-R′-O-C≡N
Wherein：R ' is alkylidene, arlydene, sub- unsaturated group or sub- alcyl.
In above-mentioned cyanate ester resin/heat conduction filler composition, cyanate ester resin includes following any one or combination：
(1) bisphenol A cyanate ester monomer
(2) bisphenol E-type cyanate monomer
(3) bisphenol E-type cyanate monomer,
(4) tetramethyl bisphenol-f type cyanate ester monomer
(5) tetramethyl bisphenol-f type cyanate ester monomer
(6) bis-phenol M types cyanate ester monomer
(7) polyfunctional group type cyanate ester monomer
(8) dicyclopentadiene bisphenol type cyanate ester monomer
In above-mentioned cyanate ester resin/heat conduction filler composition, cyanate ester resin and epoxy may be employed in cyanate ester resin
The mixture or prepolymer of resin substitute, and the epoxy resin is glycidyl ether type epoxy resin, glycidol esters epoxy
Resin, glycidyl amine epoxy resin, aliphatic epoxy compound or heterocycle and mixed type epoxide.
In above-mentioned cyanate ester resin/heat conduction filler composition, epoxy resin is bisphenol A type epoxy resin, epoxidation phenol
Urea formaldehyde, TDE-80# epoxy resin, amino tetrafunctional epoxy resin AG-80#.
Cyanate ester resin/heat conduction filler composition prepreg, including cyanate ester resin/heat conduction described in claim 1~8
The quality percentage of fill composition and asphaltic base heat conduction carbon fiber or its fabric, wherein cyanate ester resin/heat conduction filler composition
It is 37%~43% than content, the mass percentage content of asphaltic base heat conduction carbon fiber or its fabric is 57%~63%.
The application of above-mentioned cyanate ester resin/heat conduction filler composition, cyanate ester resin/heat conduction filler composition is as compound
The matrix resin of material, is used to prepare composite material；Matrix of the cyanate ester resin/heat conduction filler composition as adhesive
Resin is used to prepare adhesive；Matrix resin of the cyanate ester resin/heat conduction filler composition as coating, is used to prepare
Coating.
The present invention has the advantages that compared with prior art：
(1), the present invention is using the multi-walled carbon nanotube (OM-MWCNT) or stone by monofunctional isocyanates surface treatment
One kind in black alkene (OM-G) and combinations thereof is mixed with cyanate ester resin, thus obtains cyanate ester resin/heat filling combination
Object, said composition are suitable for the prepreg resin of fibrous composite, cured product have higher thermal conductivity factor and
Excellent performance.
(2), the composition present invention preferably employs modified multi-walled carbon nanotube and graphene is mixed with cyanate ester resin,
Graphene film has apparent synergistic effect with carbon nanotubes in the conduction process of resin, can preferably improve composite material
X, Y, the thermal conductivity of Z-direction；
(3), the present invention is using the mixture or prepolymer of cyanate ester resin and epoxy resin and modified multi-wall carbon nano-tube
Pipe or graphene mixing, compared to individually using cyanate ester resin, epoxy resin can accelerate the reaction of cyanate ester resin, with cyanate
Resin acts synergistically, and reduces its solidification temperature, extends resin storage life；
(4), the present invention in heat filling additive amount within 10% or even within 4%, it is possible to reach higher
Thermal conductivity factor overcomes and adds in excessive heat filling in the prior art and cause that the viscosity of resin is too big, poor fluidity can not be prepared
The defects of prepreg.
(5), cyanate ester resin/heat conduction filler composition and its prepreg of the present invention, wherein cyanate ester resin/heat filling
Composition may be employed thermosetting resin familiar to the person skilled in the art and its composite material and pass through various contour machining procedures
Various products are made, the excellent thermal conductivity of composite material made from cyanate ester resin/heat conduction filler composition and its prepreg；
As the matrix resin of high-performance composite materials or as High-performance adhesive and coating, available for electronics industry, aviation, boat
My god, all conglomeraties such as defence and military.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail：
The present invention provides a kind of cyanate ester resin/heat conduction filler composition, and wherein heat filling is combined with cyanate ester resin
The mass percentage content of object is respectively 0.5~10%, 90~99.5%；The heat filling refers to by simple function isocyanic acid
In the multi-walled carbon nanotube (OM-MWCNT) of ester surface treatment or the graphene (OM-G) of monofunctional isocyanates surface treatment
One or two kinds of compositions.The mass percentage content that can also select heat filling and cyanate resin composition is respectively
1.5~3.5%, 96.5~98.5%.
If heat filling is using the multi-walled carbon nanotube of monofunctional isocyanates processing and using monofunctional isocyanates
Then the mass ratio of the two is 20~80 during the composition of the graphene of processing：80~20.
In the present invention, cyanate ester resin refers to the compound that structure contains at least two cyanate groups in molecule, polymerization
Object and its mixture, general formula are shown below,
N≡C-O-R′-O-C≡N
Wherein R ' can be alkylidene, arlydene, sub- unsaturated group or sub- alcyl.
Particularly, in the preferred embodiment of cyanate ester resin/heat conduction filler composition according to the present invention, cyanate
Resin refers to containing cyanate ester monomer and their mixture selected from structural unit described in following (1)-(8)：
(1) bisphenol A cyanate ester monomer (HF-1) shown in following formula
The bisphenol A cyanate ester monomer (HF-1) is a kind of cyanate ester monomer of earliest commercialization, cheap, is fitted
In commercial Application；
(2) bisphenol E-type cyanate monomer (HF-9) shown in following formula
The bisphenol E-type cyanate monomer (HF-9) exists in the form of low-viscosity (mobile) liquid in room temperature, is suitable for the application of；
(3) bisphenol E-type cyanate monomer (HF-9) shown in following formula
(4) tetramethyl bisphenol-f type cyanate ester monomer shown in following formula
(5) tetramethyl bisphenol-f type cyanate ester monomer shown in following formula
(6) bis-phenol M types cyanate ester monomer (HF-7) shown in following formula
(7) polyfunctional group type cyanate ester monomer (HF-5) shown in following formula
(8) dicyclopentadiene bisphenol type cyanate ester monomer (HF-3) shown in following formula
In addition, cyanate ester resin can also include other kinds of cyanate resin alicyclic monomer, such as I.Hamerton exists
Other kinds of cyanate ester monomer is referred in " Chemistry and Technology of Cyanate Ester Resins "
(I.Hamerton,Chemistry and Technology of Cyanate Ester Resins,Blackie
Academic＆Professional Glasgow, London, 1994.) or Cida, Lonza, Dow and Shanghai Hui Feng science and trade
Other different structure cyanates of the companies of grade production.
Cyanate ester resin can also use the mixture or prepolymer of cyanate ester resin and epoxy resin to substitute in the present invention,
Its epoxy resin can utilize existing epoxy resin or the epoxy resin using prior art synthesis, such as the more benevolence of Wang to exist
([J] thermosetting resins, 2001,16 (1)), old equality exist in " synthesis and application of epoxy resin "《Epoxy resin and its should
With》([M] Chemical Industry Press, 2004), MING-KUNG LI SIMON etc. are in " Epoxy resin preparation
Process " ([P], EP86200962A, 1986), Peng Ping Ren etc. " new process of epoxy resin production " ([J] coatings industries,
1997,4 (26)) etc. the epoxy resin that is previously mentioned in works and article and its synthetic method.
Wherein, epoxy resin is containing selected from the epoxy monomer described in following (1)-(4) and their mixing
Object：
(1) glycidol ethers
Glycidyl ether type epoxy resin mainly has bisphenol A type epoxy resin, bisphenol-s epoxy resin, Bisphenol F type ring again
Oxygen resin, epoxidization phenolic resin.
Bisphenol A type epoxy resin is to be worth by bisphenol-A and epoxychloropropane into etherificate and closed loop two-step reaction, such as E-
55、E-51、E-20；Bisphenol-s epoxy resin be by bisphenol S and excess epoxy chloropropane in alkaline conditions polycondensation obtain it is resistance to
High temperature epoxy resins；Bisphenol f type epoxy resin is by Bisphenol F and excess epoxy chloropropane (1：10), in tetramethyl ammonium chloride and
Under the conditions of NaOH, etherified and ring-closure reaction, what polycondensation formed；Epoxy phenolics is by pf resin of low molecular weight and epoxy
Chloropropane is condensed under an acid catalysis；
(2) glycidol esters
Glycidyl ester epoxy resin is the compound for having in molecular structure two or two or more glycidol ester groups.
Such as 711# epoxy resin, TDE-80# epoxy resin, 731# epoxy resin, CY-183# epoxy resin；
(3) glycidol amine
Glycidyl amine epoxy resin be with primary amine or secondary amine synthesized with epoxychloropropane contain two or two with
The compound of upper glycidol amido.Such as amino tetrafunctional epoxy resin (AG-80#), AFG-90# epoxy resin；
(4) aliphatic epoxy compound
Aliphatic epoxy compound is to aoxidize through double bond from alicyclic containing unsaturated double-bond structure or add with hypochlorous acid
It is made into epoxidation.Such as W-95# epoxy resin, 6221# epoxy resin, 6206# epoxy resin.
In addition, also heterocycle and mixed type epoxide, such as：Glycolylurea resin, tricyanic epoxy resin, flame-retarded resin
Deng.
Epoxy resin preferably includes bisphenol A type epoxy resin, epoxidization phenolic resin, TDE-80# epoxy resin, amino four
Functional epoxy resin (AG-80#).
Heat filling is handled using monofunctional isocyanates in the present invention, and wherein monofunctional isocyanates include octadecyl
Isocyanates, hexadecyl isocyanate, dodecyl isocyanate.
Heat filling is as follows using the specific method of monofunctional isocyanates processing in the present invention：
In there-necked flask, toluene is added in, adds in multi-walled carbon nanotube (or graphene), adds in monofunctional isocyanates,
A few drop dibutyl tin laurates are added dropwise, are stirred and heated to 65~75 DEG C, when isothermal reaction 10~13 is small.After completion of the reaction,
Product is filtered, added in filter residue acetone agitator treating 2 it is small when more than, 3~4 times repeatedly, be subsequently isolated, and be dried in vacuo 22~
25h, it is isocyanate-modified multi-walled carbon nanotube (or isocyanate-modified graphene) to obtain product.The multi wall wherein added in
Carbon nanotubes or graphene, monofunctional isocyanates, the mass ratio of dibutyl tin laurate are 1:0.9~1.1:0.3~
0.6。
In cyanate ester resin/heat conduction filler composition of the present invention, it can be included into cyanate ester resin and add common change
Property agent.
In cyanate ester resin/heat conduction filler composition of the present invention, cyanate ester resin can also be a variety of cyanate resins
The mixture of fat.
The present inventor has found that the carbon nanomaterial for adding surface treatment significantly improves cyanate ester resin by experiment and research
The thermal conductivity factor of cured product, shown in following article embodiment and comparative example.
Cyanate ester resin/heat conduction filler composition proposed by the present invention can be with various increasings familiar to the person skilled in the art
Strong material, such as inorganic reinforcement such as silica, calcium carbonate, carbon nanotubes, carbon fiber, organic reinforcing such as aramid fiber
Fiber etc. is configured to various compositions, to obtain the thermosetting resin of different purposes and its product.
The preparation method of cyanate ester resin/heat conduction filler composition of the present invention, this method are included cyanate ester resin with leading
Hot filler is mixed to get cyanate ester resin/heat conduction filler composition.
As hybrid mode, it is mixed that mechanical mixture well-known to those skilled in the art, solution mixing, melting may be employed
Close, can also assisting ultrasonic disperse, high-speed stirred the methods of.
The present invention provides a kind of compositions of thermosetting resin, comprising above-mentioned cyanate ester resin/heat conduction filler composition and
Other thermosetting resins.
Other thermosetting resins can be the common thermosetting resins of familiar to the person skilled in the art other, such as Ben Bing Evil
Piperazine resin, epoxy resin, bimaleimide resin, Thermocurable polyimide etc..It, can by using different thermosetting resins
To obtain the thermosetting resin of different purposes and its product.
It is prepared the present invention also provides cyanate ester resin/heat conduction filler composition and asphaltic base heat conduction carbon fiber or its fabric
Prepreg.Wherein the mass percentage content of cyanate ester resin/heat conduction filler composition is 37%~43%, asphaltic base heat conduction carbon
The mass percentage content of fiber or its fabric is 57%~63%.
The preparation method of the prepreg of cyanate ester resin/heat conduction filler composition of the present invention, by by cyanate ester resin/lead
Hot fill composition and asphaltic base heat conduction carbon fiber or its fabric, prepare by the dipping of dry or wet.Wherein wet method is
Refer to resin solution to carry out dipping with asphaltic base heat conduction carbon fiber or its fabric and prepare prepreg；Dry method includes powder method and hot melt is set
The impregnation technologies such as fat method.
Cyanate ester resin/heat conduction filler composition and its prepreg proposed by the present invention, wherein cyanate ester resin/heat conduction are filled out
Feed composition may be employed thermosetting resin familiar to the person skilled in the art and its composite material and pass through various processing and forming works
Various products are made in skill.The heat conductivility of cyanate ester resin/heat conduction filler composition, prepreg and its composite material obtained is excellent
It is different；As the matrix resin of high-performance composite materials or as High-performance adhesive and coating, available for electronics industry, aviation,
All conglomeraties such as space flight, defence and military.
Embodiment
The present invention is described in more detail below by way of specific embodiment.
It is raw materials used in embodiment, instrument is as follows：
Bisphenol A cyanate ester monomer (HF-1)：Shangyu Shengda Biochemical Co., Ltd..
Multi-walled carbon nanotube：FloTube 9000, Beijing Tiannai Science and Technology Co., Ltd；
Graphene：graphene nanoplatelets,Strem Chemicals.
Perkin-Elmer Pyris1 type DSC testers：For measuring the specific heat capacity of cured product, test condition：N2Ring
Border, heating rate are 10 DEG C/min, Al2O3For reference substance, Range of measuring temp：0~50 DEG C.
Thermal conductivity test：Laser shines method thermal conductivity coefficient measurement instrument, LFA 447 (German Netzsch companies), 25 DEG C, GB/
T22588-2008, ASTM E 1269-5.
Real density instrument, Quantachrome Ultrapycnometer 1000 (Kang Ta companies of the U.S.).
The surface treatment of multi-walled carbon nanotube and graphene：
In 1000ml there-necked flasks (being furnished with polytetrafluoroethylmixer mixer), 500ml toluene is added in, 10 grams of multi wall carbon is added in and receives
Mitron (or 10 grams of graphenes) adds in 10 grams of octadecylisocyanates, and 1~3 drop dibutyl tin laurate, stirring is added dropwise
And be heated to 70 DEG C of isothermal reactions 12 it is small when.After completion of the reaction, product is filtered, filter residue is placed in 500ml beakers, added thereto
Enter 150~200ml acetone, when electromagnetic agitation washing 2 is small more than, be separated by filtration, repeatedly for three times, last gained black solid is through true
Sky is dry for 24 hours, and it is isocyanate-modified multi-walled carbon nanotube (or isocyanate-modified graphene) to obtain product.
Comparative example 1
5~10 grams of bisphenol A cyanate ester resins is taken to be placed in mold, are cured in vacuum drying oven.Curing process is：
100 DEG C~1 it is small when, 120 DEG C~1 it is small when, 140 DEG C~2 it is small when, 160 DEG C~2 it is small when, 180 DEG C~2 it is small when, 200 DEG C~2 is small
When, 220 DEG C~2 it is small when, 240 DEG C~1 it is small when.Cured product measures its heat conduction system using the laser method thermal conductivity coefficient measurement instrument that shines
Number is 0.148Wm-1·K-1。
Embodiment 1
Using solution blended process, by 0.5 gram of octadecylisocyanate modified multiwalled carbon nanotube and 99.5 grams of cyanates
Mixing adds in 500ml acetone solutions, when ultrasonic disperse 6 is small, stands volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~
10 grams of mixtures are placed in mold, are cured in vacuum drying oven.Curing process is：100 DEG C~1 it is small when, 120 DEG C~1 is small
When, 140 DEG C~2 it is small when, 160 DEG C~2 it is small when, 180 DEG C~2 it is small when, 200 DEG C~2 it is small when, 220 DEG C~2 it is small when, 240 DEG C~1
Hour.Cured product uses the laser method thermal conductivity coefficient measurement instrument that shines to measure its thermal conductivity factor as 0.167Wm-1·K-1。
Embodiment 2
Using solution blended process, 3 grams of octadecylisocyanate modified multiwalled carbon nanotubes are mixed with 97 grams of cyanates,
500ml acetone solutions are added in, when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；5~10 grams are taken to mix
It closes object to be placed in mold, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product uses laser
The method thermal conductivity coefficient measurement instrument of shining measures its thermal conductivity factor as 0.203Wm-1·K-1。
Embodiment 3
Using solution blended process, 10 grams of octadecylisocyanate modified multiwalled carbon nanotubes and 90 grams of cyanates are mixed
It closes, adds in 500ml acetone solutions, when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10
Gram mixture is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product uses
The laser method thermal conductivity coefficient measurement instrument that shines measures its thermal conductivity factor as 0.332Wm-1·K-1。
Embodiment 4
Using solution blended process, 0.5 gram of octadecylisocyanate modified graphene with 99.5 grams of cyanates is mixed, is added
Enter 500ml acetone solutions, when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixing
Object is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is dodged using laser
The method thermal conductivity coefficient measurement instrument of penetrating measures its thermal conductivity factor as 0.158Wm-1·K-1。
Embodiment 5
Using solution blended process, 3 grams of octadecylisocyanate modified graphenes with 97 grams of cyanates are mixed, are added in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.297Wm-1·K-1。
Embodiment 6
Using solution blended process, 8 grams of octadecylisocyanate modified graphenes with 92 grams of cyanates are mixed, are added in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.737Wm-1·K-1。
Embodiment 7
Using solution blended process, 10 grams of octadecylisocyanate modified graphenes with 90 grams of cyanates are mixed, are added in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.759Wm-1·K-1。
Embodiment 8
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=4/1 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.377Wm-1·K-1。
Embodiment 9
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=3/1 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.319Wm-1·K-1。
Embodiment 10
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=2/1 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.454Wm-1·K-1。
Embodiment 11
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=1/1 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.474Wm-1·K-1。
Embodiment 12
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=1/2 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.633Wm-1·K-1。
Embodiment 13
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=1/3 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.673Wm-1·K-1。
Embodiment 14
Using solution blended process, by octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecyl
Isocyanate-modified graphene (OM-G) is 10 grams, wherein OM-MWCNT/OM-G=1/4 total, is mixed with 90 grams of cyanates, adds in
500ml acetone solutions when ultrasonic disperse 6 is small, stand volatilization 48h；Using 50 DEG C of 48h of vacuum drying；Take 5~10 grams of mixtures
It is placed in mold, is cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product is shone using laser
Method thermal conductivity coefficient measurement instrument measures its thermal conductivity factor as 0.682Wm-1·K-1。
From above-described embodiment and comparative example result, multi-walled carbon nanotube, the stone of surface treatment for surface treatment
The composition of black alkene and the multi-walled carbon nanotube of surface treatment and the graphene of surface treatment, these heat fillings can be shown
The thermal conductivity factor for improving ethylene rhodanate resin curing product is write, heat filling content is higher, the heat conduction of ethylene rhodanate resin curing product
Coefficient is higher.
The above is only the optimal specific embodiment of the present invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (9)
1. cyanate ester resin/heat conduction filler composition, it is characterised in that：Including heat filling and cyanate ester resin, wherein heat conduction
The mass percentage content of filler is 0.5~10%, and the mass percentage content of cyanate ester resin is 90~99.5%, described to lead
Hot filler is the multi-walled carbon nanotube or the graphene using monofunctional isocyanates processing handled using monofunctional isocyanates
In one kind or combination, if heat filling be using monofunctional isocyanates handle multi-walled carbon nanotube and using simple function it is different
The combination of the graphene of cyanate processing, then the mass ratio of the two is 20~80：80~20；
The specific method that multi-walled carbon nanotube or graphene are handled using monofunctional isocyanates is as follows：
Using toluene as solvent, multi-walled carbon nanotube or graphene, monofunctional isocyanates, dibutyl tin laurate are added in, is stirred
It mixes and is heated to 65~75 DEG C, when isothermal reaction 10~13 is small；After completion of the reaction, product is filtered, acetone is added in filter residue and is stirred
Mix washing 2 it is small when more than, 3~4 times repeatedly, be subsequently isolated, and be dried in vacuo 22~25h, it is simple function isocyanide to obtain product
The multi-walled carbon nanotube of acid esters processing or the graphene of monofunctional isocyanates processing.
2. cyanate ester resin/heat conduction filler composition according to claim 1, it is characterised in that：The simple function isocyanide
Acid esters is octadecylisocyanate, hexadecyl isocyanate or dodecyl isocyanate.
3. cyanate ester resin/heat conduction filler composition according to claim 1, it is characterised in that：The multi wall of the addition
Carbon nanotubes or graphene, monofunctional isocyanates, the mass ratio of dibutyl tin laurate are 1:0.9~1.1:0.3~
0.6。
4. cyanate ester resin/heat conduction filler composition according to claim 1 or 2, it is characterised in that：The cyanate resin
The general formula of fat is as follows：
N≡C-O-R'-O-C≡N
Wherein：R' is alkylidene, arlydene, sub- unsaturated group or sub- alcyl.
5. cyanate ester resin/heat conduction filler composition according to claim 4, it is characterised in that：The cyanate ester resin
Including following any one or combination：
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
6. cyanate ester resin/heat conduction filler composition according to claim 1 or 2, it is characterised in that：The cyanate resin
The mixture of cyanate ester resin and epoxy resin may be employed in fat or prepolymer substitutes, and the epoxy resin is glycidol ethers
Epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy compound or heterocycle and mixed
Mould assembly epoxide.
7. cyanate ester resin/heat conduction filler composition according to claim 6, it is characterised in that：The epoxy resin is
Bisphenol A type epoxy resin, epoxidization phenolic resin, TDE-80# epoxy resin, amino tetrafunctional epoxy resin AG-80#.
8. cyanate ester resin/heat conduction filler composition prepreg, it is characterised in that：Including the cyanogen described in one of claim 1~7
Acid ester resin/heat conduction filler composition and asphaltic base heat conduction carbon fiber or its fabric, wherein cyanate ester resin/heat filling combination
The mass percentage content of object is 37%~43%, and the mass percentage content of asphaltic base heat conduction carbon fiber or its fabric is 57%
~63%.
9. the application of cyanate ester resin/heat conduction filler composition described in one of claim 1~7, it is characterised in that：The cyanogen
Matrix resin of the acid ester resin/heat conduction filler composition as composite material, is used to prepare composite material；The cyanate resin
Matrix resin of the fat/heat conduction filler composition as adhesive, is used to prepare adhesive；Cyanate ester resin/the heat filling
Matrix resin of the composition as coating, is used to prepare coating.
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| CN107298777B (en) * | 2017-06-22 | 2019-01-11 | 河北科技大学 | A kind of graphene-based high abrasion nitile-butadiene rubber composite material and preparation method thereof |
| CN109796759B (en) * | 2017-11-16 | 2021-12-24 | 长春长光宇航复合材料有限公司 | Cyanate ester-based carbon fiber composite material with high thermal conductivity coefficient and preparation method thereof |
| CN109266187B (en) * | 2018-08-10 | 2021-02-05 | 恒力盛泰（厦门）石墨烯科技有限公司 | Heat dissipation coating containing isocyanate modified graphene and preparation method thereof |
| CN110079087A (en) * | 2019-05-07 | 2019-08-02 | 中国电子科技集团公司第三十八研究所 | A kind of modified nano graphite/cyanate composite material, preparation method and application |
| CN110452534A (en) * | 2019-08-23 | 2019-11-15 | 付福来 | A kind of cyanate resin base composite material with excellent heat conducting performance |
| CN112251188B (en) * | 2020-10-28 | 2021-07-20 | 哈尔滨工业大学 | Heat-conducting adhesive film suitable for bonding optical load structure and preparation method thereof |
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| CN104231624B (en) * | 2014-08-22 | 2016-05-11 | 南京信息职业技术学院 | A kind of modified cyanic acid ester resin heat-conductive composite material and preparation method thereof |
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