CN103740092B - A kind of high thermal conductivity graphene/nylon composite material and preparation method thereof - Google Patents
A kind of high thermal conductivity graphene/nylon composite material and preparation method thereof Download PDFInfo
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- CN103740092B CN103740092B CN201310699879.9A CN201310699879A CN103740092B CN 103740092 B CN103740092 B CN 103740092B CN 201310699879 A CN201310699879 A CN 201310699879A CN 103740092 B CN103740092 B CN 103740092B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000004677 Nylon Substances 0.000 title claims abstract description 49
- 229920001778 nylon Polymers 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 19
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052582 BN Inorganic materials 0.000 claims abstract description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 17
- 239000004917 carbon fiber Substances 0.000 claims abstract description 17
- 150000003220 pyrenes Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 10
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 8
- 241000555268 Dendroides Species 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims description 2
- PQCZQSHMMXNPSM-UHFFFAOYSA-L copper;dicarbamothioate Chemical compound [Cu+2].NC([O-])=S.NC([O-])=S PQCZQSHMMXNPSM-UHFFFAOYSA-L 0.000 claims description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHIHUCVYAZPLQU-UHFFFAOYSA-N 4,4-diamino-1-(3,5-ditert-butyl-2-hydroxyphenyl)nonan-3-one Chemical compound C(C)(C)(C)C=1C(=C(C=C(C=1)C(C)(C)C)CCC(=O)C(CCCCC)(N)N)O BHIHUCVYAZPLQU-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- 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
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses a kind of high thermal conductivity graphene/nylon composite material and preparation method thereof.By weight, comprise nylon 30 ~ 80 parts, can 4 ~ 8 parts, swollen graphite, amphiphilic pyrene class grafts 0.5 ~ 1.5 part, high orientation silicon nitride fiber 1 ~ 20 part, 1 ~ 15 part, carbon fiber, boron nitride 5 ~ 10 parts, high temperature resistant auxiliary agent 0.02 ~ 4 part, 0.02 ~ 0.8 part, oxidation inhibitor, hydrolysis-resisting agent 1 ~ 3 part, toughner 2 ~ 6 parts.Present invention employs novel heat conduction auxiliary agent in order to improve the heat conductivility of nylon, this heat conduction auxiliary agent is can the Graphene prepared by the ultrasonic stripping method of liquid phase of swollen graphite and amphiphilic pyrene class grafts.The advantage of this novel heat conduction auxiliary agent is: be dispersed in making graphene uniform in matrix resin, can make again the interface cohesive force grow between Graphene and nylon, and consistency improves.
Description
Technical field
The present invention relates to a kind of high thermal conductivity graphene/nylon composite material and preparation method thereof, exactly relate to a kind of high thermal conductivity graphene/nylon 6 or nylon 12 or nylon 66 composite material and preparation method thereof.
Technical background
Nylon has the excellent over-all properties such as good mechanical property, good snappiness, wear resistance, oil-proofness, self lubricity, is widely used in the fields such as automobile industry, electronic apparatus industry, mechanical means, construction industry.Due to its have that the process-cycle is short, production cost is low, long service life and product design degree of freedom advantages of higher obtain applying more and more widely, application in recent years in heat-conductivity polymer composite is particularly outstanding, and the high-power LED radiator that such as DSM company produces has obtained the generally accreditation in market.
Thermally conductive material is widely used in the fields such as heat exchange engineering, Electronics and Information Engineering.For a long time, most of thermally conductive material is metallic substance, but due to the corrosion resistance difference of metallic substance and the factors such as processing characteristics is not good, product design degree of freedom is low, limits its range of application.
In order to improve the surperficial erosion resistance of thermally conductive material, usually adopt the means such as metallurgy, corrosion protection coating, but this method reduces the heat conductivility of material to a large extent and other performances of material do not obtain the improvement of essence.In recent years, along with thermally conductive material range of application is more and more extensive, require also more and more higher to the over-all properties of material.Such as not only require that material has excellent heat conductivility, also require that material has good mechanical property, high temperature resistant use properties, environmental corrosion resisting performance etc.
Traditional heat-conductive composite material generally with Si3N4, SiN, AlN and BN as heat conductive filler, but because the thermal conductivity of itself is low, therefore under high addition, just need can obtain higher thermal conductivity, but this will inevitably reduce other performances of macromolecular material itself.Since Graphene is found for 2004, it, as a kind of novel Two-dimensional Carbon nano material, has fabulous thermal conductivity, specific conductivity, is material that known physical strength is the highest and possesses the advantages such as stable chemical performance light transmission is good.The room temperature thermal conductivity of single-layer graphene reaches 4840 ~ 5300W(mK)-1, be the material that current thermal conductivity is the highest.The character of these uniquenesses can make Graphene as a kind of novel nano heat-conductive filler, thus the heat conductivility of polymkeric substance is greatly improved.
Summary of the invention
The present invention mainly solves the technical problem of the developing heat conductivility difference of existing heat-conductivity polymer composite, provides a kind of and possesses excellent heat conducting performance, good corrosion energy, high temperature resistant use properties, matrix material that comprehensive mechanical intensity is high and preparation method thereof.
Technical solution of the present invention is, is made up of the following raw material with parts by weight proportioning: nylon 30 ~ 80 parts, can 4 ~ 8 parts, swollen graphite, amphiphilic pyrene class grafts 0.5 ~ 1.5 part, high orientation silicon nitride fiber 1 ~ 20 part, 1 ~ 15 part, carbon fiber, boron nitride 5 ~ 10 parts, high temperature resistant auxiliary agent 0.02 ~ 4 part, 0.02 ~ 0.8 part, oxidation inhibitor, hydrolysis-resisting agent 1 ~ 3 part, toughner 2 ~ 6 parts.
Wherein said nylon is one or several the mixture in the nylon 6 of limiting viscosity between 1.6 ~ 3.8dL/g or nylon 12 or nylon66 fiber three kinds of materials;
Described can swollen graphite to be granularity be 60 orders can swollen graphite or 70 orders can swollen graphite or 80 orders can one or several mixture in swollen graphite three kinds of materials;
Described amphiphilic pyrene class grafts is one or several materials formed by electrophilic substitution reaction in pyrene and dendroid polyacrylic ester-poly glycol monomethyl ether segmented copolymer or dendroid polyacrylic ester-polyoxyethylene glycol ether segmented copolymer or dendroid polyoxyethylene glycol epoxy glycerite ester block copolymer three;
Described high orientation silicon nitride fiber is the high orientation silicon nitride fiber after coupling agent treatment; Coupling agent used is: silane coupling agent, titante coupling agent or complex compound class coupling agent;
Described carbon fiber is the high oriented carbon fiber after coupling agent treatment.Coupling agent used is: silane coupling agent, titante coupling agent or complex compound class coupling agent;
Described boron nitride is purity > 99%, and particle size range is the hexagonal boron nitride of 5 ~ 15 μm;
Described high temperature resistant auxiliary agent is that alkyl monothio cupric phosphate or alkenyl succinic acid copper or thiocarbamate copper or more are several composite;
Described oxidation inhibitor be N, N'-two-to be that 8:1 ~ 2:1 is composite according to mass ratio form (3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester;
Described hydrolysis-resisting agent is that one or more in carbodiimide or poly-[nitrilo methane four nitrilo [2,4,6-tri-(1-first and second base)-1,3-phenylene]] or cyanacrylate are composite;
Described toughner is POE-g-GMA or EPDM-g-GMA or EPR-g-MAH or SWR-3C or above several composite use.
Concrete preparation method's step of the present invention is as follows:
1) preparation of Graphene.First swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH and carry out sonic oscillation 3 ~ 5h, then centrifugal treating is carried out, centrifugal rotational speed is 1200 ~ 1500rpm, time is 15 ~ 30min, supernatant liquid is the graphene solution of dispersion, its concentration reaches 1.5 ~ 2mg/ml, supernatant liquor is placed dry 15 ~ 20h in 70 ~ 100 DEG C of baking ovens and obtains dry powdery Graphene.
2) by above-mentioned steps 1) in obtained graphene powder mix with nylon particle, in three-roll grinder, grinding 10 ~ 15min, for subsequent use.
3) by above-mentioned steps 2) in the particle that mixes of gained nylon/Graphene and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10 ~ 25min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
The advantage that the present invention is compared with prior art possessed is:
1) adopt and swollen graphite and amphiphilic pyrene class grafts can prepare high concentration graphene by the ultrasonic stripping method of liquid phase.First pyrene well can be combined with the Aromatic-ring stacking interaction of the Graphene of two-dirnentional structure by π-pi-conjugated double bond, secondly on pyrene, the amphiphilic group of grafting is dispersed in matrix resin with can either making graphene uniform, can make again the interface cohesive force grow between Graphene and nylon, consistency improves;
2) three roller polishings can make Graphene be coated on the surface of nylon particle well, are easy to be formed good " passage of heat ";
3) filler and the height-oriented silicon nitride fiber of the different grain size size adopted are filled in matrix resin, can form maximum degree of piling up and form excellent heat conduction network chain with fiber interaction between filler.
Embodiment
Below the preferred embodiments of the present invention are described in detail, are easy to make content characteristic of the present invention be understood by the researchist in this area, thus more full and accurate defining is made to protection scope of the present invention.
embodiment 1:
High thermal conductivity graphene/nylon composite material of the present invention, its component presses mass fraction, choose nylon 40 parts, can 4 parts, swollen graphite, amphiphilic pyrene class grafts 0.8 part, high orientation silicon nitride fiber 10 parts, 10 parts, carbon fiber, boron nitride 7 parts, high temperature resistant dose 0.1 part, 0.3 part, oxidation inhibitor, hydrolysis-resisting agent 1 part, toughner 4 parts, first swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH=6/4 and carry out sonic oscillation 3h, then centrifugal treating is carried out, centrifugal rotational speed is 1200rpm, time is 16min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed dry 15h in 70 DEG C of baking ovens and obtain dry powdery Graphene.Then obtained graphene powder is mixed with nylon particle, in three-roll grinder, grind 10min, for subsequent use.The particle finally nylon/Graphene mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 12min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
embodiment 2:
High thermal conductivity graphene/nylon composite material of the present invention, its component presses mass fraction, choose nylon 40 parts, can 5 parts, swollen graphite, amphiphilic pyrene class grafts 1 part, high orientation silicon nitride fiber 15 parts, 5 parts, carbon fiber, boron nitride 5 parts, high temperature resistant dose 0.3 part, 0.2 part, oxidation inhibitor, hydrolysis-resisting agent 1 part, toughner 6 parts, first swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH=7/3 and carry out sonic oscillation 3h, then centrifugal treating is carried out, centrifugal rotational speed is 1300rpm, time is 20min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed dry 18h in 90 DEG C of baking ovens and obtain dry powdery Graphene.Then obtained graphene powder is mixed with nylon particle, in three-roll grinder, grind 12min, for subsequent use.The particle finally nylon/Graphene mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 15min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
embodiment 3:
High thermal conductivity graphene/nylon composite material of the present invention, its component presses mass fraction, choose nylon 50 parts, can 5 parts, swollen graphite, amphiphilic pyrene class grafts 1.2 parts, high orientation silicon nitride fiber 12 parts, 8 parts, carbon fiber, boron nitride 8 parts, high temperature resistant dose 0.5 part, 0.4 part, oxidation inhibitor, hydrolysis-resisting agent 1.2 parts, toughner 8 parts, first swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH=7/5 and carry out sonic oscillation 3h, then centrifugal treating is carried out, centrifugal rotational speed is 1400rpm, time is 20min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed dry 18h in 100 DEG C of baking ovens and obtain dry powdery Graphene.Then obtained graphene powder is mixed with nylon particle, in three-roll grinder, grind 16min, for subsequent use.The particle finally nylon/Graphene mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
embodiment 4:
High thermal conductivity graphene/nylon composite material of the present invention, its component presses mass fraction, choose nylon 60 parts, can 6 parts, swollen graphite, amphiphilic pyrene class grafts 1.4 parts, high orientation silicon nitride fiber 16 parts, 4 parts, carbon fiber, boron nitride 10 parts, high temperature resistant dose 1 part, 0.8 part, oxidation inhibitor, hydrolysis-resisting agent 3 parts, toughner 6 parts, first swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH=5/4 and carry out sonic oscillation 3h, then centrifugal treating is carried out, centrifugal rotational speed is 1500rpm, time is 30min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed dry 17h in 85 DEG C of baking ovens and obtain dry powdery Graphene.Then obtained graphene powder is mixed with nylon particle, in three-roll grinder, grind 12min, for subsequent use.The particle finally nylon/Graphene mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 17min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
According to national standard, properties test is carried out to above-mentioned high thermal conductivity graphene/nylon composite material:
The results are shown in following table:
Note: strength retention refers to that obtained matrix material soaks the velocity of variation of 24 drying treatment back draft intensity relative to untreated matrix material in 80 DEG C of waters bath with thermostatic control.
Claims (8)
1. a high thermal conductivity graphene/nylon composite material, is characterized in that: be made up of the following raw material with parts by weight proportioning: nylon 30 ~ 80 parts, can 4 ~ 8 parts, swollen graphite, amphiphilic pyrene class grafts 0.5 ~ 1.5 part, high orientation silicon nitride fiber 1 ~ 20 part, 1 ~ 15 part, carbon fiber, boron nitride 5 ~ 10 parts, high temperature resistant auxiliary agent 0.02 ~ 4 part, 0.02 ~ 0.8 part, oxidation inhibitor, hydrolysis-resisting agent 1 ~ 3 part, toughner 2 ~ 6 parts; Described can swollen graphite to be granularity be 60 orders can swollen graphite or 70 orders can swollen graphite or 80 orders can one or several mixture in swollen graphite three kinds of materials.
2. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, is characterized in that: described nylon is one or several the mixture in the nylon 6 of limiting viscosity between 1.6 ~ 3.8dL/g or nylon 12 or nylon66 fiber three kinds of materials.
3. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, is characterized in that: described amphiphilic pyrene class grafts is one or several materials formed by electrophilic substitution reaction in pyrene and dendroid polyacrylic ester-poly glycol monomethyl ether segmented copolymer or dendroid polyacrylic ester-polyoxyethylene glycol ether segmented copolymer or dendroid polyoxyethylene glycol epoxy glycerite ester block copolymer three.
4. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, is characterized in that: described high orientation silicon nitride fiber is the high orientation silicon nitride fiber after coupling agent treatment; Coupling agent used is silane coupling agent, titante coupling agent or complex compound class coupling agent; Described carbon fiber is the high oriented carbon fiber after coupling agent treatment; Coupling agent used is silane coupling agent, titante coupling agent or complex compound class coupling agent.
5. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, it is characterized in that: described boron nitride is purity > 99%, particle size range is the hexagonal boron nitride of 5 ~ 15 μm.
6. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, is characterized in that: described high temperature resistant auxiliary agent is that alkyl monothio cupric phosphate or alkenyl succinic acid copper or thiocarbamate copper or more are several composite.
7. a kind of high thermal conductivity graphene/nylon composite material as claimed in claim 1, it is characterized in that: described oxidation inhibitor is N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) to be that 8:1 ~ 2:1 is composite according to mass ratio form hexanediamine and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester; Described hydrolysis-resisting agent is that one or more in carbodiimide or poly-[nitrilo methane four nitrilo [2,4,6-tri-(1-first and second base)-1,3-phenylene]] or cyanacrylate are composite; Described toughner is POE-g-GMA or EPDM-g-GMA or EPR-g-MAH or SWR-3C or above several composite use.
8. a preparation method for high thermal conductivity graphene/nylon composite material as claimed in claim 1, is characterized in that: concrete preparation method's step is as follows:
1) preparation of Graphene
First swollen graphite and amphiphilic pyrene class grafts together can be placed in the mixed solvent with certain proportion H2O/MeOH and carry out sonic oscillation 3 ~ 5h, then centrifugal treating is carried out, centrifugal rotational speed is 1200 ~ 1500rpm, time is 15 ~ 30min, supernatant liquid is the graphene solution of dispersion, its concentration reaches 1.5 ~ 2mg/ml, supernatant liquor is placed dry 15 ~ 20h in 70 ~ 100 DEG C of baking ovens and obtains dry powdery Graphene;
2) graphene powder obtained in step 1) is mixed with nylon particle, in three-roll grinder, grind 10 ~ 15min, for subsequent use;
3) by step 2) in the particle that mixes of gained nylon/Graphene and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10 ~ 25min, add after mixing in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add from adding fine mouth of screw rod by a certain percentage, temperature is 230 ~ 260 DEG C, main frame frequency is 15 ~ 25Hz, extrude through melt blending, extruded material dries up pelletizing after cold going, obtained high heat conduction nylon/graphene composite material.
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