CN110229465A - A kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof - Google Patents
A kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof Download PDFInfo
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- CN110229465A CN110229465A CN201910428463.0A CN201910428463A CN110229465A CN 110229465 A CN110229465 A CN 110229465A CN 201910428463 A CN201910428463 A CN 201910428463A CN 110229465 A CN110229465 A CN 110229465A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses polymer matrix composites of a kind of graphene/carbon nano-tube and preparation method thereof, the raw material of polymeric based carbon nano tube composite are ultra-pure multi-walled carbon nanotube of 1-10% ratio, graphene, polymeric matrix material, dispersing agent, by ultra-pure multi-walled carbon nanotube, graphene, polymeric matrix material, mixture of dispersing agents carries out radiation treatment with electron beam, carbon nanotube realizes activation modification under electron beam irradiation, polymeric matrix material realizes solidification under electron beam irradiation simultaneously, the active atoms of carbon of carbon nano tube surface also participates in the solidification of basis material, obtain containing graphene/carbon nanotube polymer composites.The present invention passes through the one-dimensional material between carbon nanotube and graphene and the synergistic effect between two-dimensional material, enhance the interaction between graphene film using carbon nanotube big L/D ratio, using the boundary strength between carbon nanotube enhancing and matrix, a kind of high performance polymer material is obtained.
Description
Technical field
The invention patent relates to polymeric material fields, and in particular to a kind of polymer matrix of graphene/carbon nano-tube is multiple
Condensation material and preparation method thereof.
Technical background
Carbon nanotube is nano material that is extremely concerned at present, being considered to have most specific physiques.Carbon nanotube it is close
Degree only has 1/10 or so of steel, but the theoretical and actual measurement Young's modulus mould in 5TPa and 1.8TPa or so, with diamond respectively
It measures almost the same, is known highest material modulus, tensile strength 200GPa is close to the nature strength of materials upper limit
100 times of steel, 20 times of carbon fiber；Its elastic strain reaches as high as 12%, about the 60 of steel times.It had both had consolidating for carbon fiber
Have property, but the soft programmable with the electrical and thermal conductivity of metal material, the heat-proof corrosion-resistant of ceramic material, textile fabric with
And the slight workability of high molecular material, just because of this, the composite material of carbon nanotube enhancing (receive by mainly polymer matrix carbon
Mitron composite material) research become hot spot.Graphene is a kind of sheet two-dimensional material of only one atomic layer level thickness, stone
Black alkene is also presently found most thin two-dimensional material.The carbon atom of sp2 hydridization is taken in the lattice of graphene comprising six, it is brilliant
Lattice structure is the planar regular hexagonal structure similar with phenyl ring.The special lattice structure of graphene imparts the outstanding electricity of graphite
, calorifics and mechanical performance.The conductivity of graphene is 104S/m, and carrier mobility rate is up to 15000cm2Vs-1..
Graphene has a good heating conduction, and what heat conduction rate was up to 5 000Wm-1K-1. graphenes has outstanding machine
Tool performance, intensity are 100 times that 130GPa is steel.In addition, graphene also has very high theoretical specific surface area, it is theoretical
These excellent properties that specific surface area is up to 2 630m2g-1. graphenes make it rapidly become worldwide research hotspot
Graphene/carbon nano-tube has excellent physical and chemical performance, such as higher electric conductivity, excellent mechanical property, height
Specific surface area and good chemical stability etc., in catalyst carrier, high molecule nano composite material, energy conversion and storage
The fields such as the flexible base material of device are widely used.
Graphene/carbon nano-tube and high molecular material are carried out compound being to improve high molecular material performance and use scope
A kind of important means, therefore be that current urgent need solves with regard to how to prepare high performance graphene/carbon nano-tube high molecular material
A critical issue.
A kind of preparation of polymeric based carbon nano tube composite of the Chinese patent application of Patent No. CN101445646
Method, the invention are related to a kind of preparation method of the polymeric based carbon nano tube composite of technical field of nano material.Step
Are as follows: the ratio for being 0.01-10% according to the mass percentage content of carbon nanotube in the composite directly adds carbon nanotube
Enter and is perhaps scattered in monomer, oligomer or the monomer or oligomer that polymeric matrix material is added in liquid medium in advance
In solution, by being mixed to get mixture；Gained mixture is carried out radiation treatment with electron beam, obtains carbon containing receive by second step
The polymer composites of mitron.The invention directly manufactures unsaturated carbon atom in carbon nano tube surface by electron beam irradiation,
And be allowed to sufficiently to participate in matrix polymerization reaction at once to prepare composite material, the boundary strength between carbon nanotube and matrix can be increased,
The modification efficiency of carbon nanotube can be improved, and it is excellent to maintain the technologies such as the environmentally friendly, efficient of electronic beam curing, low consumption, flexible, reliable
Gesture.
A kind of system of graphene/carbon nano-tube composite aerogel of the Chinese patent application of Patent No. CN106629684A
Preparation Method and graphene/carbon nano-tube composite aerogel, a kind of preparation method of graphene/carbon nano-tube composite aerogel will
Carbon nanotube is reacted after mixing the carbon nanotube after graphene oxide, oxidation and reducing agent, is obtained water-setting with oxidizing
Glue, the reactant obtained after the hydrogel is mixed with enhancing solution obtain the graphene/carbon nano-tube after drying and answer
Aeroge is closed, the present invention passes through the one-dimensional material between carbon nanotube and graphene and the synergistic effect between two-dimensional material, benefit
Enhance the interaction between graphene film with carbon nanotube big L/D ratio, the mechanical performance of aeroge can be significantly improved.
The Chinese patent application of Patent No. CN107446231A is a kind of by graphene, carbon nanotube and fullerene common
Modified composite polyethylene material and preparation method thereof, which includes following components: 50~100 parts of polyethylene；Graphene 0.1
~1 part；0.1~1 part of carbon nanotube；Fuller olefinic carbon 60 .1~1 part；2~10 parts of polyethylene of maleic anhydride grafting；Antioxidant 1~
3 parts；1~3 part of plasticizer；1~2 part of coupling agent.Two-dimensional graphene, one-dimensional carbon nanotube and zero dimension fullerene are mixed in the present invention
It closes to build the antistatic network of three-dimensional carbon material, conductive network is constructed in base polyethylene using the carbon material of less ratio.
This composite processing simple process, can be mass, and the product obtained by single injection-molded can be in antistatic neck
It is applied in domain.
A kind of graphene/silicon/carbon nano tube compound material of the Chinese patent application of Patent No. CN105576203A and
Preparation method and application, graphene/silicon/carbon nano tube compound material be graphene, silicon materials and carbon nanotube it is compound one
Kind Si-C composite material.Preparation method: graphene powder, carbon nanotube are added in nmp solution, make its dispersion with sonic oscillation
Uniformly, nano silica fume is added, sonic oscillation is uniformly dispersed；Obtained mixed solution is dry, drying is ground to get graphite
Alkene/silicon/carbon nano tube compound material.Graphene/silicon/carbon nano tube compound material can be used as negative electrode material applied to lithium-ion electric
Pond.The characteristics such as high, high-efficient, good cycle with capacity.With relatively simple step by graphene, silicon materials and carbon nanometer
Pipe progress is compound, and improves volume of the silicon materials in charge and discharge process by the special construction of graphene and new material and imitate
It answers, improves the electric conductivity of silicon materials, capacity is high, high-efficient, good cycle.
Such as above-mentioned several patents, the relevant technical products in this field are disclosed, but how to prepare high performance graphite
Alkene/carbon nanotube high molecular material problem is that technical problems to be solved are badly in need of in this field.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of polymer matrixes of graphene/carbon nano-tube
Composite material and preparation method.
In order to solve the above-mentioned technical problem, used technical solution is: a kind of polymer matrix of graphene/carbon nano-tube
Composite material and preparation method, it is characterised in that the raw material of the polymeric based carbon nano tube composite are 1-10%
Ultra-pure multi-walled carbon nanotube, graphene, polymeric matrix material, the dispersing agent of ratio, specific preparation step are as follows:
(1) carbon nanotube of 1~10% ratio, 0.1%~1% graphene, by institute are added in dispersing liquid medium
Mixture carries out ultrasonic vibration and is uniformly dispersed, add the monomer of 90~95% polymeric matrix material, oligomer or
Monomer and oligomer are sufficiently mixed and uniformly obtain containing graphene/carbon nanotube polymeric matrix mixture；
(2) gained mixture is subjected to radiation treatment with electron beam, graphene/carbon nano-tube is realized under electron beam irradiation
Activation modification, while polymeric matrix material realizes solidification under electron beam irradiation；
(3) further curing and drying processing is carried out in the environment of 120 DEG C~140 DEG C to mixture, makes graphene/carbon
The active atoms of carbon of nanotube surface participates in the solidification of basis material, obtains the polymer composites of carbon nanotubes；
Further, ultra-pure multi-walled carbon nanotube is to be by or without modification, modification
Physics and chemical modification processing, its diameter are 6~10nm, and length is 10~30 μm；
Further, the polymeric matrix is bisphenol A type epoxy resin, bisphenol f type epoxy resin, alicyclic epoxy
Resin etc. can one of electron beam curing polymer or a variety of；
Further, the decentralized medium is ethyl alcohol, n-hexane, acetone, ethyl acetate, methylene chloride, chloroform, tetrachloro
Change one of carbon, petroleum ether, benzene, toluene, tetrahydrofuran, acetonitrile, dinethylformamide or N-Methyl pyrrolidone or more
Kind；
Further, the graphene/carbon nano-tube and the ratio of decentralized medium are 1g: 100ml.
Advantage for present invention: (1) by one-dimensional material between carbon nanotube and graphene and two-dimensional material it
Between synergistic effect, enhance the interaction between graphene film using carbon nanotube big L/D ratio.(2) carbon nanotube enhances
Boundary strength between matrix.(3) have preparation process simple, high production efficiency.(4) high molecular material obtained has excellent
Intensity, toughness, electric conductivity etc..
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
It is as defined in the appended claims that the modification of form falls within the application.
Embodiment
A kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof, it is characterised in that described is poly-
The raw material for closing object base carbon nanotube composite material are ultra-pure multi-walled carbon nanotube, graphene, the polymeric matrix of 6% ratio
Material, dispersing agent, specific preparation step are as follows:
(1) be added the carbon nanotube of 6% ratio in dispersing liquid medium, 0.5% graphene, by gained mixture into
Row ultrasonic vibration is uniformly dispersed, and adds monomer, oligomer or the monomer and oligomer of 94.5% polymeric matrix material,
It is sufficiently mixed and uniformly obtains containing graphene/carbon nanotube polymeric matrix mixture；
(2) gained mixture is subjected to radiation treatment with electron beam, graphene/carbon nano-tube is realized under electron beam irradiation
Activation modification, while polymeric matrix material realizes solidification under electron beam irradiation；
(3) further curing and drying processing is carried out in the environment of 120 DEG C to mixture, makes graphene/carbon nano-tube
The active atoms of carbon on surface participates in the solidification of basis material, obtains the polymer composites of carbon nanotubes；
Further, ultra-pure multi-walled carbon nanotube is to be by or without modification, modification
Physics and chemical modification processing, its diameter are 8nm, and length is 20 μm；
Further, the polymeric matrix is bisphenol A type epoxy resin, bisphenol f type epoxy resin, alicyclic epoxy
Resin etc. can one of electron beam curing polymer or a variety of；
Further, the decentralized medium is ethyl alcohol, n-hexane, acetone, ethyl acetate, methylene chloride, chloroform, tetrachloro
Change one of carbon, petroleum ether, benzene, toluene, tetrahydrofuran, acetonitrile, dinethylformamide or N-Methyl pyrrolidone or more
Kind；
Further, the graphene/carbon nano-tube and the ratio of decentralized medium are 1g: 100ml.
It above are only the specific embodiment of the present invention, but the design concept of the present invention is not limited to this, all benefits
It is made a non-material change to the present invention with this design, should belong to the behavior for invading the scope of protection of the invention.But it is all
Without departing from the content of technical solution of the present invention, according to the technical essence of the invention any type of letter to the above embodiments
Single modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (5)
1. a kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof, it is characterised in that the polymerization
The raw material of object base carbon nanotube composite material are ultra-pure multi-walled carbon nanotube, the graphene, polymer matrix of 1~10% ratio
Body material, dispersing agent, specific preparation step are as follows:
(1) carbon nanotube of 1~10% ratio is added in dispersing liquid medium, 0.1%~1% graphene mixes gained
It closes object progress ultrasonic vibration to be uniformly dispersed, adds the monomer, oligomer or monomer of 90~95% polymeric matrix material
And oligomer, it is sufficiently mixed and uniformly obtains containing graphene/carbon nanotube polymeric matrix mixture；
(2) gained mixture is subjected to radiation treatment with electron beam, graphene/carbon nano-tube realizes activation under electron beam irradiation
It is modified, while polymeric matrix material realizes solidification under electron beam irradiation；
(3) further curing and drying processing is carried out in the environment of 120 DEG C~140 DEG C to mixture, makes graphene/carbon nanometer
The active atoms of carbon of pipe surface participates in the solidification of basis material, obtains the polymer composites of carbon nanotubes.
2. the polymer matrix composite and preparation method thereof of graphene/carbon nano-tube according to claim 1, feature
It is that ultra-pure multi-walled carbon nanotube is by or without modification, modification is physics and change
Modification is learned, its diameter is 6~10nm, and length is 10~30 μm.
3. the polymer matrix composite and preparation method thereof of graphene/carbon nano-tube according to claim 1, feature
It is that the polymeric matrix is that bisphenol A type epoxy resin, bisphenol f type epoxy resin, cycloaliphatic epoxy resin etc. can electronics
One of beam curable polymer is a variety of.
4. the polymer matrix composite and preparation method thereof of graphene/carbon nano-tube according to claim 1, feature
Be the decentralized medium be ethyl alcohol, n-hexane, acetone, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, petroleum ether,
One of benzene, toluene, tetrahydrofuran, acetonitrile, dinethylformamide or N-Methyl pyrrolidone are a variety of.
5. the polymer matrix composite and preparation method thereof of graphene/carbon nano-tube according to claim 1, feature
The ratio for being the graphene/carbon nano-tube and decentralized medium is 1g: 100ml.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963813A (en) * | 2019-12-30 | 2020-04-07 | 华碳研发(深圳)有限公司 | Ceramic material containing carbon nano tube and preparation method thereof |
| CN112456479A (en) * | 2020-11-17 | 2021-03-09 | 安徽理工大学 | Preparation method of uniformly dispersed graphene/carbon nanotube composite material |
| CN115304799A (en) * | 2022-09-22 | 2022-11-08 | 青岛理工大学 | Electron beam radiation-induced crosslinking method for reinforcing carbon nano-particle/epoxy resin interface and obtained cured resin |
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| CN101445646A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials |
| CN101734650A (en) * | 2009-12-23 | 2010-06-16 | 沈阳建筑大学 | Method for preparing graphene-carbon nano tube hybrid composite |
| CN102807737A (en) * | 2012-08-07 | 2012-12-05 | 上海交通大学 | Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material |
| WO2015050352A1 (en) * | 2013-10-01 | 2015-04-09 | 코닝정밀소재 주식회사 | Method for preparing carbon nanotube-graphene composite, and carbon nanotube-graphene composite prepared thereby |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445646A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials |
| CN101734650A (en) * | 2009-12-23 | 2010-06-16 | 沈阳建筑大学 | Method for preparing graphene-carbon nano tube hybrid composite |
| CN102807737A (en) * | 2012-08-07 | 2012-12-05 | 上海交通大学 | Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material |
| WO2015050352A1 (en) * | 2013-10-01 | 2015-04-09 | 코닝정밀소재 주식회사 | Method for preparing carbon nanotube-graphene composite, and carbon nanotube-graphene composite prepared thereby |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963813A (en) * | 2019-12-30 | 2020-04-07 | 华碳研发(深圳)有限公司 | Ceramic material containing carbon nano tube and preparation method thereof |
| CN112456479A (en) * | 2020-11-17 | 2021-03-09 | 安徽理工大学 | Preparation method of uniformly dispersed graphene/carbon nanotube composite material |
| CN115304799A (en) * | 2022-09-22 | 2022-11-08 | 青岛理工大学 | Electron beam radiation-induced crosslinking method for reinforcing carbon nano-particle/epoxy resin interface and obtained cured resin |
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Application publication date: 20190913 |