CN105368046A - Composition of cyanate ester resin and thermal conducting filler, and prepreg and application thereof - Google Patents
Composition of cyanate ester resin and thermal conducting filler, and prepreg and application thereof Download PDFInfo
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- CN105368046A CN105368046A CN201510850002.4A CN201510850002A CN105368046A CN 105368046 A CN105368046 A CN 105368046A CN 201510850002 A CN201510850002 A CN 201510850002A CN 105368046 A CN105368046 A CN 105368046A
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- China
- Prior art keywords
- cyanate ester
- resin
- ester resin
- heat conduction
- filler composition
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- 229920005989 resin Polymers 0.000 title claims abstract description 134
- 239000011347 resin Substances 0.000 title claims abstract description 134
- 239000004643 cyanate ester Substances 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000000945 filler Substances 0.000 title claims abstract description 59
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 32
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 74
- 239000003822 epoxy resin Substances 0.000 claims description 52
- 229920000647 polyepoxide Polymers 0.000 claims description 52
- 230000008569 process Effects 0.000 claims description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 35
- 238000001291 vacuum drying Methods 0.000 claims description 33
- 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 25
- 239000011231 conductive filler Substances 0.000 claims description 20
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 17
- 229930185605 Bisphenol Natural products 0.000 claims description 15
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 14
- -1 glycidyl ester Chemical class 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 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 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 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000003756 stirring Methods 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
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims description 3
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000007123 defense Effects 0.000 abstract 1
- 150000001913 cyanates Chemical class 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 229920001187 thermosetting polymer Polymers 0.000 description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 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 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000004381 surface treatment Methods 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
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-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
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 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
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 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
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012856 packing Methods 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
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 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
- 229920003987 resole Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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 invention relates to a composition of cyanate ester resin and thermal conducting filler, and prepreg and application thereof. The composition comprises, by mass, 0.5 to 10% of the thermal conducting filler and 90 to 99.5% of the cyanate ester resin, wherein the thermal conducting filler is one or a combination selected from the group consisting of monofunctional isocyanate treated multi-walled carbon nanotubes or monofunctional isocyanate treated graphene; if the thermal conducting filler is the combination of the monofunctional isocyanate treated multi-walled carbon nanotubes and the monofunctional isocyanate treated graphene, a mass ratio of the monofunctional isocyanate treated multi-walled carbon nanotubes and the monofunctional isocyanate treated graphene is 20-80: 80-20; and the composition can be prepared into the prepreg by mixing with continuous fibers or fabrics. The composition and the prepreg thereof provided by the invention have excellent thermal conductivity, can be used as a matrix resin of a high-performance composite material or used as a high-performance adhesive and a coating, and can be applied in a plurality of industries like electronic industry, aviation industry, space industry and national defense military industry.
Description
Technical field
The present invention relates to cyanate ester resin/heat conduction filler composition, prepreg and application thereof, this prepreg can be used for for the preparation of high performance composite, 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 materials.
The synthesis of cyanate resin alicyclic monomer has multiple method, the most frequently used and to realize industrialized be in the presence of a base, and halogen cyan and phenolic compound react prepares cyanate ester monomer.There are three cyclizations in cyanate ester resin under heat or catalyst action, generates the macromole of the high crosslink density network structure containing triazine ring.The cyanate ester resin of this structure has low-k and minimum dielectric loss tangent value, high glass-transition temperature, low rate of moisture absorption, low-shrinkage and the feature such as excellent mechanical property and adhesive property.Cyanate ester resin has the processing characteristics similar to epoxy resin, can solidify, and do not have volatile small molecule to produce in the curing process at 177 DEG C.And it has the resistance to elevated temperatures suitable with bimaleimide resin, there are the dielectric properties more excellent than polyamide-imide, there is the resistance to flame energy suitable with resol.
About the background technology of cyanate and primary synthetic methods thereof can be precious in " high-performance resin matrix " (Chemical Industry Press with reference to Chen Xiang, version in 1999), Yan Fusheng etc. " synthesis of bisphenol A cyanate ester resin " ([J]. engineering plastics apply, 1999, 27 (8)), SNOWAW is at " Thesynthesismanufactureandcharacterizationofcyanateester monomers " ([J] .SAMPEJ, 2000 (36)), Hamerton etc. are at " Recentdevelopmentsinthechemistryofcyanateester " ([J] .PolymInt, 1998, 47 (4)), ChaplinA etc. are at " Developmentofnovelfunctionalizedarylcyanateesteroligomer s1.Synthesisandthermalcharacterizationofthemonomers " ([J] .Macromolecules, 1994, 27 (18)) method etc. mentioned in works and article and research background.
Although cyanate ester resin has excellent performance, the thermal conductivity of its cured product is still on the low side, which has limited its application in thermally conductive material field.For improving the thermal conductivity of ethylene rhodanate resin curing product, report part cyanate ester resin composite material system.Such as close sub-man, 2013-University Of Suzhou, the research [academic dissertation] of high heat conduction aluminium nitride-carbon nano-tube/polymer based composites, mainly inquire into aluminium nitride-carbon nanotube/cyanate ester resin composite material, prepared aluminium nitride-content of carbon nanotubes and be respectively 40 ~ 47.5% and 1.5 ~ 2.5%, its thermal conductivity can reach 2.28 ~ 5Wm
-1k
-1but wherein heat conductive filler content is very high, be unsuitable for being used as prepreg resin.
Such as (1) Su Lei, 2012-Institutes Of Technology Of Nanjing, the preparation [academic dissertation] of cyanate resin base heat conductive insulating matrix material; (2) Zhao Chunbao, Su Lei etc., the fabrication & properties research of cyanate ester resin/ZnOw matrix material, New Chemical Materials, 2013,41 (11), 62-64; (3) Zhao Chunbao, Su Lei etc., the fabrication & properties research of cyanate ester resin/oxidized graphite flake matrix material, functional materials, 2013,44 (16), mainly adopt silane coupling agent (KH550) to carry out surface treatment to four acicular type zinc oxide crystal whisker (T-ZnOw), hexagonal boron nitride (h-BN) in the above-mentioned report of 2301-2304., select amino dodecane (DDA) to carry out organic modification of surface to graphite oxide (GO); And prepared a series of cyanate resin base heat conductive insulating such as T-ZnOw/CE, BN/CE, BN-ZnOw/CE, GO-DDA/CE matrix material, when wherein ZnOw content is 12%, the thermal conductivity of matrix material reaches 0.79Wm
-1k
-1; When BN volume parts is 24%, the thermal conductivity of matrix material reaches 1.33Wm
-1k
-1; After adding the mixed fillers of 20% volume fraction (BN-ZnOw), the thermal conductivity of matrix material reaches 1.19Wm
-1k
-1; When GO-DDA content 1%, thermal conductivity reaches 0.43Wm
-1k
-1.Above-mentioned work can prepare multiple heat-conductive composite material, but is not suitable for preparing prepreg heat-conducting resin, and the packing density mentioned above being specially is large, causes composite weight and strengthens, be not suitable for spacecraft structural weight being had to strict demand; Silane coupling agent is low-molecular material, may separate out under space environment, can not meet under composite space environment the requirement can coagulating volatile matter; The amount added is in addition all more than 10%, and the viscosity of gained resin is too large, poor fluidity cannot prepare prepreg.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, provide cyanate ester resin/heat conduction filler composition, said composition is suitable for the prepreg resin as fibre composite, and its cured product has higher thermal conductivity and excellent performance.
Another object of the present invention is to provide cyanate ester resin/heat conduction filler composition prepreg and application thereof.
Above-mentioned purpose of the present invention is mainly achieved by following technical solution:
Cyanate ester resin/heat conduction filler composition, comprise heat conductive filler and cyanate ester resin, wherein the mass percentage content of heat conductive filler is 0.5 ~ 10%, the mass percentage content of cyanate ester resin is 90 ~ 99.5%, described heat conductive filler is adopt the multi-walled carbon nano-tubes of monofunctional isocyanates process or adopt the one in the Graphene of monofunctional isocyanates process or combination, if heat conductive filler is the combination of the Graphene adopting the multi-walled carbon nano-tubes of monofunctional isocyanates process and adopt monofunctional isocyanates process, then the mass ratio of the two is 20 ~ 80:80 ~ 20.
In above-mentioned cyanate ester resin/heat conduction filler composition, monofunctional isocyanates is octadecylisocyanate, hexadecyl isocyanate or dodecyl isocyanate.
In above-mentioned cyanate ester resin/heat conduction filler composition, adopt the concrete grammar of monofunctional isocyanates process multi-walled carbon nano-tubes or Graphene as follows:
Be solvent with toluene, add multi-walled carbon nano-tubes or Graphene, monofunctional isocyanates, dibutyl tin laurate, stir and be heated to 65 ~ 75 DEG C, isothermal reaction 10 ~ 13 hours; After completion of the reaction, product is filtered, adds acetone agitator treating in filter residue more than 2 hours, 3 ~ 4 times repeatedly, be separated subsequently, and vacuum-drying 22 ~ 25h, obtain product and be isocyanate-modified multi-walled carbon nano-tubes or isocyanate-modified Graphene.
In above-mentioned cyanate ester resin/heat conduction filler composition, the mass ratio of the multi-walled carbon nano-tubes added or Graphene, monofunctional isocyanates, dibutyl tin laurate is 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 group, arylidene, sub-unsaturated group or sub-alicyclic radical.
In above-mentioned cyanate ester resin/heat conduction filler composition, cyanate ester resin comprises 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 type 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 can adopt the mixture of cyanate ester resin and epoxy resin or prepolymer to substitute, and described epoxy resin is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy compound or heterocycle and mixed type epoxy compounds.
In above-mentioned cyanate ester resin/heat conduction filler composition, epoxy resin is bisphenol A type epoxy resin, epoxidization phenolic resin, TDE-80# epoxy resin, amino four functional epoxy resin AG-80#.
Cyanate ester resin/heat conduction filler composition prepreg, comprise cyanate ester resin/heat conduction filler composition described in claim 1 ~ 8 and asphaltic base heat conduction carbon fiber or its fabric, wherein the mass percentage content of cyanate ester resin/heat conduction filler composition is 37% ~ 43%, and 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 as the matrix resin of matrix material, for the preparation of matrix material; Described cyanate ester resin/heat conduction filler composition as the matrix resin of sizing agent, for the preparation of sizing agent; Described cyanate ester resin/heat conduction filler composition as the matrix resin of coating, for the preparation of coating.
The present invention compared with prior art has following beneficial effect:
(1), the present invention adopts the one in monofunctional isocyanates surface-treated multi-walled carbon nano-tubes (OM-MWCNT) or Graphene (OM-G) and composition thereof to mix with cyanate ester resin, obtain cyanate ester resin/heat conduction filler composition thus, said composition is suitable for the prepreg resin as fibre composite, and its cured product has higher thermal conductivity and excellent performance.
(2), the present invention preferably adopts the multi-walled carbon nano-tubes of modification and the composition of Graphene to mix with cyanate ester resin, graphene film and carbon nanotube have obvious synergistic effect in the conduction process of resin, can better improve the thermal conductivity of the X of matrix material, Y, Z-direction;
(3), the present invention adopts the multi-walled carbon nano-tubes of the mixture of cyanate ester resin and epoxy resin or prepolymer and modification or Graphene to mix, compare and adopt cyanate ester resin separately, epoxy resin can accelerate the reaction of cyanate ester resin, act synergistically with cyanate ester resin, reduce its solidification value, extend resin preservation period;
(4), in the present invention the addition of heat conductive filler within 10%, even within 4%, just can reach higher thermal conductivity, overcome in prior art and add too much heat conductive filler and cause the defect that the viscosity of resin is too large, poor fluidity cannot prepare prepreg.
(5), cyanate ester resin/heat conduction filler composition of the present invention and prepreg thereof, wherein cyanate ester resin/heat conduction filler composition thermosetting resin that those skilled in the art can be adopted to be familiar with and matrix material thereof make various goods by various contour machining procedure, the excellent thermal conductivity of the matrix material that cyanate ester resin/heat conduction filler composition and prepreg thereof obtain; As the matrix resin of high performance composite, or be used as High-performance adhesive and coating, can be used for all conglomeraties such as electronic industry, Aeronautics and Astronautics, defence and military.
Embodiment
Below by specific embodiment, the present invention is described in further detail:
The invention provides a kind of cyanate ester resin/heat conduction filler composition, wherein the mass percentage content of heat conductive filler and cyanate resin composition is respectively 0.5 ~ 10%, 90 ~ 99.5%; Described heat conductive filler refers to one or both compositions in monofunctional isocyanates surface-treated multi-walled carbon nano-tubes (OM-MWCNT) or monofunctional isocyanates surface-treated Graphene (OM-G).Also the mass percentage content of heat conductive filler and cyanate resin composition can be selected to be respectively 1.5 ~ 3.5%, 96.5 ~ 98.5%.
If when heat conductive filler is the composition adopting the multi-walled carbon nano-tubes of monofunctional isocyanates process and the Graphene of employing monofunctional isocyanates process, the mass ratio of the two is 20 ~ 80:80 ~ 20.
In the present invention, cyanate ester resin refers to that in molecule, structure contains the compound, polymkeric substance and composition thereof of at least two cyanate groups, and general formula is shown below,
N≡C-O-R′-O-C≡N
Wherein R ' can be alkylidene group, arylidene, sub-unsaturated group or sub-alicyclic radical.
Especially, in the preferred implementation of cyanate ester resin/heat conduction filler composition according to the present invention, cyanate ester resin refers to cyanate ester monomer and their mixture containing being selected from structural unit described in following (1)-(8):
(1) the bisphenol A cyanate ester monomer (HF-1) shown in following formula
This bisphenol A cyanate ester monomer (HF-1), be a commercial class cyanate ester monomer the earliest, it is cheap, is suitable for industrial application;
(2) the bisphenol E-type cyanate monomer (HF-9) shown in following formula
This bisphenol E-type cyanate monomer (HF-9), exists with low-viscosity (mobile) liquid form in room temperature, is suitable for application;
(3) the bisphenol E-type cyanate monomer (HF-9) shown in following formula
(4) the tetramethyl-bisphenol-f type cyanate ester monomer shown in following formula
(5) the tetramethyl-bisphenol-f type cyanate ester monomer shown in following formula
(6) bis-phenol M type cyanate ester monomer (HF-7) shown in following formula
(7) the polyfunctional group type cyanate ester monomer (HF-5) shown in following formula
(8) the dicyclopentadiene bisphenol type cyanate ester monomer (HF-3) shown in following formula
In addition; cyanate ester resin can also comprise the cyanate resin alicyclic monomer of other kinds; such as I.Hamerton mentions the cyanate ester monomer (I.Hamerton of other kinds in " ChemistryandTechnologyofCyanateEsterResins "; ChemistryandTechnologyofCyanateEsterResins; BlackieAcademic & ProfessionalGlasgow; London; 1994.), or the company such as Cida, Lonza, Dow and Shanghai Hui Feng science and trade produce other different structure cyanates.
In the present invention, cyanate ester resin can also adopt the mixture of cyanate ester resin and epoxy resin or prepolymer to substitute, its epoxy resin can utilize existing epoxy resin, or utilize the epoxy resin that prior art is synthesized, the many benevolence of such as Wang in " Synthesis and application of epoxy resin " ([J]. thermosetting resin, 2001, 16 (1)), old equality " epoxy resin and application thereof " ([M]. Chemical Industry Press, 2004), MING-KUNGLISIMON etc. are at " Epoxyresinpreparationprocess " ([P], EP86200962A, 1986), Peng Ping Ren etc. " epoxy resin produce novel process " ([J]. coatings industry, 1997, 4 (26)) epoxy resin etc. mentioned in works and article and synthetic method thereof.
Wherein, epoxy resin is containing being selected from the epoxy monomer described in following (1)-(4) and their mixture:
(1) Racemic glycidol ethers
Glycidyl ether type epoxy resin mainly contains again bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxidization phenolic resin.
Bisphenol A type epoxy resin enters etherificate by dihydroxyphenyl propane and epoxy chloropropane and closed loop two-step reaction is worth, such as E-55, E-51, E-20; Bisphenol-s epoxy resin is by bisphenol S and the excess epoxy chloropropane high-temperature-resistant epoxy resin that obtains of polycondensation in the basic conditions; Bisphenol f type epoxy resin is by Bisphenol F and excess epoxy chloropropane (1:10), under tetramethyl ammonium chloride and NaOH condition, through etherificate and ring-closure reaction, polycondensation; Epoxy phenolics be by pf resin of low molecular weight and epoxy chloropropane under an acid catalysis condensation form;
(2) glycidyl ester class
Glycidyl ester epoxy resin is the compound having more than two or two Racemic glycidol ester groups in molecular structure.Such as 711# epoxy resin, TDE-80# epoxy resin, 731# epoxy resin, CY-183# epoxy resin;
(3) Racemic glycidol amine
Glycidyl amine epoxy resin is the compound containing two or two or more Racemic glycidol amido synthesized with primary amine or secondary amine and epoxy chloropropane.Such as amino four functional epoxy resins (AG-80#), AFG-90# epoxy resin;
(4) aliphatic epoxy compound
Aliphatic epoxy compound is oxidized through double bond from containing the alicyclic of unsaturated double-bond structure or obtain with hypochlorous acid addition epoxidation.Such as W-95# epoxy resin, 6221# epoxy resin, 6206# epoxy resin.
In addition, heterocycle and mixed type epoxy compounds is also had, as: glycolylurea resin, tricyanic epoxy resin, flame-retarded resin etc.
Epoxy resin preferably includes bisphenol A type epoxy resin, epoxidization phenolic resin, TDE-80# epoxy resin, amino four functional epoxy resins (AG-80#).
In the present invention, heat conductive filler adopts monofunctional isocyanates process, and wherein monofunctional isocyanates comprises octadecylisocyanate, hexadecyl isocyanate, dodecyl isocyanate.
In the present invention, heat conductive filler adopts the concrete grammar of monofunctional isocyanates process as follows:
In there-necked flask, add toluene, add multi-walled carbon nano-tubes (or Graphene), add monofunctional isocyanates, drip several dibutyl tin laurates, stir and be heated to 65 ~ 75 DEG C, isothermal reaction 10 ~ 13 hours.After completion of the reaction, product is filtered, adds acetone agitator treating in filter residue more than 2 hours, 3 ~ 4 times repeatedly, be separated subsequently, and vacuum-drying 22 ~ 25h, obtain product and be isocyanate-modified multi-walled carbon nano-tubes (or isocyanate-modified Graphene).The mass ratio of the multi-walled carbon nano-tubes wherein added or Graphene, monofunctional isocyanates, dibutyl tin laurate is 1:0.9 ~ 1.1:0.3 ~ 0.6.
In cyanate ester resin/heat conduction filler composition of the present invention, can draw together in cyanate ester resin and add conventional properties-correcting agent.
In cyanate ester resin/heat conduction filler composition of the present invention, cyanate ester resin can also be the mixture of multiple cyanate ester resin.
The present inventor finds through experiment and research, adds the thermal conductivity that surface-treated carbon nanomaterial significantly improves ethylene rhodanate resin curing product, as shown in Examples below and comparative example.
The various strongtheners that cyanate ester resin/heat conduction filler composition that the present invention proposes can be familiar with those skilled in the art, as inorganic reinforcement such as silicon-dioxide, calcium carbonate, carbon nanotube, carbon fiber etc., organic reinforcing such as aramid fiber etc. is mixed with various composition, to obtain thermosetting resin and the goods thereof of different purposes.
The preparation method of cyanate ester resin/heat conduction filler composition of the present invention, the method comprises cyanate ester resin and heat conductive filler is mixed to get cyanate ester resin/heat conduction filler composition.
As hybrid mode, can adopt the mixing of mechanically mixing well-known to those skilled in the art, solution, melting mixing, also can the method such as assisting ultrasonic dispersion, high-speed stirring.
The invention provides a kind of compositions of thermosetting resin, comprise above-mentioned cyanate ester resin/heat conduction filler composition and other thermosetting resins.
Other thermosetting resins can be other conventional thermosetting resins that those skilled in the art are familiar with, such as benzoxazine colophony, epoxy resin, bimaleimide resin, Thermocurable polyimide etc.By adopting different thermosetting resins, thermosetting resin and the goods thereof of different purposes can be obtained.
The prepreg that the present invention also provides cyanate ester resin/heat conduction filler composition to prepare with asphaltic base heat conduction carbon fiber or its fabric.Wherein the mass percentage content of cyanate ester resin/heat conduction filler composition is 37% ~ 43%, and the mass percentage content of asphaltic base heat conduction carbon 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/heat conduction filler composition and asphaltic base heat conduction carbon fiber or its fabric, through dry method or wet method dipping and prepare.Wherein wet method refers to that resin solution and asphaltic base heat conduction carbon fiber or its fabric carry out dipping and prepare prepreg; Dry method comprises the impregnation technology such as powder method and thermoplastic resin method.
Cyanate ester resin/heat conduction filler composition that the present invention proposes and prepreg thereof, wherein cyanate ester resin/heat conduction filler composition thermosetting resin that those skilled in the art can be adopted to be familiar with and matrix material thereof make various goods by various contour machining procedure.The excellent thermal conductivity of cyanate ester resin/heat conduction filler composition, prepreg and obtained matrix material thereof; As the matrix resin of high performance composite, or be used as High-performance adhesive and coating, can be used for all conglomeraties such as electronic industry, Aeronautics and Astronautics, defence and military.
embodiment
Below by way of specific embodiment, the present invention is described in more detail.
Raw materials used in embodiment, instrument is as follows:
Bisphenol A cyanate ester monomer (HF-1): Shangyu Shengda Biochemical Co., Ltd..
Multi-walled carbon nano-tubes: FloTube9000, Beijing Tiannai Science and Technology Co., Ltd;
Graphene: graphenenanoplatelets, StremChemicals.
Perkin-ElmerPyris1 type DSC tester: for measuring the specific heat capacity of cured product, test condition: N
2environment, temperature rise rate is 10 DEG C/min, Al
2o
3for reference substance, Range of measuring temp: 0 ~ 50 DEG C.
Thermal conductivity test: laser shines method thermal conductivity coefficient measurement instrument, LFA447 (German Netzsch company), 25 DEG C, GB/T22588-2008, ASTME1269-5.
True density instrument, QuantachromeUltrapycnometer1000 (Kang Ta company of the U.S.).
The surface treatment of multi-walled carbon nano-tubes and Graphene:
In 1000ml there-necked flask (being furnished with polytetrafluoroethylmixer mixer), add 500ml toluene, add 10 grams of multi-walled carbon nano-tubes (or 10 grams of Graphenes), add 10 grams of octadecylisocyanates, drip 1 ~ 3 dibutyl tin laurate, stir and be heated to 70 DEG C of isothermal reactions 12 hours.After completion of the reaction, product is filtered, filter residue is placed in 500ml beaker, add 150 ~ 200ml acetone wherein, induction stirring washs more than 2 hours, filtering separation, three times repeatedly, last gained black solid, through vacuum-drying 24h, obtains product and is isocyanate-modified multi-walled carbon nano-tubes (or isocyanate-modified Graphene).
Comparative example 1
Get 5 ~ 10 grams of bisphenol A cyanate ester resins and be placed in mould, be cured in vacuum drying oven.Curing process is: 100 DEG C ~ 1 hour, 120 DEG C ~ 1 hour, 140 DEG C ~ 2 hours, 160 DEG C ~ 2 hours, 180 DEG C ~ 2 hours, 200 DEG C ~ 2 hours, 220 DEG C ~ 2 hours, 240 DEG C ~ 1 hour.Cured product adopts laser to shine, and to record its thermal conductivity be 0.148Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 1
Adopt solution blended process, 0.5 gram of octadecylisocyanate modified multiwalled carbon nanotube is mixed with 99.5 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Curing process is: 100 DEG C ~ 1 hour, 120 DEG C ~ 1 hour, 140 DEG C ~ 2 hours, 160 DEG C ~ 2 hours, 180 DEG C ~ 2 hours, 200 DEG C ~ 2 hours, 220 DEG C ~ 2 hours, 240 DEG C ~ 1 hour.Cured product adopts laser to shine, and to record its thermal conductivity be 0.167Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 2
Adopt solution blended process, 3 grams of octadecylisocyanate modified multiwalled carbon nanotubes are mixed with 97 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.203Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 3
Adopt solution blended process, 10 grams of octadecylisocyanate modified multiwalled carbon nanotubes are mixed with 90 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.332Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 4
Adopt solution blended process, 0.5 gram of octadecylisocyanate modified graphene is mixed with 99.5 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.158Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 5
Adopt solution blended process, 3 grams of octadecylisocyanate modified graphenes are mixed with 97 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.297Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 6
Adopt solution blended process, 8 grams of octadecylisocyanate modified graphenes are mixed with 92 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.737Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 7
Adopt solution blended process, 10 grams of octadecylisocyanate modified graphenes are mixed with 90 grams of cyanates, adds 500ml acetone solution, ultrasonic disperse 6 hours, leave standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.759Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 8
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=4/1, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.377Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 9
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=3/1, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.319Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 10
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=2/1, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.454Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 11
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=1/1, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.474Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 12
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=1/2, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.633Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 13
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=1/3, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.673Wm to method thermal conductivity coefficient measurement instrument
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Embodiment 14
Adopt solution blended process, octadecylisocyanate modified multiwalled carbon nanotube (OM-MWCNT), octadecylisocyanate modified graphene (OM-G) are added up to 10 grams, wherein OM-MWCNT/OM-G=1/4, mix with 90 grams of cyanates, add 500ml acetone solution, ultrasonic disperse 6 hours, leaves standstill volatilization 48h; Again through vacuum-drying 50 DEG C of 48h; Get 5 ~ 10 grams of mixtures and be placed in mould, be cured in vacuum drying oven.Its curing process is consistent with embodiment 1.Cured product adopts laser to shine, and to record its thermal conductivity be 0.682Wm to method thermal conductivity coefficient measurement instrument
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From above-described embodiment and comparative example result, for surface-treated multi-walled carbon nano-tubes, surface-treated Graphene, and the composition of surface-treated multi-walled carbon nano-tubes and surface-treated Graphene, these heat conductive fillers can significantly improve the thermal conductivity of ethylene rhodanate resin curing product, heat conductive filler content is higher, and the thermal conductivity of ethylene rhodanate resin curing product is higher.
The above; be only the embodiment of the best of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
The content be not described in detail in specification sheets of the present invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. cyanate ester resin/heat conduction filler composition, it is characterized in that: comprise heat conductive filler and cyanate ester resin, wherein the mass percentage content of heat conductive filler is 0.5 ~ 10%, the mass percentage content of cyanate ester resin is 90 ~ 99.5%, described heat conductive filler is adopt the multi-walled carbon nano-tubes of monofunctional isocyanates process or adopt the one in the Graphene of monofunctional isocyanates process or combination, if heat conductive filler is the combination of the Graphene adopting the multi-walled carbon nano-tubes of monofunctional isocyanates process and adopt monofunctional isocyanates process, then the mass ratio of the two is 20 ~ 80:80 ~ 20.
2. cyanate ester resin/heat conduction filler composition according to claim 1, is characterized in that: described monofunctional isocyanates is octadecylisocyanate, hexadecyl isocyanate or dodecyl isocyanate.
3. cyanate ester resin/heat conduction filler composition according to claim 1 and 2, is characterized in that: adopt the concrete grammar of monofunctional isocyanates process multi-walled carbon nano-tubes or Graphene as follows:
Be solvent with toluene, add multi-walled carbon nano-tubes or Graphene, monofunctional isocyanates, dibutyl tin laurate, stir and be heated to 65 ~ 75 DEG C, isothermal reaction 10 ~ 13 hours; After completion of the reaction, product is filtered, adds acetone agitator treating in filter residue more than 2 hours, 3 ~ 4 times repeatedly, be separated subsequently, and vacuum-drying 22 ~ 25h, obtain product and be isocyanate-modified multi-walled carbon nano-tubes or isocyanate-modified Graphene.
4. cyanate ester resin/heat conduction filler composition according to claim 3, is characterized in that: described in the multi-walled carbon nano-tubes that adds or Graphene, monofunctional isocyanates, dibutyl tin laurate mass ratio be 1:0.9 ~ 1.1:0.3 ~ 0.6.
5. cyanate ester resin/heat conduction filler composition according to claim 1 and 2, is characterized in that: the general formula of described cyanate ester resin is as follows:
N≡C-O-R′-O-C≡N
Wherein: R ' is alkylidene group, arylidene, sub-unsaturated group or sub-alicyclic radical.
6. cyanate ester resin/heat conduction filler composition according to claim 5, is characterized in that: described cyanate ester resin comprises 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 type cyanate ester monomer
(7) polyfunctional group type cyanate ester monomer
(8) dicyclopentadiene bisphenol type cyanate ester monomer
7. cyanate ester resin/heat conduction filler composition according to claim 1 and 2, it is characterized in that: described cyanate ester resin can adopt the mixture of cyanate ester resin and epoxy resin or prepolymer to substitute, and described epoxy resin is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy compound or heterocycle and mixed type epoxy compounds.
8. cyanate ester resin/heat conduction filler composition according to claim 7, is characterized in that: described epoxy resin is bisphenol A type epoxy resin, epoxidization phenolic resin, TDE-80# epoxy resin, amino four functional epoxy resin AG-80#.
9. cyanate ester resin/heat conduction filler composition prepreg, it is characterized in that: comprise cyanate ester resin/heat conduction filler composition described in claim 1 ~ 8 and asphaltic base heat conduction carbon fiber or its fabric, wherein the mass percentage content of cyanate ester resin/heat conduction filler composition is 37% ~ 43%, and the mass percentage content of asphaltic base heat conduction carbon fiber or its fabric is 57% ~ 63%.
10. the application of the cyanate ester resin/heat conduction filler composition described in claim 1 ~ 8, is characterized in that: described cyanate ester resin/heat conduction filler composition as the matrix resin of matrix material, for the preparation of matrix material; Described cyanate ester resin/heat conduction filler composition as the matrix resin of sizing agent, for the preparation of sizing agent; Described cyanate ester resin/heat conduction filler composition as the matrix resin of coating, for the preparation of coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510850002.4A CN105368046B (en) | 2015-11-27 | 2015-11-27 | Cyanate ester resin/heat conduction filler composition, prepreg and its application |
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| CN201510850002.4A CN105368046B (en) | 2015-11-27 | 2015-11-27 | Cyanate ester resin/heat conduction filler composition, prepreg and its application |
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| CN109796759A (en) * | 2017-11-16 | 2019-05-24 | 长春长光宇航复合材料有限公司 | A kind of high thermal conductivity coefficient cyanate base carbon fiber composite material 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 |
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| CN112251188A (en) * | 2020-10-28 | 2021-01-22 | 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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| CN107298777A (en) * | 2017-06-22 | 2017-10-27 | 河北科技大学 | A kind of graphene-based high abrasion nitile-butadiene rubber composite material and preparation method thereof |
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| 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 |
| CN112251188A (en) * | 2020-10-28 | 2021-01-22 | 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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