CN107236148B - Graphene and polyolefin composite material and preparation method thereof - Google Patents
Graphene and polyolefin composite material and preparation method thereof Download PDFInfo
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- CN107236148B CN107236148B CN201710302879.9A CN201710302879A CN107236148B CN 107236148 B CN107236148 B CN 107236148B CN 201710302879 A CN201710302879 A CN 201710302879A CN 107236148 B CN107236148 B CN 107236148B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 159
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 31
- -1 polyethylene Polymers 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- 239000004698 Polyethylene Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229920013639 polyalphaolefin Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 8
- 238000004108 freeze drying Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000007731 hot pressing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004616 structural foam Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
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- 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
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- 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
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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Abstract
The invention provides a graphene and polyolefin composite material and a preparation method thereof. The preparation method comprises the following steps: dispersing graphene oxide in a solvent to obtain a suspension; reacting the suspension for 12-24 h at 100-200 ℃ to obtain a foam graphene precursor; dissolving a foamy graphene precursor in water, freeze-drying at-80 to-10 ℃, and roasting for 1 to 3 hours at 700 to 1200 ℃ in an inert atmosphere to obtain foamy graphene; and soaking the foamed graphene into a polyolefin solution, and evaporating to dryness to obtain the graphene and polyolefin composite material. The invention also provides a graphene and polyolefin composite material, which is prepared by the preparation method. The preparation method of the graphene and polyolefin composite material is cheap and can be produced in a large scale.
Description
Technical field
The present invention relates to a kind of composite material and preparation method more particularly to the composite woods of a kind of graphene and polyolefin
Material and preparation method thereof, belongs to technical field of nano material.
Background technique
Graphene is between a kind of carbon atom be in hexagonal annular plates, be a two dimension being made of single layer of carbon atom
The basal plane that space infinitely extends, this unique structure make it have excellent mechanics, calorifics and electric property, it is considered to be multiple
The ideal additive of condensation material.
Graphene is compound with polyolefine material, the mechanical property, hot property and electric property of polyolefine material can be improved
Deng being expected to open up many new application fields.But graphene is rolled into a ball with generation very easy in polyolefine material recombination process
It is poly-, have a significant impact to its performance tool.
Appearance with three-dimensional networks structural foam shape graphene provides newly for the research and development of composite polyolefine material
Opportunity.Foam-like graphene is the honeycomb skeleton knot that multiple two-dimensional graphene films are joined together to form to three-dimensional communication
Structure, they are rich in macropore and meso-hole structure, have high specific surface and the porosity more than 99.9%, density ratio air is also
Gently, while it also remains with the excellent electricity of graphene, calorifics, mechanical property.Meanwhile such grapheme foam also has very
Good oil absorption.If such foam-like graphene is compound with polyolefin, can be very good to solve asking for graphene reunion
Topic.The Chinese patent application of Publication No. CN102732037A discloses one kind on foam metal by chemical vapor deposition system
It obtains grapheme foam and polymer is compound, resulting composite material has good mechanical property and electric conductivity.
However, preparing foam-like graphene by chemical vapor deposition on foam metal, cost of material is very expensive,
And after preparing graphene, it is also necessary to after foam metal acid corrosion, can just obtain foam-like graphene, technique also compares
Complexity cannot be prepared on a large scale, but also can generate a large amount of pollution.These factors are all unfavorable for its large-scale industry and answer
With.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide it is a kind of cheap, can be mass produced
The preparation method of the composite material of foam-like graphene and polyolefin based on graphene oxide.
In order to achieve the above technical purposes, the present invention provides the preparation sides of a kind of graphene and the composite material of polyolefin
The preparation method of the composite material of method, the graphene and polyolefin the following steps are included:
In a solvent by graphene oxide dispersion, suspension is obtained, wherein the concentration of suspension is 0.1-10mg/mL；
Suspension is reacted into 12h-24h at 100 DEG C -200 DEG C, obtains foam-like graphene precursor；
Foam-like graphene precursor is soluble in water, it is freeze-dried at -80 DEG C to -10 DEG C, under an inert atmosphere, 700
At DEG C -1200 DEG C, 1h-3h is roasted, foam-like graphene is obtained；
Foam-like graphene is dipped into polyolefin solution, is evaporated, the composite material of graphene and polyolefin is obtained,
In, foam-like graphene ratio shared in the composite material of the graphene and polyolefin is 0.01wt%-20wt%, polyene
Hydrocarbon ratio shared in the composite material of the graphene and polyolefin is 80wt%-99.99wt%.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that the solvent used for water,
Ethyl alcohol, methanol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that the polyolefin of use is molten
Liquid solvent for use is containing there are six one of to the alkane of 12 carbon, halogenated hydrocarbons, benzene,toluene,xylene and tetrahydrofuran
Or several combination.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that the polyolefin of use is molten
Polyolefin in liquid is the copolymer of polyethylene, poly alpha olefin or ethylene and alpha-olefin.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that the polyolefin of use is molten
The mass concentration of liquid is 1%-80%.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that by foam-like graphene
Precursor is soluble in water, and the solvent that will be filled in the foam-like graphene precursor of solvent is replaced into water.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that when being freeze-dried,
The step of water is drained into end freeze-drying.
In the preparation method of the composite material of graphene and polyolefin of the invention, it is preferable that the graphite oxide of use
Alkene is the two-dimensional surface containing oxygen-containing functional group on the sheet molecular structure skeleton rearranged by carbon atom according to hexagonal lattice
Material.
The preparation method of the composite material of graphene and polyolefin of the invention, specifically includes the following steps:
In a solvent by ultrasonic disperse by graphene oxide, finely dispersed suspension is obtained；
It says that suspension is transferred in high pressure solvent thermal response kettle, high-temperature solvent thermal response is carried out at 100 DEG C -200 DEG C, instead
It is 12h-24h between seasonable, obtains foam-like graphene precursor；
The foamy graphite alkene precursor that will be filled with solvent is soluble in water, and the solvent in foam-like graphene precursor is replaced into
Water；
The foam-like graphene precursor that will be filled with water carries out freeze-drying process at -80 DEG C to -10 DEG C, in inert atmosphere
After carrying out high-temperature roasting 1h-3h at 700 DEG C -1200 DEG C in environment, foam-like graphene is obtained；
Foam-like graphene is dipped into polyolefin solution, after boiling off the solvent in polyolefin solution and drying, is obtained
The composite material of graphene and polyolefin.
The present invention also provides the composite material of a kind of graphene and polyolefin, the composite materials of the graphene and polyolefin
It is to be prepared by the preparation method of the composite material of above-mentioned graphene and polyolefin.
The preparation method of the composite material of graphene and polyolefin of the present invention is by forming foam-like stone for graphene oxide
Black alkene, it is then compound with polyolefin, it avoids graphene and polyolefin compound tense generates reunion.
The preparation method of the composite material of graphene and polyolefin obtains through the invention graphene and polyolefin are answered
Condensation material relative to straight polymer, the composite material of graphene and polyolefin that the present invention obtains have good mechanical property,
Hot property and electric property, yield strength can be improved 5 times relative to pure polyolefine material maximum.
The preparation method of the composite material of graphene and polyolefin of the present invention be it is a kind of cheap, can be with large scale preparation
Foam-like graphene based on graphene oxide is compound with polyolefin, greatly reduces preparation cost, is conducive to its large-scale work
Industry application.
Detailed description of the invention
Fig. 1 is foam-like graphene/polyethylene based on graphene oxide in embodiment 3, embodiment 4 and embodiment 5
The load-deformation curve of composite material and pure polyethylene.
Fig. 2 is foam-like graphene/polyhexene based on graphene oxide in embodiment 6, embodiment 7 and embodiment 8
The load-deformation curve of composite material and pure polyhexene.
Fig. 3 is foam-like graphene/EP rubbers composite material and pure the third rubber of second in embodiment 9 and embodiment 10
The load-deformation curve of glue.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of foam-like graphene based on graphene oxide is present embodiments provided, through the following steps that being prepared into
It arrives:
Graphene oxide is well-dispersed in ethyl alcohol after ultrasonic agitation is handled, obtains graphene dispersing solution；
Dispersion liquid is transferred in polytetrafluoroethyllining lining, high temperature and pressure solvent thermal reaction kettle, reaction kettle is sealed,
It is put into the baking oven that temperature is 180 DEG C, and react 12 hours at such a temperature；
After cooling room temperature, the foam-like graphene for being full of ethyl alcohol is taken out from reaction vessel, it will be in foam-like graphene
Ethyl alcohol changes water into, and the foam-like graphene that then will be filled with water is freeze-dried at -60 DEG C, finally by the graphene of freezing processing
Material nitrogen atmosphere, 800 DEG C at a temperature of carry out roasting 1 hour, obtain foam-like grapheme material.
Embodiment 2
A kind of foam-like graphene based on graphene oxide is present embodiments provided, through the following steps that being prepared into
It arrives:
Graphene oxide is well-dispersed in n,N-Dimethylformamide after ultrasonic agitation is handled, obtains graphene
Dispersion liquid；
Dispersion liquid is transferred in polytetrafluoroethyllining lining, high temperature and pressure solvent thermal reaction kettle, reaction kettle is sealed,
It is put into the baking oven that temperature is 190 DEG C, and react 12 hours at such a temperature；
After cooling room temperature, the foam-like graphene for being full of n,N-Dimethylformamide is taken out from reaction vessel, by foam
N,N-Dimethylformamide in shape graphene changes water into, and the foam-like graphene that then will be filled with water freezes at -50 DEG C to be done
It is dry, finally by the grapheme material of freezing processing nitrogen atmosphere, 700 DEG C at a temperature of carry out roasting 2 hours, obtain foam-like
Grapheme material.
Embodiment 3
A kind of foam-like graphene/composite polyethylene material that graphene content is 5wt% is present embodiments provided, is
It is prepared by following steps:
Polyethylene is prepared using alpha-diimine nickel catalyst vinyl polymerization；
0.95g polyethylene is dissolved in 100mL toluene；
The foam-like graphene that 0.05g is prepared by embodiment 1 is soaked into the toluene solution of the polyethylene, under vacuum
Heating obtains foam-like graphene and polyethylene mixture after steaming toluene；
The mixture is put into vacuum drying oven, after 90 DEG C of vacuum drying, obtains the foam-like that graphene content is 5%
Graphene/composite polyethylene material.
The foam-like prepared graphene/composite polyethylene material is subjected to hot pressing, is allowed to form sheet specimens.It is cut
It is cut into standard batten, carry out Mechanics Performance Testing is stretched to it, and its result and the mechanical property of pure polyethylene are compared
Compared with.Specific load-deformation curve is as shown in Figure 1.
Embodiment 4
A kind of foam-like graphene/composite polyethylene material that graphene content is 10wt% is present embodiments provided,
Through the following steps that be prepared:
Polyethylene used in the present embodiment and foam-like graphene are also same as Example 3, but the mixing of the two
Ratio is that graphene content is 10wt% in foam-like graphene/composite polyethylene material.
The foam-like prepared graphene/composite polyethylene material is subjected to hot pressing, is allowed to form sheet specimens.It is cut
It is cut into standard batten, carry out Mechanics Performance Testing is stretched to it.Specific load-deformation curve is as shown in Figure 1.
Embodiment 5
A kind of foam-like graphene/composite polyethylene material that graphene content is 20wt% is present embodiments provided,
Through the following steps that be prepared:
Polyethylene used in the present embodiment and foam-like graphene are also same as Example 3, but the mixing of the two
Ratio is that graphene content is 20wt% in foam-like graphene/composite polyethylene material.
The foam-like prepared graphene/composite polyethylene material is subjected to hot pressing, is allowed to form sheet specimens.Then will
It is cut into standard batten, and carry out Mechanics Performance Testing is stretched to it.Specific load-deformation curve is as shown in Figure 1.
Embodiment 6
A kind of foam-like graphene/polyhexene composite material that graphene content is 5% is present embodiments provided, is logical
Cross what following steps were prepared:
Polyhexene is prepared using alpha-diimine nickel catalyst hexene oligomerization；
0.95g polyhexene is dissolved in 100mL chloroform；
Then foam-like graphene prepared by 0.05g embodiment 2 is soaked into the chloroformic solution of the polyhexene, in vacuum
Under conditions of heating chloroform is steamed after foam-like graphene and polyhexene mixture；
Mixture is put into vacuum drying oven, after 70 DEG C of vacuum drying, obtains the foam-like stone that graphene content is 5%
Black alkene/polyhexene composite material.
The foam-like prepared graphene/polyhexene composite material is subjected to hot pressing, is allowed to form sheet specimens.It is cut
It is cut into standard batten, carry out Mechanics Performance Testing is stretched to it, and its result and the mechanical property of pure polyhexene are compared
Compared with.Specific load-deformation curve is as shown in Figure 2.
Embodiment 7
A kind of foam-like graphene/composite polyethylene material that graphene content is 10wt% is present embodiments provided,
Through the following steps that be prepared:
Polyethylene used in the present embodiment and foam-like graphene are also same as Example 6, but the mixing of the two
Ratio is that graphene content is 10wt% in foam-like graphene/composite polyethylene material.
The foam-like prepared graphene/composite polyethylene material is subjected to hot pressing, is allowed to form sheet specimens.It is cut
It is cut into standard batten, carry out Mechanics Performance Testing is stretched to it.Specific load-deformation curve is as shown in Figure 2.
Embodiment 8
A kind of foam-like graphene/composite polyethylene material that graphene content is 20wt% is present embodiments provided,
Through the following steps that be prepared:
Polyethylene used in the present embodiment and foam-like graphene are also same as Example 6, but the mixing of the two
Ratio is that graphene content is 20wt% in foam-like graphene/composite polyethylene material.
The foam-like prepared graphene/composite polyethylene material is subjected to hot pressing, is allowed to form sheet specimens.Then will
It is cut into standard batten, and carry out Mechanics Performance Testing is stretched to it.Specific load-deformation curve is as shown in Figure 2.
Embodiment 9
A kind of foam-like graphene/EP rubbers composite material that graphene content is 4.29% is present embodiments provided,
It is through the following steps that be prepared:
The bright Sheng EP G2050 bibasic ethylene propylene rubber of 0.9671g is dissolved in 100mL methylene chloride；
The foam-like graphene that 0.0429g is prepared by embodiment 1 is soaked into the dichloromethane solution of the EP rubbers,
Foam-like graphene and EP rubbers mixture are obtained after heating steams methylene chloride under conditions of vacuum；
Mixture is put into vacuum drying oven, after 60 DEG C of vacuum drying, obtains the foam that graphene content is 4.29%
Shape graphene/EP rubbers composite material.
The foam-like prepared graphene/EP rubbers composite material is subjected to hot pressing, is allowed to form sheet specimens.By its
Be cut into standard batten, stretch carry out Mechanics Performance Testing to it, and by its result and the mechanical property of pure EP rubbers into
Row compares.Specific load-deformation curve is as shown in Figure 3.
Embodiment 10
A kind of foam-like graphene/polyhexene composite material that graphene content is 7.23% is present embodiments provided,
Through the following steps that be prepared:
EP rubbers used in the present embodiment and foam-like graphene also with EP rubbers used in embodiment 9 with
And foam-like graphene is identical, but the mixed proportion of the two is that graphene contains in foam-like graphene/polyhexene composite material
Amount is 7.23%.
The foam-like prepared graphene/EP rubbers composite material is subjected to hot pressing, is allowed to form sheet specimens.By its
It is cut into standard batten, carry out Mechanics Performance Testing is stretched to it.Specific load-deformation curve is as shown in Figure 3.
Above embodiments explanation, the preparation method of the composite material of graphene and polyolefin of the present invention be it is a kind of cheap,
Can be with large-scale producing method, the composite material of the graphene and polyolefin that are prepared is compared to straight polymer stress-strain
Performance improves a lot.
Claims (7)
1. a kind of preparation method of the composite material of graphene and polyolefin, which is characterized in that the graphene and polyolefin are answered
The preparation method of condensation material the following steps are included:
In a solvent by graphene oxide dispersion, suspension is obtained, wherein the concentration of the suspension is 0.1-10mg/mL；Its
In, the solvent is ethyl alcohol, methanol, n,N-Dimethylformamide, n,N-dimethylacetamide or N-Methyl pyrrolidone；
The suspension is reacted into 12h-24h at 100 DEG C -200 DEG C, obtains foam-like graphene precursor；
The foam-like graphene precursor is soluble in water, and the solvent that will be filled in the foam-like graphene precursor of solvent is replaced into
Water is freeze-dried at -80 DEG C to -10 DEG C, under an inert atmosphere, at 700 DEG C -1200 DEG C, is roasted 1h-3h, is obtained foam-like
Graphene；
The foam-like graphene is dipped into polyolefin solution, is evaporated, the composite material of graphene and polyolefin is obtained,
In, foam-like graphene ratio shared in the composite material of the graphene and polyolefin is 0.01wt%-20wt%,
Polyolefin ratio shared in the composite material of the graphene and polyolefin is 80wt%-99.99wt%.
2. the preparation method of the composite material of graphene according to claim 1 and polyolefin, which is characterized in that described poly-
Olefin solution solvent for use is containing there are six into the alkane of 12 carbon, halogenated hydrocarbons, benzene,toluene,xylene and tetrahydrofuran
One or more of combinations.
3. the preparation method of the composite material of graphene according to claim 1 or 2 and polyolefin, which is characterized in that institute
State the copolymer that the polyolefin in polyolefin solution is polyethylene, poly alpha olefin or ethylene and alpha-olefin.
4. the preparation method of the composite material of graphene according to claim 2 or 3 and polyolefin, which is characterized in that institute
The mass concentration for stating polyolefin solution is 1%-80%.
5. the preparation method of the composite material of graphene according to claim 1 and polyolefin, which is characterized in that carry out cold
When being lyophilized dry, water is drained into the step of end is freeze-dried.
6. the preparation method of the composite material of graphene according to claim 1 and polyolefin, which is characterized in that the oxygen
Graphite alkene is two containing oxygen-containing functional group on the sheet molecular structure skeleton rearranged by carbon atom according to hexagonal lattice
Dimensional plane material.
7. the composite material of a kind of graphene and polyolefin, which is characterized in that the composite material of the graphene and polyolefin is logical
Cross what the preparation method of the composite material of graphene and polyolefin described in any one of claims 1-6 was prepared.
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| CN102732037A (en) * | 2011-04-08 | 2012-10-17 | 中国科学院金属研究所 | Graphene foam/polymer high-conductivity composite material preparation method and application thereof |
| CN102826543A (en) * | 2012-09-19 | 2012-12-19 | 北京理工大学 | Preparation method of foamable three-dimensional graphene |
| CN103482615A (en) * | 2013-09-09 | 2014-01-01 | 东南大学 | Preparation method of foamed graphene-ZnO composite material |
| CN105384165A (en) * | 2015-12-18 | 2016-03-09 | 首都师范大学 | Spongy-like lightweight graphene aerogel preparation method |
| CN105837852A (en) * | 2016-03-09 | 2016-08-10 | 杭州师范大学 | Hydrophobic and oleophobic open-cell foam material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102732037A (en) * | 2011-04-08 | 2012-10-17 | 中国科学院金属研究所 | Graphene foam/polymer high-conductivity composite material preparation method and application thereof |
| CN102826543A (en) * | 2012-09-19 | 2012-12-19 | 北京理工大学 | Preparation method of foamable three-dimensional graphene |
| CN103482615A (en) * | 2013-09-09 | 2014-01-01 | 东南大学 | Preparation method of foamed graphene-ZnO composite material |
| CN105384165A (en) * | 2015-12-18 | 2016-03-09 | 首都师范大学 | Spongy-like lightweight graphene aerogel preparation method |
| CN105837852A (en) * | 2016-03-09 | 2016-08-10 | 杭州师范大学 | Hydrophobic and oleophobic open-cell foam material and preparation method thereof |
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