CN109021798A - A kind of graphene conductive coating for protective film - Google Patents
A kind of graphene conductive coating for protective film Download PDFInfo
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- CN109021798A CN109021798A CN201810562817.6A CN201810562817A CN109021798A CN 109021798 A CN109021798 A CN 109021798A CN 201810562817 A CN201810562817 A CN 201810562817A CN 109021798 A CN109021798 A CN 109021798A
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- graphene
- conductive coating
- modified graphene
- polyaniline
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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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
- C09D5/24—Electrically-conducting paints
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The graphene conductive coating and preparation method thereof that the invention discloses a kind of for protective film; the graphene conductive coating includes the component of following mass percent: polyurethane aqueous dispersions 45% ~ 60%; modified graphene Polyaniline 20% ~ 24%; dispersing agent 0.5 ~ 3.0%; defoaming agent 0.1% ~ 1.0%; antitack agent 1.0% ~ 5.0%, balance deionized water.The present invention utilizes biomass dispersion liquid modified graphene and compound with polyaniline; modified graphene Polyaniline is prepared; and the graphene conductive coating for protective film is finally prepared, graphene conductive coating obtained has excellent storage stability and has good conductive property the graphene conductive film that can be prepared that thickness is uniform, paint film electric conductivity is uniform.
Description
Technical field
The present invention relates to protective film technical fields, more particularly, to a kind of graphene conductive for protective film
Coating.
Background technique
It, generally can be in quotient situations such as colliding, scratch during transportation in order to prevent after the completion of many commodity production
Product surface covers one layer of protective film.Commodity after transit is complete, need to tear protective film, therefore, using peelable painting
Material protection commodity surface is becoming increasingly popular.But existing Stripable paint does not have electric conductivity, peelable guarantor obtained
Shield Thin film conductive performance is poor, and the electrostatic that commodity generate during transportation cannot exclude, and brings inconvenience to Commodity Transportation, even endangers
Danger.
About conductive coating, when conductive coating is coated on the object with high resistivity, there is conduction electric current, exclude product
The effect of tired electrostatic charge and electromagnetic shielding, occupies an important position in information and electronic field, is widely used in aviation, boat
It, electronic computer, measurement and control system, communication equipment, medical equipment, auto industry, sensor, consumer electronic product etc.
Numerous areas.
Conductive filler is the important component of conductive coating, and the selection of conductive filler, mainly selection is closed as needed
Suitable conductive filler type, shape and dosage.Common conductive filler includes: metal system filler, such as silver powder, nickel powder and copper powder
Deng；Carbon filler, such as graphite, carbon black, carbon fiber and carbon nanotube；Metal oxide system filler, such as tin oxide, zinc oxide
Deng；And compounded mix etc..Often spherical, sheet, needle-shaped can be made according to the difference of preparation process in the shape of conductive filler,
And the various shapes such as fibrous powder.Under normal circumstances, the particle of conductive filler is smaller, and the electric conductivity of coating is better, and makes
It is got well than with the electric conductivity of ball filler with laminal filter.The dosage selection of conductive filler is also very heavy for the property of slurry
: the very few filler that will lead to of dosage can not form continuous network, influence the electric conductivity of coating；And dosage excessively can then make to apply
Layer strength reduction.
Graphene has good conductive property, and the addition of graphene can effectively improve the electric conductivity of material.But by
In the mechanical feature of graphene itself, graphene sheet layer is neither hydrophilic nor oleophylic, since π-π acts on the group of being easy between lamella
It is poly-, the storage stability of the conductive coating added with graphene is influenced, so that graphene conductive coating is easy sedimentation, it has not been convenient to apply
Work, coating thickness is not uniform enough, and paint film electric conductivity is inhomogenous, it is difficult to protect internal base material.
Therefore, it is badly in need of developing the graphene conductive coating excellent for the storage stability of peelable protective film.
Summary of the invention
The present invention is to overcome the defect of protective film electric conductivity difference described in the above-mentioned prior art, provides a kind of graphene
Conductive film, the graphene conductive film provided conduct electricity very well, and have the function of antistatic, being capable of effective protection commodity list
Face.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of graphene conductive coating for protective film, the component including following mass percent:
Polyurethane aqueous dispersions 45%~60%, modified graphene Polyaniline 20%~24%, dispersing agent 0.5
~3.0%, defoaming agent 0.1%~1.0%, antitack agent 1.0%~5.0%, balance deionized water；
The preparation method of the modified graphene Polyaniline includes the following steps:
S1. by peanut shell, melamine and 0.8~1.5mol/L NaOH solution according to mass ratio be 1~1.3:1.0~
After the ratio mixing of 1.5:50, uniform sizing material is made, is then diluted with water to 2~3 times, stirs evenly, bottom is discarded after standing
Precipitating, obtains biomass dispersion liquid；
S2. the biomass dispersion liquid of S1. and graphene oxide solution are mixed to get reaction solution, in 180~200 DEG C of conditions
15~18 DEG C of lower hydro-thermal reaction, obtains modified graphene dispersion liquid after dialysis treatment；The content of biomass in the reaction solution
For 3.0~4.0mg/mL, the content of graphene oxide is 0.5~2.0mg/mL in the reaction solution；
S3. the polymerization reaction that aniline is carried out in the modified graphene dispersion liquid of S2., it is multiple to obtain modified graphene polyaniline
Close object.
The graphene oxide solution can be obtained by those skilled in the art according to prior art preparation, also commercially available
It obtains.
By peanut hull biologic matter modified graphene and gather provided by the present invention for the graphene conductive coating of protective film
Aniline is compound and the auxiliary agents such as polyurethane aqueous dispersions, antitack agent is cooperated to be prepared, and graphene conductive coating obtained has
Excellent storage stability, plug and play is easy for construction, and coating thickness is uniform, can be used for peelable protective film.
Peanut shell is a kind of common agricultural by-products, and yield is big, and there are no be fully used.Contain fibre in peanut shell
The biomass abundant such as element are tieed up, the present invention is by a large amount of the study found that peanut shell, melamine and sodium hydroxide solution are ground
Biomass dispersion liquid is prepared in mill, and biomass dispersion liquid obtained passes through special item under the melamine cooperation of certain content
Hydro-thermal reaction generates carbon nano-particle on the surface of graphene under part, and the class π-π effect of melamine and graphene surface is so that three
Poly cyanamid can induce the biomass of peanut shell to be anchored and generate carbon nano-particle on the surface of graphene, to obtain modified graphite
Alkene.Meanwhile graphene oxide is restored by hydrothermal, restores electric conductivity.Modified graphene obtained has good
Electric conductivity, and be easy to disperse again in water, and do not allow easy to reunite.The poly- of aniline is carried out in modified graphene dispersion liquid
Reaction is closed, modified graphene Polyaniline is prepared.
Polyaniline is linear polymer, and polyaniline realizes polyaniline by the carbon nano-particle on winding modified graphene surface
With effective compound, close effect of modified graphene, the molecular resin chain of polyaniline molecule chain and coating is intertwine with each other, so that changing
Property graphene is not easily settled in coating, and dispersibility further increases.
Modified graphene and polyaniline interact to form continuous conductive layer, the conductive particle of conductive layer in coating matrix
Existing face and face contact between son, it is also wired to be contacted with line, so that conductive coating has preferable electric conductivity.Due to modified stone
Black alkene Polyaniline has excellent dispersibility, enables conductive coating in the case where guaranteeing adhesive force, increase changes
The additional amount of property graphene Polyaniline, therefore, graphene conductive coating provided by the invention not only has excellent storage
Deposit stability, moreover it is possible to obtain the promotion of electric conductivity.
Graphene conductive coating provided by the invention can be prepared in non-conductive substrate peelable by the method for brushing
From protective film.
Preferably, the uniform sizing material is made up of ceramic ball grinder ball milling.Preferably, the fineness of the uniform sizing material is
30μm。
Preferably, the time of standing be 20~for 24 hours.
Preferably, the content of graphene oxide is 1.0~1.5mg/mL in the reaction solution.
Graphene oxide content is lower in reaction solution, that is, when being less than 1.0mg/mL, biomass is relatively more, so obtained
Modified graphene surface can generate more carbon particles, keep the dispersibility of modified graphene more preferable, to promote modified graphite
The dispersibility of alkene Polyaniline, and then the storage stability of conductive coating is improved, still, the presence of carbon particle may interfere with
Modified graphene carries out face and face contact, is unfavorable for modified graphene by surface-to-surface contact to form conductive non-individual body, makes to make
The electric conductivity decline of the conductive coating obtained.And graphene oxide too high levels in reaction solution, that is, when being greater than 1.5mg/mL, due to changing
Property graphene surface carbon particle it is less, the stable storing of conductive coating obtained decline, but since modified graphene more holds
Surface-to-surface contact is easily formed, so the electric conductivity of conductive coating improves.When graphene oxide in reaction solution content 1.0~
When within the scope of 1.5mg/mL, peelable graphene conductive coating obtained can obtain excellent storage stability and good simultaneously
Electric conductivity.Correspondingly, as can graphene conductive film made from peelable graphene conductive coating to be able to maintain thickness equal
Even, paint film electric conductivity stable uniform, and have good conductive property, anti-static electrification is good.
Preferably, the content of graphene oxide is 1.5mg/mL in the reaction solution.
When the content of graphene oxide in reaction solution is 1.5mg/mL, content of the graphene oxide with respect to peanut hull biologic matter
Just suitable, the storage stability and electric conductivity of peelable graphene conductive coating obtained are more preferable, and graphene obtained is led
The film thickness of conductive film is more uniform, paint film electric conductivity more stable uniform, and anti-static electrification is more preferable.
Preferably, the polymerization reaction of aniline includes the following steps: in step S3.
Mixed dispersion liquid is prepared in modified graphene, aniline, acid-mixed conjunction, then adds dropwise under the conditions of 0~3 DEG C and contains
There is the ammonium persulfate solution of acid, after reacting 5~10h, is washed, is lyophilized to obtain modified graphene Polyaniline；It is described to change
Property graphene and the mass ratio of aniline be 1:1~8, the molar ratio of ammonium persulfate and aniline is 1:2~3.
The concentration of modified graphene can be dense for the generally common graphene dispersing solution in this field in the mixed dispersion liquid
Degree.The dispersibility of the modified graphene of the application is significantly better than existing graphene or functionalization graphene, therefore in general stone
It can be well dispersed within the scope of black alkene dispersion liquid concentration.Preferably, in the mixed dispersion liquid modified graphene concentration be 2~
3mg/mL。
Acid in the mixed dispersion liquid can be sulfuric acid, hydrochloric acid or phosphoric acid.Preferably, the concentration of the sulfuric acid is 0.5
~1.0mol/L.
Polyaniline linear molecule is anchored at modified graphite by the carbon particle on winding modified graphene surface to realize
Alkene surface, modified graphene are worked in coordination with polyaniline, well dispersed in conductive coating system, and storage stability is splendid.
Polyaniline is compound with modified graphene as conducting polymer, not only enhances the dispersion performance of modified graphene, is promoted conductive
The storage stability of coating additionally aids and forms more continuous electric conductors in coating paint film, to improve conductive coating
Electric conductivity.
Opposite modified graphene, when polyphenyl amine content is too low, since modified graphene surface is not anchored enough gather
Aniline, polyaniline can not effectively promote the dispersion performance of modified graphene, the storage stability of conductive coating obtained promoted compared with
It is few；When polyphenyl amine content is relatively excessively high, polyaniline can effectively promote the dispersion performance of modified graphene, still, excessively
Polyaniline by hinder modified graphene contact with each other to form continuous conduction body, be merely capable of forming polyaniline continuous conduction body,
The electric conductivity of conductive coating obtained is promoted less.
It is therefore preferred that the mass ratio of the modified graphene and aniline is 1:4~6.
The mass ratio of modified graphene and polyaniline is 1:4~6, and the content of polyaniline can both improve modified graphite just
The dispersibility of alkene will not hinder modified graphene to contact with each other to be formed and continuously lead to promoting the storage stability of conductive coating
Electric body.
Preferably, the mass ratio of the modified graphene and aniline is 1:5.
The mass ratio of modified graphene and aniline is 1:5, and the storage stability and electric conductivity of conductive coating obtained are more
Good, the film thickness of corresponding graphene conductive film is more uniform, paint film electric conductivity is more uniform, and antistatic performance is more
It is good.
Preferably, the polyurethane aqueous dispersions are that fatty polyurethane aqueous dispersion or aromatic urethane are aqueous
Dispersion.
Preferably, the polyurethane aqueous dispersions are Royal DSM NeoPac E-251.
Preferably, the dispersing agent is polycarboxylic acids ammonium salt or sodium salt dispersing agent.Preferably, the dispersing agent is Shenzhen Hai Chuan
Chemical industry SN-5027 or U.S. ROHM AND HAAS Orotan731A.
Preferably, the defoaming agent is mineral oil or organic silicon defoamer.Defoaming agent is a kind of with compared with low surface tension
With high surfaces activity, the substance of foam in liquid can be suppressed or eliminated.
Preferably, the defoaming agent is the Foamex-902W of the BYK-019 or TEGO company of Bi Ke company of Germany.
Preferably, the antitack agent is silicone oil or wax emulsion.
Preferably, the antitack agent is the compound of polythene wax emulsion or dimethyl silicone polymer and atoleine.More
Preferably, the antitack agent is the beautiful conjunction 3415 in Shanghai.
The present invention protects the preparation method of above-mentioned graphene conductive film simultaneously, and the preparation method includes the following steps:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water is uniformly mixed, and peelable graphene conductive coating is prepared；Peelable graphene conductive coating obtains stone by brushing
Black alkene conductive film.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is prepared using biomass dispersion liquid modified graphene and compound with polyaniline containing modified graphene
Polyaniline, and the graphene conductive coating for protective film is finally prepared, graphene conductive coating obtained
With excellent storage stability and have good conductive property, can be prepared thickness uniformly, paint film electric conductivity it is equal
The anti-static effect of one graphene conductive film, graphene conductive film is good, being capable of effective protection commodity surface.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of modified graphene made from embodiment 1.Scale is 500nm in figure.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
The equal cocoa of raw material in embodiment is by being commercially available；
In embodiment and comparative example, polyurethane aqueous dispersions are Royal DSM NeoPac E-251；Dispersing agent is Shen Zhenhai
River chemical industry SN-5027；Defoaming agent is the BYK-019 of Bi Ke company of Germany；Antitack agent, which is that Shanghai is beautiful, closes 3415.
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
(1) preparation of the graphene oxide of embodiment and comparative example
After mixing by crystalline flake graphite and potassium permanganate 1:5~7 in mass ratio, it is added to containing the concentrated sulfuric acid and concentrated phosphoric acid
Reactor in, 40~50 DEG C are stirred to react 10~12h, add ice water and hydrogen peroxide is cooled to room temperature, be centrifuged, wash,
1.0~2.0mg/mL graphene oxide solution is made into after dialysis.
(2) unmodified graphene is prepared
1mg/mL graphene oxide solution is prepared, hydrazine hydrate is added and ammonium hydroxide, 85~95 DEG C of 4~6h of reaction are centrifuged, wash
It washs, be lyophilized and be ground to 150~300 mesh, graphene is made.
Embodiment 1
A) modified graphene Polyaniline is prepared
Peanut shell is respectively placed in ethyl alcohol and deionized water to drying after being cleaned by ultrasonic at least 7min, then according to peanut
The ratio that the mass ratio of shell, melamine and 1.0mol/LNaOH solution is 1.2:1.2:50 mixes, and is ground using ceramic ball grinder
Uniform sizing material is worn into, the fineness of uniform sizing material is 30 μm；The quality of peanut shell is 2.0g；2 times are diluted with water to, is sufficiently stirred；
After for 24 hours, bottom sediment is discarded, obtains biomass dispersion liquid；
Biomass dispersion liquid and graphene oxide water solution are mixed to get reaction solution, control biomass content in reaction solution and are
3.0mg/mL, graphene oxide content is 1.5mg/mL in reaction solution；By reaction solution under the conditions of 180~200 DEG C hydro-thermal 16h,
Modified graphene dispersion liquid is obtained, graphene surface has loaded nano carbon particle, so that graphene dispersion is good；Pass through
The bag filter of 1000D is dialysed, and salt, alkali or small organic molecule in modified graphene dispersion liquid are removed；Freeze-drying obtains modified stone
Black alkene；
Modified graphene is dispersed in water, aniline, sulfuric acid is added, obtains mixed dispersion liquid；At a temperature of 0~3 DEG C by
The ammonium persulfate solution containing sulfuric acid is added dropwise, washed, be lyophilized to obtain modified graphene Polyaniline；Modified graphene with
The mass ratio of aniline is 1:4, and the molar ratio of ammonium persulfate and aniline is 1:2, reaction time 8h, modified graphene dispersion liquid
Concentration is 2mg/mL；The concentration of sulfuric acid is 0.6mol/L in mixed dispersion liquid and ammonium persulfate solution；
B) conductive coating is prepared
The composition of conductive coating are as follows:
Preparation step:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water, which sequentially adds in stirred tank, to stir evenly, and graphene conductive coating is prepared.
Embodiment 2
A) modified graphene Polyaniline is prepared
Peanut shell is respectively placed in ethyl alcohol and deionized water to drying after being cleaned by ultrasonic at least 7min, then according to peanut
The ratio that the mass ratio of shell, melamine and 0.8mol/LNaOH solution is 1.0:1.5:50 mixes, and is ground using ceramic ball grinder
Uniform sizing material is worn into, the fineness of uniform sizing material is 30 μm；The quality of peanut shell is 2.0g；2 times are diluted with water to, is sufficiently stirred；
After 22h, bottom sediment is discarded, obtains biomass dispersion liquid；
Biomass dispersion liquid and graphene oxide water solution are mixed to get reaction solution, control biomass content in reaction solution and are
3.5mg/mL, graphene oxide content is 1.0mg/mL in reaction solution；By reaction solution under the conditions of 180~200 DEG C hydro-thermal 15h,
Modified graphene dispersion liquid is obtained, graphene surface has loaded nano carbon particle, so that graphene dispersion is good；Pass through 800D
Bag filter dialysis, remove modified graphene dispersion liquid in salt, alkali or small organic molecule；Freeze-drying, obtains modified graphene；
Modified graphene is dispersed in water, aniline, sulfuric acid is added, obtains mixed dispersion liquid；At a temperature of 0~3 DEG C by
The ammonium persulfate solution containing sulfuric acid is added dropwise, washed, be lyophilized to obtain modified graphene Polyaniline；Modified graphene with
The mass ratio of aniline is 1:1, and the molar ratio of ammonium persulfate and aniline is 1:3, reaction time 6h, modified graphene dispersion liquid
Concentration is 2mg/mL；The concentration of sulfuric acid is 0.5mol/L in mixed dispersion liquid and ammonium persulfate solution；
B) conductive coating is prepared
The composition of conductive coating are as follows:
Preparation step:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water, which sequentially adds in stirred tank, to stir evenly, and graphene conductive coating is prepared.
Embodiment 3
A) modified graphene Polyaniline is prepared
Peanut shell is respectively placed in ethyl alcohol and deionized water to drying after being cleaned by ultrasonic at least 7min, then according to peanut
The ratio that the mass ratio of shell, melamine and 1.3mol/LNaOH solution is 1.3:1.3:50 mixes, and is ground using ceramic ball grinder
Uniform sizing material is worn into, the fineness of uniform sizing material is 30 μm；The quality of peanut shell is 2.0g；3 times are diluted with water to, is sufficiently stirred；
After 23h, bottom sediment is discarded, obtains biomass dispersion liquid；
Biomass dispersion liquid and graphene oxide water solution are mixed to get reaction solution, control biomass content in reaction solution and are
3.0mg/mL, graphene oxide content is 0.5mg/mL in reaction solution；By reaction solution under the conditions of 180~200 DEG C hydro-thermal 18h,
Modified graphene dispersion liquid is obtained, graphene surface has loaded nano carbon particle, so that graphene dispersion is good；Pass through
The bag filter of 1000D is dialysed, and salt, alkali or small organic molecule in modified graphene dispersion liquid are removed；Freeze-drying obtains modified stone
Black alkene；
Modified graphene is dispersed in water, aniline, sulfuric acid is added, obtains mixed dispersion liquid；At a temperature of 0~3 DEG C by
The ammonium persulfate solution containing sulfuric acid is added dropwise, washed, be lyophilized to obtain modified graphene Polyaniline；Modified graphene with
The mass ratio of aniline is 1:6, and the molar ratio of ammonium persulfate and aniline is 1:2, reaction time 10h, modified graphene dispersion liquid
Concentration be 3mg/mL；The concentration of sulfuric acid is 0.8mol/L in mixed dispersion liquid and ammonium persulfate solution；
B) conductive coating is prepared
The composition of conductive coating are as follows:
Preparation step:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water, which sequentially adds in stirred tank, to stir evenly, and graphene conductive coating is prepared.
Embodiment 4
A) modified graphene Polyaniline is prepared
Peanut shell is respectively placed in ethyl alcohol and deionized water to drying after being cleaned by ultrasonic at least 7min, then according to peanut
The ratio that the mass ratio of shell, melamine and 1.5mol/LNaOH solution is 1.1:1.0:50 mixes, and is ground using ceramic ball grinder
Uniform sizing material is worn into, the fineness of uniform sizing material is 30 μm；The quality of peanut shell is 2.0g；2 times are diluted with water to, is sufficiently stirred；
After for 24 hours, bottom sediment is discarded, obtains biomass dispersion liquid；
Biomass dispersion liquid and graphene oxide water solution are mixed to get reaction solution, control biomass content in reaction solution and are
4.0mg/mL, graphene oxide content is 2.0mg/mL in reaction solution；By reaction solution under the conditions of 180~200 DEG C hydro-thermal 16h,
Modified graphene dispersion liquid is obtained, graphene surface has loaded nano carbon particle, so that graphene dispersion is good；Pass through
The bag filter of 1000D is dialysed, and salt, alkali or small organic molecule in modified graphene dispersion liquid are removed；Freeze-drying obtains modified stone
Black alkene；
Modified graphene is dispersed in water, aniline, sulfuric acid is added, obtains mixed dispersion liquid；At a temperature of 0~3 DEG C by
The ammonium persulfate solution containing sulfuric acid is added dropwise, washed, be lyophilized to obtain modified graphene Polyaniline；Modified graphene with
The mass ratio of aniline is 1:8, and the molar ratio of ammonium persulfate and aniline is 1:2, reaction time 8h, modified graphene dispersion liquid
Concentration is 2mg/mL；The concentration of sulfuric acid is 1.0mol/L in mixed dispersion liquid and ammonium persulfate solution；
B) conductive coating is prepared
The composition of conductive coating are as follows:
Preparation step:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water, which sequentially adds in stirred tank, to stir evenly, and graphene conductive coating is prepared.
Embodiment 5
The present embodiment and the difference of embodiment 1 are that graphene oxide content is 0.5mg/mL in reaction solution；Other experiment steps
Rapid and raw material additional amount is same as Example 1.
Embodiment 6
The present embodiment and the difference of embodiment 1 are that graphene oxide content is 1.0mg/mL in reaction solution；Other experiment steps
Rapid and raw material additional amount is same as Example 1.
Embodiment 7
The present embodiment and the difference of embodiment 1 are that graphene oxide content is 2.0mg/mL in reaction solution；Other experiment steps
Rapid and raw material additional amount is same as Example 1.
Embodiment 8
The present embodiment and the difference of embodiment 1 are that the mass ratio of modified graphene and aniline is 1:1；Other experimental procedures
And raw material additional amount is same as Example 1.
Embodiment 9
The present embodiment and the difference of embodiment 1 are that the mass ratio of modified graphene and aniline is 1:5；Other experimental procedures
And raw material additional amount is same as Example 1.
Embodiment 10
The present embodiment and the difference of embodiment 1 are that the mass ratio of modified graphene and aniline is 1:6；Other experimental procedures
And raw material additional amount is same as Example 1.
Embodiment 11
The present embodiment and the difference of embodiment 1 are that the mass ratio of modified graphene and aniline is 1:8；Other experimental procedures
And raw material additional amount is same as Example 1.
Comparative example 1
In water by graphene dispersion, aniline, sulfuric acid is added, obtains mixed dispersion liquid；Add dropwise at a temperature of 0~3 DEG C
Ammonium persulfate solution containing sulfuric acid is washed, is lyophilized to obtain graphene Polyaniline；The mass ratio of graphene and aniline
For 1:4, the molar ratio of ammonium persulfate and aniline is 1:2, and reaction time 8h, the concentration of graphene dispersing solution is 2mg/mL；It is mixed
The concentration for closing sulfuric acid in dispersion liquid and ammonium persulfate solution is 0.6mol/L；
B) conductive coating is prepared
The composition of conductive coating are as follows:
Preparation step:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and go from
Sub- water, which sequentially adds in stirred tank, to stir evenly, and graphene conductive coating is prepared.
Comparative example 2
The difference of this comparative example and embodiment 1 is, using etc. 1, the 6- hexamethylene diamines of amount of substances substitute melamine；Other
Experimental procedure and raw material additional amount are same as Example 1.
Comparative example 3
The difference of this comparative example and embodiment 1 is that the mass ratio of peanut shell, melamine and 1.0mol/LNaOH solution is
1.2:0.8:50；Other experimental procedures and raw material additional amount are same as Example 1.
Comparative example 4
The difference of this comparative example and embodiment 1 is that the mass ratio of peanut shell, melamine and 1.0mol/LNaOH solution is
1.2:1.7:50；Other experimental procedures and raw material additional amount are same as Example 1.
Performance test
Using the pattern of modified graphene made from transmissioning electric mirror test embodiment 1, as a result as shown in Figure 1.
The performance of graphene conductive coating made from embodiment 1~11 is as shown in table 1；
The performance of graphene conductive coating made from comparative example 1~4 is as shown in table 2.
The property representation of peelable graphene conductive coating is as follows:
Condition in container is tested according to GB/T 3186-2006 method；
Storage stability is tested according to GB/T 6753.3-86 method, and coating sealed package exists 4 parts of samples
It is stood in 50 DEG C of environment, 30 days whens check the settling phase of first part of sample；
In addition, extend the time again, 35 days, 40 days, 45 days whens, successively check the settling phase of remaining 3 parts of samples respectively.
Conductive coating is made in graphene conductive coating, test performance:
Sheet resistance is tested according to GB/T 1410-2006 method.
It is brushed in non-conductive planar substrates using graphene conductive coating, obtains the graphene with a thickness of 150~200 μm
Conductive film, tests multiple spot film thickness, and whether detection film thickness is uniform；
Test the stripping performance of graphene conductive film.
The performance of graphene conductive coating made from 1 embodiment 1~11 of table
The performance of graphene conductive coating made from 2 comparative example 1~4 of table
As shown in Figure 1, modified graphene surface made from embodiment 1 has more carbon particle.Embodiment 2~7 is made
Modified graphene pattern it is similar to Example 1；The pattern of modified graphene made from embodiment 8~11 and 1 phase of embodiment
Together.
As shown in Table 1, state is normal, test storage stability discovery to embodiment 1~11 in a reservoir, after 30 days according to
It is so suspended state, does not settle, is 10 grades, there is excellent storage stability；Further study the storage pole of conductive coating
Limit, it is found that embodiment 1,3,5,6,9,10 and 11 is still suspended state after 35 days.As it can be seen that graphene provided by the invention
Conductive coating has very excellent storage stability.It is corresponding, the thickness of the graphene conductive film as made from embodiment 1~11
Uniformly, paint film electric conductivity is uniform, has good conductive property, and easily peelable for degree.
And comparative example 1 uses unmodified graphene, it is poor to be prepared graphene conductive coating storage stability, is 4
Grade.Comparative example 2 does not use melamine, but uses 1,6- hexamethylene diamine, and with graphene surface π-π can not occur for 1,6- hexamethylene diamine
Effect, it may be difficult to peanut hull biologic matter be guided to grow carbon particle, graphene conductive coating storage obtained on the surface of graphene
Stability is poor, is 6 grades.In addition, very few and excessive melamine is respectively adopted in comparative example 3 and comparative example 4, equally it is difficult to make
Standby to obtain the graphene conductive coating of excellent in stability, the storage stability of graphene conductive coating obtained is 6 grades, is not achieved
10 grades.Using graphene conductive film made from the poor comparative example 1~4 of stability, in uneven thickness, paint film electric conductivity is not
It is uniform, it is impossible to be used in prepare peelable protective film.
By comparing embodiment 1 and 5~7, it is known that 6 better performances of embodiment 1 and embodiment, embodiment 1 and embodiment 6
Under conditions of with excellent storage stability, also there is good electric conductivity.And then electric conductivity is slightly worse for embodiment 5, it is real
Applying example 7, then storage stability is slightly worse, it is difficult to while there is excellent storage stability and good electric conductivity.Therefore, it aoxidizes
When the content of graphene is 1.0~1.5mg/mL, graphene conductive coating property obtained is more preferable, moreover, graphene oxide
Conductive coating overall performance obtained is best when content is 1.5mg/mL.
According to embodiment 1 and 8~11 it is found that graphene conductive coating made from embodiment 1,9~10 has excellent storage
Stability is deposited, but also is able to maintain good electric conductivity；And embodiment 8 due to polyaniline with respect to modified graphene content compared with
Low, polyaniline is higher with respect to modified graphene content in embodiment 11, and being difficult to be prepared both has excellent stable storing
The conductive coating that property has good conductive property again.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (9)
1. a kind of graphene conductive coating for protective film, which is characterized in that the component including following mass percent:
Polyurethane aqueous dispersions 45% ~ 60%, modified graphene Polyaniline 20% ~ 24%, dispersing agent 0.5 ~ 3.0%, defoaming
Agent 0.1% ~ 1.0%, antitack agent 1.0% ~ 5.0%, balance deionized water；
The preparation method of the modified graphene Polyaniline includes the following steps:
It S1. is 1 ~ 1.3:1.0 ~ 1.5:50 according to mass ratio by peanut shell, melamine and 0.8 ~ 1.5mol/L NaOH solution
Ratio mixing after, uniform sizing material is made, is then diluted with water to 2 ~ 3 times, stirs evenly, bottom sediment is discarded after standing, obtain
To biomass dispersion liquid；
S2. the biomass dispersion liquid of S1. and graphene oxide solution are mixed to get reaction solution, are lauched in 180 ~ 200 DEG C of conditions
15 ~ 18 DEG C of thermal response, modified graphene dispersion liquid is obtained after dialysis treatment；In the reaction solution content of biomass be 3.0 ~
4.0mg/mL, the content of graphene oxide is 0.5 ~ 2.0mg/mL in the reaction solution；
S3. the polymerization reaction that aniline is carried out in the modified graphene dispersion liquid of S2., it is compound to obtain modified graphene polyaniline
Object.
2. graphene conductive coating according to claim 1, which is characterized in that graphene oxide contains in the reaction solution
Amount is 1.0 ~ 1.5mg/mL.
3. graphene conductive coating according to claim 2, which is characterized in that graphene oxide contains in the reaction solution
Amount is 1.5mg/mL.
4. graphene conductive coating according to claim 1, which is characterized in that the polymerization reaction packet of aniline in step S3.
Include following steps:
Mixed dispersion liquid is prepared in modified graphene, aniline, acid-mixed conjunction, then dropwise plus containing sour under the conditions of 0 ~ 3 DEG C
Ammonium persulfate solution, react 5 ~ 10h after, washed, be lyophilized to obtain modified graphene Polyaniline；The modified graphite
The mass ratio of alkene and aniline is 1:1 ~ 8, and the molar ratio of ammonium persulfate and aniline is 1:2 ~ 3.
5. graphene conductive coating according to claim 4, which is characterized in that the quality of the modified graphene and aniline
Than for 1:4 ~ 6.
6. graphene conductive coating according to claim 5, which is characterized in that the quality of the modified graphene and aniline
Than for 1:5.
7. graphene conductive coating according to claim 1, which is characterized in that the polyurethane aqueous dispersions are fat
Race's polyurethane aqueous dispersions or aromatic urethane water-borne dispersions.
8. graphene conductive coating according to claim 1, which is characterized in that the antitack agent is silicone oil or wax emulsion.
9. the preparation method of any one of the claim 1 ~ 8 graphene conductive coating, includes the following steps:
By polyurethane aqueous dispersions, modified graphene Polyaniline, dispersing agent, defoaming agent, antitack agent and deionized water
It is uniformly mixed, graphene conductive coating is prepared.
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