CN108840332A - A kind of preparation method, graphite nano plate and its application of large scale graphite nano plate - Google Patents
A kind of preparation method, graphite nano plate and its application of large scale graphite nano plate Download PDFInfo
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- CN108840332A CN108840332A CN201810877231.9A CN201810877231A CN108840332A CN 108840332 A CN108840332 A CN 108840332A CN 201810877231 A CN201810877231 A CN 201810877231A CN 108840332 A CN108840332 A CN 108840332A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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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
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
Abstract
This hair discloses the preparation method based on expanded graphite preparation large scale graphite nano plate, belongs to technical field of nano material.The present invention removes expanded graphite using expanded graphite simple and easy to get as raw material, using concentrated acid, obtains graphite nano plate after washing, drying.The technique preparation process is simple, and obtained graphite nano plate piece diameter is uniform, and defect is few, low in cost, it is easy to accomplish large-scale production has a extensive future in functional composite material and anticorrosive paint field.
Description
Technical field
The present invention relates to a kind of preparation methods of large scale graphite nano plate, belong to carbon material preparation technical field.
Background technique
Nano material since the advent of the world is received significant attention due to its performance for being different from traditional material.Nano material is because of it
Nanostructure has some unique effects：Surface and interfacial effect, small-size effect, quantum size effect etc..By nanometer material
Material is applied in traditional coating, can be obviously improved the performance of coating, such as electric conductivity, corrosion resistance, shock resistance.Graphite
Nanometer sheet is a kind of novel nano-carbon material, and monoatomic layer is formed by connecting with carbon atom sp2 hydridization, long-range π-pi-conjugated
Structure makes it have the properties such as good electricity, optics and mechanics.Graphite nano plate maintains the crystal structure of natural graphite, ruler
It is very little to be significantly less than natural graphite, it is added into coating, may be uniformly dispersed in coating, it is thermal conductivity, electric conductivity, corrosion-resistant
Property etc. is obviously improved.It can be seen that graphite nano plate electronic radiation, industrial exhaust heat utilize, heavy antisepsis field suffer from it is wide
Application prospect.
Currently, people usually prepare graphite nano plate with ultrasound stripping method.Although ultrasonic stripping method theoretically can big face
Product prepares graphite nano plate, but its limits throughput, and obtained graphite nano plate piece diameter is uneven, size is smaller, so this method
Still there is significant limitation.
Summary of the invention
The technical problem to be solved in the present invention is that in view of the deficiencies of the prior art, creatively propose strong acid stripping method,
There is provided a kind of low cost, yield is high, quality is good, can scale industrial production large scale Nano graphite is prepared based on expanded graphite
The preparation method of piece.
The present invention provides a kind of using the method for directly preparing large scale graphite nano plate using concentrated acid.
The present invention can be achieved by the following technical programs：
The preparation method that graphite nano plate is prepared based on expanded graphite, including following preparation step are provided：
Expanded graphite is added in concentrated acid, 25 DEG C is being kept above while stirring 0.5h or more, be cooled to room temperature, pass through
Repeated filtration washing, is then dried, and graphite nano plate is made.
The expanded graphite is to expand to be formed one or more by natural graphite or synthetic graphite, and expanded graphite carbon contains
90% or more amount, 32~1200 mesh of partial size.
In preparation step, the concentrated acid concentration defines difference, concentrated nitric acid > 35wt.%, sulfuric acid > according to different sour types
50wt.%, concentrated hydrochloric acid > 20wt.%, concentrated phosphoric acid > 50wt.%, hydrofluoric acid > 25wt.%；Preferably, the concentrated acid is dense nitre
Sour (40~65wt.%).
In preparation step, the mixing speed is higher than 10rpm；Preferably, the mixing speed is 20~60rpm.
In preparation step, the mixing time is 0.5~300h；Preferably, the mixing time is 2~10h.
In preparation step, the washing medium is that water, alcohols, ketone etc. are one or more；Preferably, the washing medium
For deionized water.
In preparation step, the drying process is using constant pressure and dry, is dried under reduced pressure, is spray-dried, fluidized drying, freezing
One of drying, infrared drying, microwave drying or hygroscopic desiccation are a variety of.
In preparation step, the graphite nano plate microscopic size being prepared is 10~1000 μm, and thickness is less than 50nm；Due to
Agglomeration, some prepared graphite nano plate macro-sizes have been even more than 1000 μm.
The present invention also provides a kind of graphite nano plate being prepared using the above method and its in heat-conductive composite material and
The application of anticorrosive paint.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention uses concentrated acid for medium using expanded graphite as raw material, and stirring can be prepared by stone under the conditions of being higher than 25 DEG C
Black nanometer sheet.Moreover, being obtained by this legal system, graphite nano plate piece diameter is larger, defect is few, quality is high.Graphite nano plate of the present invention
Preparation method is low in cost to be easy to get, and method is easy, it is easy to accomplish large-scale production.It is received by graphite prepared by the method provided by the present invention
Rice piece thermal coefficient be up to 1000W/mK, heat-conductive composite material field with good application prospect；It is provided by the present invention
The graphite nano plate of method preparation have biggish diameter ratio (>100), excellent flexibility, the infiltration of good water-fast and gas
Property, excellent chemical stabilization, excellent thermal stability, good electric conductivity etc., applied in functional composite material field and anti-corrosion
Layer field, especially have in fields such as thermally conductive corrosion-inhibiting coating, flue gas corrosion-inhibiting coating, anticorrosion coat, anti-static coatings it is extensive
Application prospect.
Detailed description of the invention
Fig. 1 is graphite nano plate SEM figure prepared by embodiment 1；
Fig. 2 is graphite nano plate SEM figure prepared by embodiment 2；
Fig. 3 is graphite nano plate SEM figure prepared by embodiment 3；
Fig. 4 is the graphite nano plate Raman spectrogram of Examples 1 to 3 preparation；
Fig. 5 is the XPS C1s spectrum of (a) (b) graphite nano plate afterwards before 65wt.% nitric acid treatment at 70 DEG C.
Specific embodiment
Further illustrate that the present invention, following embodiment, application examples, comparative example are only schematically real below with reference to specific example
Example, application examples are applied, is not constituted improper limitations of the present invention.The present invention can be limited and be covered by summary of the invention it is a variety of not
Implement with mode, unless specifically indicated, reagent, compound and the equipment that the present invention uses is the art conventional reagents, change
Close object and equipment.
Embodiment 1
By the E300 flame retardant expansible graphite of business through 990 DEG C of expanding treatment 10s of Muffle furnace, expanded graphite is obtained.It will be swollen
Graphite and 68wt.% nitric acid are according to 1：The two, is uniformly mixed, mixing is equal by 100 mass ratio mixing with 30rpm mixing speed
Even be placed in 70 DEG C of water-baths reacts 4h.After the reaction was completed, it is repeatedly washed using deionized water to neutrality, constant pressure and dry is for 24 hours
Obtain graphite nano plate.
As shown in Figure 1, prepared graphite nano plate is averaged, piece diameter is 120 μm, thickness 34nm.
Further test shows that the radial thermal coefficient of prepared graphite nano plate is 1331W/mK, conductivity is
6501S/m。
Embodiment 2
By EG150 expansible graphite through 990 DEG C of expanding treatment 10s of Muffle furnace, expanded graphite is obtained.By expanded graphite with
98wt.% sulfuric acid is according to 1：The two, is uniformly mixed with 30rpm mixing speed, is uniformly mixed and is placed on by 50 mass ratio mixing
8h is reacted in 50 DEG C of water-baths.After the reaction was completed, it is repeatedly washed using deionized water to neutrality, constant pressure and dry obtains graphite for 24 hours
Nanometer sheet.
As shown in Fig. 2, the average piece diameter for preparing resulting graphite nano plate is 13 μm, thickness 14nm.
Embodiment 3
EG-A300 expansible graphite microwave bulking is handled into 30s, obtains expanded graphite.By expanded graphite and 80wt.% phosphorus
Acid is according to 1：The two, is uniformly mixed with 20rpm mixing speed, is uniformly mixed and is placed on 70 DEG C of water-baths by 50 mass ratio mixing
Middle reaction 3h.After the reaction was completed, it is repeatedly washed using deionized water to neutrality, constant pressure and dry obtains graphite nano plate for 24 hours.
As shown in figure 3, the average piece diameter for preparing resulting graphite nano plate is 25 μm, thickness 16nm.
As shown in figure 4, the Raman spectrum display I of graphite nano plate prepared by Examples 1 to 3D:IGLess than 0.1, show material
Defect it is less.
As shown in figure 5, graphite nano plate prepared by embodiment 1 is handled 5h in 70 DEG C of 65wt.%, material before and after the processing
XPS C1s spectrum does not change substantially, shows the not oxidized of material, has good chemical-resistant.
Application examples 1
Graphite nano plate is made using embodiment 1 in the application example, with epoxy resin with mass ratio 1：4 obtained composite heat-conducting materials
Material, is tested through Conduction Coefficient Detector Basing, and the thermal coefficient of composite material is 0.92W/mK, and pure epoxy resin thermal coefficient is only
0.17W/mK, heating conduction promote 541%.
Application examples 2
Graphite nano plate is made using embodiment 2 in the application example, with epoxy resin with mass ratio 1：4 obtained composite heat-conducting materials
Material, is tested through Conduction Coefficient Detector Basing, and the thermal coefficient of composite material is 0.89W/mK, and pure epoxy resin thermal coefficient is
0.17W/mK, heating conduction promote 523%.
Application examples 3
Graphite nano plate is made using embodiment 1 in the application example, is doped into epoxy lacquer coat by 1wt.%, coating layer thickness is
50 ± 1 μm, after impregnating 7d in 3.5wt.%NaCl solution, through electro-chemical test, composite coating impedance value is 1.7 × 109
Ω·cm2, and blank coating is only 9.2 × 106Ω·cm2, antiseptic property is obviously improved.
Application examples 4
Graphite nano plate is made using embodiment 3 in the application example, is doped into fluorine carbon metal paint coating by 1wt%, applies thickness
Degree is 50 ± 1 μm, and after impregnating 7d in 3.5wt.%NaCl solution, through electro-chemical test, coating impedance value is 2.9 × 108
Ω cm2, blank coating are 1.2 × 106Ω cm2, antiseptic property are obviously improved.
Application examples 5
Graphite nano plate is made using embodiment 1 in this comparative example, is doped into phenolic aldehyde vinyl modified epoxy-based lacquers by 10wt.%
Coating, coating layer thickness are 180 ± 1 μm.Glass flake-phenolic aldehyde vinyl modified epoxy lacquer coat is prepared using same process.?
After being impregnated one month in 20wt.% sulfuric acid, carries out electro-chemical test and show, graphite nano plate-phenolic aldehyde vinyl modified epoxy-based lacquers
Coating impedance value is 5.7 × 109Ω·cm2, and glass flake-phenolic aldehyde vinyl modified epoxy-based lacquers coating impedance value be only 2.6 ×
108Ω·cm2, it was demonstrated that this legal system obtains graphite nano plate antiseptic property better than glass flake.Cold shock testing further displays,
Graphite nano plate-phenolic aldehyde vinyl modified epoxy lacquer coat cold-hot impact property is excellent (- 10 DEG C of low temperature, 80 DEG C of high temperature), warp
It recycles for 100 times or more, has no coating breaks down and matrix stripping；Glass flake-phenolic aldehyde vinyl modified epoxy lacquer coat cold-hot
Impact property is poor, through 23 times recycle, though coating has no rupture, with matrix stripping.
Claims (8)
1. a kind of preparation method of large scale graphite nano plate, which is characterized in that expanded graphite is added in concentrated acid, is being kept
In higher than 25 DEG C environment while 0.5h or more is stirred, is cooled to room temperature after removing, is washed by repeated filtration, is then done
It is dry, graphite nano plate is made.
2. preparation method according to claim 1, which is characterized in that expanded graphite carbon content described in preparation step 90%
More than, 32~1200 mesh of partial size.
3. preparation method according to claim 1, which is characterized in that expanded graphite described in preparation step and concentrated acid quality
Than being 1:1~20000.
4. preparation method according to claim 1, which is characterized in that concentrated acid concentration described in preparation step, according to difference
Sour type defines difference, concentrated nitric acid > 35wt%, sulfuric acid > 50wt%, concentrated hydrochloric acid > 20wt%, concentrated phosphoric acid > 50wt%, hydrogen fluorine
Sour > 25wt%.
5. preparation method according to claim 1, which is characterized in that stirring rate described in preparation step be 10rpm with
On.
6. preparation method according to claim 1, which is characterized in that the graphite nano plate lateral dimension being prepared is 10
~1000 μm, thickness be less than 50nm.
7. the preparation method for preparing graphite nano plate based on expanded graphite described in any one according to claim 1~6 is prepared into
The graphite nano plate arrived.
8. application of the graphite nano plate as claimed in claim 7 in functional composite material and corrosion-inhibiting coating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN106800295A (en) * | 2016-12-31 | 2017-06-06 | 南京新月材料科技有限公司 | A kind of method that utilization potassium bichromate prepares big lamella graphene oxide |
-
2018
- 2018-08-03 CN CN201810877231.9A patent/CN108840332A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN106800295A (en) * | 2016-12-31 | 2017-06-06 | 南京新月材料科技有限公司 | A kind of method that utilization potassium bichromate prepares big lamella graphene oxide |
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Application publication date: 20181120 |