CN107418052A - A kind of graphene microchip/polymer composites and preparation method thereof - Google Patents
A kind of graphene microchip/polymer composites and preparation method thereof Download PDFInfo
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- CN107418052A CN107418052A CN201710647907.0A CN201710647907A CN107418052A CN 107418052 A CN107418052 A CN 107418052A CN 201710647907 A CN201710647907 A CN 201710647907A CN 107418052 A CN107418052 A CN 107418052A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 194
- 229920000642 polymer Polymers 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 24
- 238000013329 compounding Methods 0.000 claims abstract description 50
- 239000007822 coupling agent Substances 0.000 claims abstract description 41
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 41
- 239000000376 reactant Substances 0.000 claims description 26
- -1 Polyethylene Polymers 0.000 claims description 24
- 239000008188 pellet Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 241000446313 Lamella Species 0.000 claims description 4
- 239000004425 Makrolon Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 238000012360 testing method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 8
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 19
- 239000000498 cooling water Substances 0.000 description 15
- 238000000465 moulding Methods 0.000 description 9
- 238000007731 hot pressing Methods 0.000 description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K2201/001—Conductive additives
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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides a kind of graphene microchip/polymer composites, it is prepared by the raw material including following components：The parts by weight of parts by weight of polymer 85~99；Compound the parts by weight of graphene sheet layer 1 parts by weight~15；The parts by weight of parts by weight of lubricant 0.1~5；The parts by weight of parts by weight of coupling agent 0.01~0.5；The compounding graphene sheet layer is made up of the different graphene microchip in piece footpath.Compared with prior art, the present invention is from the theory for influenceing material property, make full use of the quality of material self attributes, by improving material build-in attribute, to compound reinforcement of the graphene sheet layer as composite, so as to be effectively improved the stripping of graphene sheet layer and dispersion effect, obtained product has more excellent conduction, heat conductivility on the basis of stable mechanical property.Test result indicates that the electrical conductivity of graphene microchip/polymer composites provided by the invention can reach 7.5 × 10‑1S/m, thermal conductivity can reach 0.981W/mk, and tensile strength can reach 34.8MPa.
Description
Technical field
It is that to be related to a kind of graphene microchip/polymer compound more specifically the present invention relates to technical field of composite materials
Material and preparation method thereof.
Background technology
Member of the graphene microchip as newfound carbon-based material, the advantages of combining other carbon system fillers, have and lead
Electric critical content is low, electrical conductivity, thermal conductivity and excellent in mechanical performance, and cost is lower than single-layer graphene, is the modification of polymer
Provide new developing direction.Polymer matrix can be greatly enhanced in polymer by, which being added using graphene microchip as reinforcing material, answers
The electrical conductivity and thermal conductivity of condensation material, there is wide answer in fields such as conductive material, Heat Conduction Material, shielding material, Electronic Packagings
Use prospect.
In order to realize the preparation of the low cost of graphene microchip/polymer composites, large-scale, researcher is carried out
Extensive research.At present, melt-blending process is adapted to industrialized production, turned into most because having versatility, the feature of environmental protection and economy
The preparation method of tool prospect and accepted extensively.However, because the specific surface area and surface free energy of graphene microchip are big, graphite
There is very strong electrostatic force and Van der Waals force in the piece interlayer of alkene microplate, therefore, it is in the polymer generally with the reunion bodily form
State is present, and is unfavorable for the improvement of polymer matrix composite performance, graphene microchip when being prepared in particular by melting mixing method
Stripping and dispersion effect it is bad.Have been reported and show, the stripping of graphene microchip and dispersion effect to polymer crystallinity with
And conductive network is built and had significant effect, so that its graphene microchip/polymer composites performance prepared is present very
Big difference.
At present, prior art generally use improves the shearing force in the processing field of force, and graphene microchip is shelled with reaching
From and by its uniformly it is low it is scattered in the polymer, so as to change its combination property.But the improvement of above-mentioned technical proposal compared with
Difference, and be related to the improvement of plant equipment and be difficult to and promote.
The content of the invention
In view of this, it is an object of the invention to provide a kind of graphene microchip/polymer composites and its preparation side
Method, the preparation method can be effectively improved stripping and the dispersion effect of graphene sheet layer by improving material build-in attribute, prepare
Obtained product has good combination property.
The invention provides a kind of graphene microchip/polymer composites, by the raw material preparation including following components
Into：
The parts by weight of parts by weight of polymer 85~99；
Compound the parts by weight of graphene sheet layer 1 parts by weight~15；
The parts by weight of parts by weight of lubricant 0.1~5；
The parts by weight of parts by weight of coupling agent 0.01~0.5；
The compounding graphene sheet layer is made up of the different graphene microchip in piece footpath.
Preferably, the piece footpath of the graphene microchip is 5 μm~100 μm, and lamellar spacing is 5nm~100nm.
Preferably, the different graphene microchip in described footpath be selected from piece footpath be 5 μm~20 μm graphene microchip, piece footpath be
Two kinds in 30 μm~50 μm of graphene microchip and the graphene microchip that piece footpath is 60 μm~100 μm.
Preferably, the polymer be selected from polyethylene, polypropylene, polystyrene, polyvinyl chloride, makrolon, polyamide,
Polyformaldehyde, SAN, acrylonitrile-butadiene-styrene copolymer, polysulfones, polyethylene terephthalate
One or more in ester, polybutylene terephthalate (PBT), polyphenylene sulfide and polyether-ketone.
Preferably, the coupling agent is selected from silane coupler, titanate coupling agent, aluminate coupling agent and phosphate coupling
One or more in agent.
Present invention also offers a kind of preparation side of graphene microchip/polymer composites described in above-mentioned technical proposal
Method, comprise the following steps：
A) polymer, compounding graphene sheet layer, lubricant and coupling agent are mixed, obtains reactant mixture；The compounding
Graphene sheet layer is made up of the different graphene microchip in piece footpath；
B) reactant mixture for obtaining step a) carries out melt blending, then extruded, granulation, obtains pellet；
C) pellet for obtaining step b) is carried out hot-forming, after cooling, obtains graphene microchip/polymer composite
Material.
Preferably, the step a) is specially：
The ethanol solution for compounding graphene sheet layer and coupling agent carried out into first time to mix, after drying, then with polymer, profit
Lubrication prescription carries out second and mixed, and obtains reactant mixture.
Preferably, the mode of the first time mixing is ultrasonic agitation, and the time is 10min~30min；
The temperature of the drying is 80 DEG C~100 DEG C, and the time is 10h~18h；
The temperature of second of mixing is 70 DEG C~105 DEG C, and the time is 5min~15min.
Preferably, melt blending described in step b) is carried out using double screw extruder, the length of the double screw extruder
Footpath ratio is (25~60)：1；Screw speed is 100rpm~400rpm, and temperature is 150 DEG C~250 DEG C.
Preferably, temperature hot-forming described in step c) is 180 DEG C~250 DEG C, and pressure is 10MPa~20MPa, when
Between be 5min~10min.
The invention provides a kind of graphene microchip/polymer composites, by the raw material preparation including following components
Into：The parts by weight of parts by weight of polymer 85~99；Compound the parts by weight of graphene sheet layer 1 parts by weight~15；The parts by weight of lubricant 0.1~
5 parts by weight；The parts by weight of parts by weight of coupling agent 0.01~0.5；The compounding graphene sheet layer is by the different graphene microchip in piece footpath
Composition.Compared with prior art, the present invention makes full use of the excellent of material self attributes from the theory for influenceing material property
It is bad, by improving material build-in attribute, to compound reinforcement of the graphene sheet layer as composite, so as to be effectively improved graphene
The stripping of lamella and dispersion effect, obtained product have more excellent conduction, heat conduction on the basis of stable mechanical property
Performance.Test result indicates that the electrical conductivity of graphene microchip/polymer composites provided by the invention can reach 7.5 ×
10-1S/m, thermal conductivity can reach 0.981W/mk, and tensile strength can reach 34.8MPa.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for graphene microchip/polymer composites that embodiment 1 provides；
Fig. 2 is the graphene of different piece footpaths size in graphene microchip/polymer composites that embodiment 1~3 provides
Conductive network Structure Comparison figure after microplate compounding.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
The invention provides a kind of graphene microchip/polymer composites, by the raw material preparation including following components
Into：
The parts by weight of parts by weight of polymer 85~99；
Compound the parts by weight of graphene sheet layer 1 parts by weight~15；
The parts by weight of parts by weight of lubricant 0.1~5；
The parts by weight of parts by weight of coupling agent 0.01~0.5；
The compounding graphene sheet layer is made up of the different graphene microchip in piece footpath.
In the present invention, for the graphene microchip/polymer composites using polymer as matrix, graphene microchip is increasing
Strong material, the present invention is by improving material build-in attribute, to compound reinforcement of the graphene sheet layer as composite, so as to effectively
Improve graphene sheet layer stripping and dispersion effect, so as to get product there is good combination property.
In the present invention, the polymer is preferably selected from polyethylene, polypropylene, polystyrene, polyvinyl chloride, poly- carbonic acid
It is ester, polyamide, polyformaldehyde, SAN, acrylonitrile-butadiene-styrene copolymer, polysulfones, poly- to benzene two
One or more in formic acid glycol ester, polybutylene terephthalate (PBT), polyphenylene sulfide and polyether-ketone, more preferably poly- second
Alkene, polypropylene, polystyrene, polyvinyl chloride, makrolon or acrylonitrile-butadiene-styrene copolymer.In the present invention,
The polyethylene includes high density polyethylene (HDPE) well known to those skilled in the art, low density polyethylene (LDPE) and haloflex.This
Invention is not particularly limited to the source of the polymer, using commercial goods well known to those skilled in the art.At this
In invention, the graphene microchip/polymer composites include the polymer of the parts by weight of 85 parts by weight~99, preferably 90 weights
Measure the parts by weight of part~95.
In the present invention, the compounding graphene sheet layer is made up of the different graphene microchip in piece footpath.In the present invention, institute
The piece footpath for stating graphene microchip is preferably 5 μm~100 μm；The graphene microchip in different piece footpaths carries out compounding, and can to change melting mixed
The complexity for the graphene microchip for refining the field of force to peel off and in dispersed polymer, obtains having preferable conductive network structure
Composite.In the present invention, the different graphene microchip in described footpath be selected from piece footpath be 5 μm~20 μm graphene microchip,
Two kinds in the graphene microchip that piece footpath is 30 μm~50 μm of graphene microchip and piece footpath is 60 μm~100 μm.The present invention is excellent
Choosing is compounded two kinds of different graphene microchips in piece footpath to obtain compounding graphene sheet layer, the big graphene microchip in described footpath
The mass ratio of small graphene microchip is preferably 9 with piece footpath：1~1：9, more preferably 8：2~5：5.
In the present invention, the lamellar spacing of the graphene microchip is preferably 5nm~100nm.
The present invention is not particularly limited to the source of the graphene microchip, using well known to those skilled in the art commercially available
Commodity, it is preferred to use graphene microchip KNG180, graphene microchip CZ030, graphene microchip G5, graphene microchip
KNG182 and graphene microchip KNG150.In the preferred embodiment of the invention, the compounding graphene sheet layer is by thickness
100nm, the graphene microchip KNG180 that piece footpath is 100 μm and thickness is 30nm, piece footpath is 40 μm graphene microchip CZ030 by
Mass ratio 8：2 compositions；In presently preferred embodiment, the compounding graphene sheet layer is 100nm, piece by thickness
The graphene microchip KNG180 that footpath the is 100 μm and graphene microchip G5 in mass ratio 5 that thickness is 5nm, piece footpath is 8 μm：5 groups
Into；In presently preferred embodiment, the compounding graphene sheet layer by thickness is 30nm, the stone that piece footpath is 40 μm
The black alkene microplate CZ030 and graphene microchip G5 in mass ratio 8 that thickness is 5nm, piece footpath is 8 μm：2 compositions；It is another in the present invention
In individual preferred embodiment, the compounding graphene sheet layer by thickness is 100nm, the graphene microchip KNG182 that piece footpath is 40 μm
The graphene microchip KNG180 in mass ratio 9 that with thickness be 100nm, piece footpath is 100 μm：1 composition；Presently preferred
Embodiment in, the compounding graphene sheet layer by thickness is 5nm, the graphene microchip G5 that piece footpath is 8 μm and thickness are
100nm, the graphene microchip KNG182 in mass ratio 7 that piece footpath is 40 μm：3 compositions；In presently preferred embodiment
In, the compounding graphene sheet layer by thickness is 100nm, the graphene microchip KNG180 that piece footpath is 100 μm and thickness be 5nm,
Piece footpath is 8 μm of graphene microchip G5 in mass ratio 6：4 compositions；In presently preferred embodiment, the compounding
The graphene microchip KNG180 that graphene sheet layer by thickness is 100nm, piece footpath is 100 μm and thickness are 5nm, piece footpath is 8 μm
Graphene microchip G5 in mass ratio 3：7 compositions.
In the present invention, the graphene microchip/polymer composites include the compounding stone of the parts by weight of 1 parts by weight~15
The parts by weight of black alkene lamella, preferably 6 parts by weight~12.
In the present invention, the lubricant is preferably selected from polypropylene wax, Tissuemat E, magnesium stearate, methyl-silicone oil and hard
One or more in resin acid zinc, more preferably polypropylene wax or Tissuemat E.The present invention does not have to the source of the lubricant
It is specifically limited, using above-mentioned polypropylene wax well known to those skilled in the art, Tissuemat E, magnesium stearate, methyl-silicone oil and hard
The commercial goods of resin acid zinc.In the present invention, the graphene microchip/polymer composites include 0.1 parts by weight~5
The parts by weight of the lubricant of parts by weight, preferably 0.5 parts by weight~3.
In the present invention, the coupling agent is preferably selected from silane coupler, titanate coupling agent, aluminate coupling agent and phosphorus
One or more in acid esters coupling agent, more preferably silane coupler or titanate coupling agent.The present invention is to the coupling agent
Source be not particularly limited, using above-mentioned silane coupler, titanate coupling agent and phosphoric acid well known to those skilled in the art
The commercial goods of ester coupling agent.In the present invention, the graphene microchip/polymer composites include 0.01 parts by weight
The parts by weight of the coupling agent of~0.5 parts by weight, preferably 0.05 parts by weight~0.45.
Present invention also offers a kind of preparation side of graphene microchip/polymer composites described in above-mentioned technical proposal
Method, comprise the following steps：
A) polymer, compounding graphene sheet layer, lubricant and coupling agent are mixed, obtains reactant mixture；The compounding
Graphene sheet layer is made up of the different graphene microchip in piece footpath；
B) reactant mixture for obtaining step a) carries out melt blending, then extruded, granulation, obtains pellet；
C) pellet for obtaining step b) is carried out hot-forming, after cooling, obtains graphene microchip/polymer composite
Material.
The present invention first mixes polymer, compounding graphene sheet layer, lubricant and coupling agent, obtains reactant mixture.
In the present invention, the polymer, compounding graphene sheet layer, lubricant and coupling agent are identical with described in above-mentioned technical proposal,
It will not be repeated here.In the present invention, process polymer, compounding graphene sheet layer, lubricant and coupling agent mixed is preferred
Specially：
The ethanol solution for compounding graphene sheet layer and coupling agent carried out into first time to mix, after drying, then with polymer, profit
Lubrication prescription carries out second and mixed, and obtains reactant mixture.The present invention enters the ethanol solution for compounding graphene sheet layer and coupling agent
Row mixes for the first time, can be well mixed compounding graphene sheet layer and coupling agent.In the present invention, the first time mixes
Mode is preferably to be stirred by ultrasonic；The present invention is not particularly limited to the equipment of the ultrasonic agitation, using those skilled in the art
Well known ultrasonic pond.In the present invention, the time of the first time mixing is preferably 10min~30min, more preferably
20min。
In the present invention, the purpose of the drying is to remove ethanol completely；The present invention does not have to the equipment of the drying
It is specifically limited, using baking oven well known to those skilled in the art.In the present invention, the temperature of the drying is preferably 80 DEG C
~100 DEG C, more preferably 90 DEG C；The time of the drying is preferably 10h~18h, more preferably 12h~15h.
In the present invention, second of mixing is carried out preferably in high-speed mixer；The temperature of second of mixing
Preferably 70 DEG C~105 DEG C, more preferably 70 DEG C~80 DEG C；The time of second of mixing is preferably 5min~15min, more
Preferably 5min~10min.
After obtaining the reactant mixture, the present invention by obtained reactant mixture carry out melt blending, then it is extruded, make
Grain, obtains pellet.In the present invention, the melt blending is preferably carried out using double screw extruder；The double screw extruder
Draw ratio be preferably (25~60)：1, more preferably 40：1.In the present invention, the screw speed of the melt blending is preferably
100rpm~400rpm, more preferably 200rpm~300rpm；The temperature of the melt blending is preferably 150 DEG C~250 DEG C, more
Preferably 160 DEG C~210 DEG C.
The present invention is not particularly limited to the process of the extrusion, and the product after melt blending is extruded using die head.
The present invention is not particularly limited to the equipment of the granulation, using pelleter well known to those skilled in the art.The present invention
Before being granulated, preferably also include being cooled down the product after extrusion, it is not specifically limited to this by the present invention.
After obtaining the pellet, the present invention by obtained pellet carry out it is hot-forming, after cooling, obtain graphene microchip/
Polymer composites.In the present invention, the hot-forming process is entered preferably in hot pressing die using flat board moulding press
OK；The flat board moulding press preferably carries out the pre-heat treatment, the temperature of the pre-heat treatment is preferably before progress is hot-forming
10min~20min, more preferably 15min.
In the present invention, the hot-forming temperature is preferably 180 DEG C~250 DEG C, more preferably 205 DEG C~210 DEG C；
The hot-forming pressure is preferably 10MPa~20MPa, more preferably 12MPa~15MPa；The hot-forming time
Preferably 5min~10min.
In the present invention, the cooling is preferably carried out using recirculated cooling water；The time of the cooling be preferably 5min~
10min。
The invention provides a kind of graphene microchip/polymer composites, by the raw material preparation including following components
Into：The parts by weight of parts by weight of polymer 85~99；Compound the parts by weight of graphene sheet layer 1 parts by weight~15；The parts by weight of lubricant 0.1~
5 parts by weight；The parts by weight of parts by weight of coupling agent 0.01~0.5；The compounding graphene sheet layer is by the different graphene microchip in piece footpath
Composition.Compared with prior art, the present invention makes full use of the excellent of material self attributes from the theory for influenceing material property
It is bad, by improving material build-in attribute, to compound reinforcement of the graphene sheet layer as composite, so as to be effectively improved graphene
The stripping of lamella and dispersion effect, obtained product have more excellent conduction, heat conduction on the basis of stable mechanical property
Performance.Test result indicates that the electrical conductivity of graphene microchip/polymer composites provided by the invention can reach 7.5 ×
10-1S/m, thermal conductivity can reach 0.981W/mk, and tensile strength can reach 34.8MPa.
In addition, improvement of the present invention without plant equipment, simple to operate, cost is low；Graphite is prepared using melting mixing method
Alkene microplate/polymer composites, take into full account that the method realizes scale, quantity-produced possibility, possess easy processing, easily
The advantage of shaping；Environmentally safe meanwhile the preparation method step is simple, production efficiency is high, is adapted to industrialized production.
In order to further illustrate the present invention, it is described in detail below by following examples.It is former used in following examples
Material is commercial goods；Wherein, the trade mark of polypropylene (PP) be platform mould Ningbo, 3204；Graphene microchip is by Xiamen Kai Na graphite
Alkene Technology Co., Ltd. provides；The trade mark of polystyrene (PS) is that Zhenjiang is very beautiful, PG-33；Acrylonitrile-butadiene-styrene (ABS) is total to
The trade mark of polymers (ABS) is Ineos, 720；The trade mark of polyvinyl chloride (PVC) is upper chlorine Hu Feng, S-02；High density polyethylene (HDPE)
(HDPE) the trade mark is U.S. Nexus Resin, 1062；The trade mark of makrolon (PC) is Jiaxing Supreme Being people, 3810.
Embodiment 1
(1) the graphene microchip KNG180 and thickness that be 100nm by thickness, piece footpath is 100 μm are 30nm, piece footpath is 40 μm
Graphene microchip CZ030 in mass ratio 8：2 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 6g steps (1) to obtain, be added to silane coupling A 151 ethanol solution (by
0.18g silane coupling As 151 and 100mL ethanol mix) in, progress high-speed stirred 20min in ultrasonic pond is placed in, then put
In 90 DEG C of baking ovens dry 15h, ethanol is removed completely, then by its with 94g PP, 1g polypropylene wax micro mists in mixed at high speed
5min is mixed at 70 DEG C in machine, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 40：1 twin-screw squeezes
Go out machine, screw speed 200rpm, then each area's temperature is extruded, cooling water channel through die head successively between 160 DEG C~210 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
15min) hot-forming 5min (exhaust 12 times) under 205 DEG C, 12MPa, after circulating cooling water cooling 5min, it is micro- to obtain graphene
Piece/polymer composites.
The scanning electron microscope (SEM) photograph for graphene microchip/polymer composites that embodiment 1 provides is as shown in Figure 1.Can by Fig. 1
Know, the preparation method that the embodiment of the present invention 1 provides can be effectively improved the stripping of graphene sheet layer by improving material build-in attribute
From and dispersion effect.
Comparative example 1
The preparation method provided using embodiment 1, difference are：It is micro- as 30nm, graphene that piece footpath is 40 μm using thickness
Piece CZ030 (6g) replaces compounding graphene sheet layer.
Comparative example 2
The preparation method provided using embodiment 1, difference are：Using thickness as 100nm, the graphene that piece footpath is 100 μm
Microplate KNG180 (6g) replaces compounding graphene sheet layer.
With Chinese national standard conduction national standard GB/T15662-1995, heat conduction American Standard ASTM-E1461 and mechanical property national standard GB/
T1040.2-2006 is as testing standard, the graphene microchip/polymer composites provided embodiment 1 and comparative example 1~2
Electric conductivity, heat conductivility and mechanical property tested, the results are shown in Table 1.
The properties data for graphene microchip/polymer composites that the embodiment 1 of table 1 and comparative example 1~2 provide
| Electrical conductivity (S/m) | Thermal conductivity (W/mk) | Tensile strength (MPa) | |
| Embodiment 1 | 3.3×10-6 | 0.524 | 32.8 |
| Comparative example 1 | 5.0×10-7 | 0.463 | 32.1 |
| Comparative example 2 | 7.0×10-10 | 0.423 | 30.1 |
As shown in Table 1, graphene microchip/polymer composites that the embodiment of the present invention 1 provides are in stable mechanical property
On the basis of, electric conductivity and heat conductivility have obtained very big lifting, have good combination property.
It follows that the present invention makes full use of the quality of material self attributes, carried from the theory for influenceing material property
Going out material compounding improves the method for material property.Graphene microchip/polymer that preparation method provided by the invention obtains is compound
The features such as material has more excellent conduction, heat conductivility, and product size stability is good.In addition, the present invention is set without machinery
Standby improvement, simple to operate, cost is low；Graphene microchip/polymer composites are prepared using melting mixing method, taken into full account
The method realizes scale, quantity-produced possibility, possesses easy processing, the advantage of easy-formation；Meanwhile the preparation method step
Simply, environmentally safe, production efficiency is high, is adapted to industrialized production.
Embodiment 2
(1) the graphene microchip KNG180 that be 100nm by thickness, piece footpath is 100 μm and thickness are 5nm, piece footpath is 8 μm
Graphene microchip G5 in mass ratio 5：5 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 9g steps (1) to obtain, the ethanol solution of silane coupler is added to (by 0.27g
Silane coupler and 100mL ethanol mix) in, progress high-speed stirred 30min in ultrasonic pond is placed in, then be placed in 100 DEG C of bakings
12h is dried in case, ethanol is removed completely, then mixes it in high-speed mixer with 91g PP, 1g polypropylene waxes at 80 DEG C
10min is closed, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 25：1 twin-screw squeezes
Go out machine, screw speed 100rpm, then each area's temperature is extruded, cooling water channel through die head successively between 170 DEG C~220 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
10min) hot-forming 5min (exhaust 10 times) under 205 DEG C, 10MPa, after circulating cooling water cooling 8min, it is micro- to obtain graphene
Piece/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 2/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 2 provides is 9.0 × 10-7S/m, heat
Conductance is 0.486W/mk, tensile strength 31.8MPa.
Embodiment 3
(1) the graphene microchip CZ030 that be 30nm by thickness, piece footpath is 40 μm and the stone that thickness is 5nm, piece footpath is 8 μm
Black alkene microplate G5 in mass ratio 8：2 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 12g steps (1) to obtain, be added to titanate coupling agent ethanol solution (by
0.3g titanate coupling agents and 100mL ethanol mix) in, progress high-speed stirred 30min in ultrasonic pond is placed in, then be placed in 90
18h is dried in DEG C baking oven, ethanol is removed completely, then by its with 88g ABS, 0.5g Tissuemat Es 80 in high-speed mixer
15min is mixed at DEG C, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 60：1 twin-screw squeezes
Go out machine, screw speed 300rpm, then each area's temperature is extruded, cooling water channel through die head successively between 160 DEG C~210 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
20min) hot-forming 10min (exhaust 15 times) under 210 DEG C, 15MPa, after circulating cooling water cooling 10min, obtain graphene
Microplate/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 3/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 3 provides is 1.0 × 10-1S/m, heat
Conductance is 0.723W/mk, tensile strength 34.8MPa.
In graphene microchip/polymer composites that embodiment 1~3 provides, the graphene microchip of different piece footpaths size
Conductive network Structure Comparison figure after compounding is as shown in Figure 2.
Embodiment 4
(1) the graphene microchip KNG182 and thickness that be 100nm by thickness, piece footpath is 40 μm are 100nm, piece footpath is 100 μ
M graphene microchip KNG180 in mass ratio 9：1 is compounded, and obtains compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 2g steps (1) to obtain, be added to aluminate coupling agent ethanol solution (by
0.05g zinc stearates coupling agent and 100mL ethanol mix) in, progress high-speed stirred 10min in ultrasonic pond is placed in, then put
In 85 DEG C of baking ovens dry 15h, ethanol is removed completely, then by its with 98g PVC, 1g methyl-silicone oils in high-speed mixer
10min is mixed at 70 DEG C, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 40：1 twin-screw squeezes
Go out machine, screw speed 250rpm, then each area's temperature is extruded, cooling water channel through die head successively between 150 DEG C~200 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
20min) hot-forming 5min (exhaust 8 times) under 180 DEG C, 20MPa, after circulating cooling water cooling 5min, it is micro- to obtain graphene
Piece/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 4/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 4 provides is 2.0 × 10-6S/m, heat
Conductance is 0.512W/mk, tensile strength 32.8MPa.
Embodiment 5
(1) the graphene microchip G5 that be 5nm by thickness, piece footpath is 8 μm and the graphite that thickness is 100nm, piece footpath is 40 μm
Alkene microplate KNG182 in mass ratio 7：3 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 10g steps (1) to obtain, be added to titanate coupling agent ethanol solution (by
0.32g titanate coupling agents and 100mL ethanol mix) in, progress high-speed stirred 20min in ultrasonic pond is placed in, then be placed in
In 95 DEG C of baking ovens dry 12h, ethanol is removed completely, then by its with 90g HDPE, 3g Tissuemat Es in high-speed mixer
10min is mixed at 85 DEG C, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 25：1 twin-screw squeezes
Go out machine, screw speed 150rpm, then each area's temperature is extruded, cooling water channel through die head successively between 180 DEG C~230 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
15min) hot-forming 6min (exhaust 12 times) under 215 DEG C, 18MPa, after circulating cooling water cooling 6min, it is micro- to obtain graphene
Piece/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 5/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 5 provides is 2.5 × 10-3S/m, heat
Conductance is 0.734W/mk, tensile strength 33.2MPa.
Embodiment 6
(1) the graphene microchip KNG180 that be 100nm by thickness, piece footpath is 100 μm and thickness are 5nm, piece footpath is 8 μm
Graphene microchip G5 in mass ratio 6：4 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 9g steps (1) to obtain, the ethanol solution of silane coupler is added to (by 0.27g
Silane coupler and 100mL ethanol mix) in, progress high-speed stirred 12min in ultrasonic pond is placed in, then be placed in 90 DEG C of baking ovens
Middle dry 10h, ethanol is removed completely, then mixed it in high-speed mixer at 80 DEG C with 91g PP, 1g polypropylene waxes
8min, obtain reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 40：1 twin-screw squeezes
Go out machine, screw speed 200rpm, then each area's temperature is extruded, cooling water channel through die head successively between 160 DEG C~210 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
12min) hot-forming 8min (exhaust 20 times) under 205 DEG C, 15MPa, after circulating cooling water cooling 10min, obtain graphene
Microplate/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 6/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 6 provides is 4.5 × 10-5S/m, heat
Conductance is 0.541W/mk, tensile strength 33.9MPa.
Embodiment 7
(1) the graphene microchip KNG180 that be 100nm by thickness, piece footpath is 100 μm and thickness are 5nm, piece footpath is 8 μm
Graphene microchip G5 in mass ratio 3：7 are compounded, and obtain compounding graphene sheet layer；
(2) the compounding graphene sheet layer for taking 15g steps (1) to obtain, be added to titanate coupling agent ethanol solution (by
0.45g stearic acid coupling agent and 100mL ethanol mix) in, progress high-speed stirred 20min in ultrasonic pond is placed in, then be placed in
In 85 DEG C of baking ovens dry 18h, ethanol is removed completely, then by its with 85g PBT, 3g Tissuemat Es in high-speed mixer
15min is mixed at 105 DEG C, obtains reactant mixture；
(3) reactant mixture for obtaining step (2) is precisely sent into draw ratio with drawing-in device as 25：1 twin-screw squeezes
Go out machine, screw speed 400rpm, then each area's temperature is extruded, cooling water channel through die head successively between 180 DEG C~250 DEG C
Cooling and pelleter are granulated, and obtain pellet；Pellet is finally put into hot pressing die, using flat board moulding press (preheating time
20min) hot-forming 5min (exhaust 20 times) under 250 DEG C, 20MPa, after circulating cooling water cooling 8min, it is micro- to obtain graphene
Piece/polymer composites.
The graphene microchip that the method for testing provided using embodiment 1 is provided embodiment 7/polymer composites are carried out
Test, the results showed that, the electrical conductivity for graphene microchip/polymer composites that embodiment 7 provides is 7.5 × 10-1S/m, heat
Conductance is 0.981W/mk, tensile strength 34.3MPa.
The described above of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Most wide scope.
Claims (10)
1. a kind of graphene microchip/polymer composites, are prepared by the raw material including following components：
The parts by weight of parts by weight of polymer 85~99；
Compound the parts by weight of graphene sheet layer 1 parts by weight~15；
The parts by weight of parts by weight of lubricant 0.1~5；
The parts by weight of parts by weight of coupling agent 0.01~0.5；
The compounding graphene sheet layer is made up of the different graphene microchip in piece footpath.
2. graphene microchip/polymer composites according to claim 1, it is characterised in that the graphene microchip
Piece footpath be 5 μm~100 μm, lamellar spacing is 5nm~100nm.
3. graphene microchip/polymer composites according to claim 1, it is characterised in that described footpath is different
Graphene microchip is selected from graphene microchip, the graphene microchip that piece footpath is 30 μm~50 μm and the piece footpath that piece footpath is 5 μm~20 μm
For two kinds in 60 μm~100 μm of graphene microchips.
4. graphene microchip/polymer composites according to claim 1, it is characterised in that the polymer is selected from
Polyethylene, polypropylene, polystyrene, polyvinyl chloride, makrolon, polyamide, polyformaldehyde, SAN, third
Alkene nitrile-BS, polysulfones, polyethylene terephthalate, polybutylene terephthalate (PBT), polyphenyl
One or more in thioether and polyether-ketone.
5. graphene microchip/polymer composites according to claim 1, it is characterised in that the coupling agent is selected from
One or more in silane coupler, titanate coupling agent, aluminate coupling agent and phosphate coupling agent.
6. a kind of preparation method of graphene microchip/polymer composites described in any one of Claims 1 to 5, including with
Lower step：
A) polymer, compounding graphene sheet layer, lubricant and coupling agent are mixed, obtains reactant mixture；The compounding graphite
Alkene lamella is made up of the different graphene microchip in piece footpath；
B) reactant mixture for obtaining step a) carries out melt blending, then extruded, granulation, obtains pellet；
C) pellet for obtaining step b) is carried out hot-forming, after cooling, obtains graphene microchip/polymer composites.
7. preparation method according to claim 6, it is characterised in that the step a) is specially：
The ethanol solution for compounding graphene sheet layer and coupling agent carried out into first time to mix, after drying, then with polymer, lubricant
Carry out second to mix, obtain reactant mixture.
8. preparation method according to claim 7, it is characterised in that the mode of the first time mixing is ultrasonic agitation,
Time is 10min~30min；
The temperature of the drying is 80 DEG C~100 DEG C, and the time is 10h~18h；
The temperature of second of mixing is 70 DEG C~105 DEG C, and the time is 5min~15min.
9. preparation method according to claim 6, it is characterised in that melt blending is squeezed using twin-screw described in step b)
Go out machine progress, the draw ratio of the double screw extruder is (25~60)：1；Screw speed is 100rpm~400rpm, and temperature is
150 DEG C~250 DEG C.
10. preparation method according to claim 6, it is characterised in that hot-forming temperature described in step c) is 180
DEG C~250 DEG C, pressure is 10MPa~20MPa, and the time is 5min~10min.
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| CN109836699A (en) * | 2018-07-19 | 2019-06-04 | 广州梵泰新材料科技有限公司 | A kind of polypropylene scratch-resistant material and preparation method thereof that graphene is modified |
| CN109401012A (en) * | 2018-10-30 | 2019-03-01 | 福州大学 | A kind of graphene microchip/high-density polyethylene composite material and preparation method thereof |
| CN109912887A (en) * | 2019-03-15 | 2019-06-21 | 广东工业大学 | A kind of nanometer of removing composite material, preparation method and applications |
| CN112546868A (en) * | 2019-09-10 | 2021-03-26 | 河南烯力新材料科技有限公司 | Composite filtering structure, manufacturing method thereof and filter element |
| CN112546868B (en) * | 2019-09-10 | 2022-11-04 | 河南烯力新材料科技有限公司 | Composite filtering structure, manufacturing method thereof and filter element |
| CN111117043A (en) * | 2020-03-04 | 2020-05-08 | 福州大学 | Heat treatment enhanced graphene microchip/high-density polyethylene composite material and preparation method thereof |
| CN111117043B (en) * | 2020-03-04 | 2021-09-28 | 福州大学 | Heat treatment enhanced graphene microchip/high-density polyethylene composite material and preparation method thereof |
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