CN109666350A - A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene - Google Patents
A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene Download PDFInfo
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- CN109666350A CN109666350A CN201710958202.0A CN201710958202A CN109666350A CN 109666350 A CN109666350 A CN 109666350A CN 201710958202 A CN201710958202 A CN 201710958202A CN 109666350 A CN109666350 A CN 109666350A
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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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- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The present invention provides a kind of waterborne conductive coatings, including water-base resin, highly conductive graphene slurry and auxiliary agent.The present invention selects graphene raw material, it is added using highly conductive graphene, again in the auxiliary agent of water paint, specific type has been selected as slurry auxiliary agent and highly conductive graphene is mixed and has formed slurry, it is mixed again as entirety with other compositions, enable graphene evenly dispersed in coating, to obtain the conductive water paint of the excellent special type of various aspects of performance, show higher electric conductivity and electromagnetic shielding performance, but also have hardness high, adhesive force is good, corrosion resistance and good, other pollution-free equal characteristics, it can adapt to various market-oriented demands.Preparation method simple process, mild condition, safety and environmental protection simultaneously, are more suitable technology mass production.
Description
Technical field
The invention belongs to technical field of aqueous paint, it is related to a kind of waterborne conductive coating and preparation method thereof, more particularly to
A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene.
Background technique
Graphene (Graphene) is a kind of new material of individual layer laminated structure being made of carbon atom, as one kind by carbon
The two dimensional crystal of former molecular only one layer of atomic thickness, it is at present into material most thin in application field and most tough
Material, 200 times more taller than steel of breaking strength, there are also elasticity well, and stretch range can reach the 20% of own dimensions；
Meanwhile graphene also has excellent electric conductivity, can reduce internal resistance, improves the cyclical stability of supercapacitor；In addition, stone
Black alkene is almost fully transparent, the light of absorption 2.3%, and very fine and close, even (helium is former for the smallest gas atom
Son) it can not also penetrate.These features make it be highly suitable for a variety of subjects and field, also have just because of graphene upper
Many excellent physical chemical property are stated, in energy storage material, environmental project, sensing sensitive aspect is widely used, referred to as
" dark fund " or " king of new material ", and potential application prospect is vast, has become global focus at present and grinds
Study carefully hot spot, while also having moved towards industrialization from conceptual phase about derivatives such as graphenes, causes the extensive ginseng of all trades and professions
With.
With the continuous development of electronic information technology, electronic product has been more and more widely used each in life
Field also releases a large amount of electromagnetic radiation while their work brings great convenience, endanger the strong of people
Health.The shell of the equipment such as audio-video instrument, accurate medical instrument, computer, mobile phone mostly uses greatly plastic casing, and plastic casing holds
It is easy to produce static electricity.Thus it is guaranteed that the normal work of electronic electric equipment, protects human health and ecological natural activity etc., needs
These equipment and device are shielded to reduce electromagnetic radiation and electromagnetic interference.Commonly prevent electromagnetic radiation method be
The surface of ground forms conductive layer, so that ground is had conduction electric current and excludes the ability of accumulation electrostatic charge, so that playing prevents electricity
The effect of magnetic radiation interference.And conductive coating has superior antistatic and electromagnetic shielding performance, it may be convenient to spraying or brush
It is applied to material surface of various shapes, forms electromagnetic shielding conductive layer, so that material be made to achieve the purpose that shield electromagnetic wave.Mesh
Before, the conductive coating of most frostings uses solvent type conductive coating, this causes serious shadow to environment and people's health
It rings.Waterborne conductive coating comes into being as a result, but existing waterborne conductive coating comes with some shortcomings: aqueous coating attachment
Power is low, is easy to fall off；Silver system Electrical Conductivity of Conductive Coating can be good, but is easy to appear the phenomenon that silver migrates；Copper- based conductive paint holds
Easily be oxidized etc..
There is respectively excellent characteristic just because of graphene, in recent years, the water paint containing graphite alkenes material produces
Product gradually have relevant report, and graphene is used in waterborne conductive coating as disclosed in CN106590400A, but
In practical application, there is also many problems and restraining factors, such as graphene easily to reunite for graphene.Due to graphene and its
Derivative specific surface area is larger, there is stronger model ylid bloom action power each other, reunites and wrapping phenomena is obvious, prevent it from steady
Fixed dispersion also is easy to reunite again to be difficult to open together after dispersion.Thus, water paint is added using graphene as filler
In, the effect is unsatisfactory, although having numerous studies by way of adding different types of dispersing agent or modification to improve stone
The dispersion effect of black alkene, but effect is still poor in practical application, and can also additionally introduce other impurities, makes to follow-up study
At negative effect.
Therefore, a kind of waterborne conductive coating how is obtained, the performance of waterborne conductive coating can be further increased, it has also become
Many application vendors and line research staff's urgent problem to be solved.
Graphene is preferably distributed in coating system, is the key factor of influence coating property, and.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of waterborne conductive coating and preparation method thereof,
Especially a kind of waterborne conductive coating containing highly conductive graphene, the present invention provide waterborne conductive coating, and graphene can be equal
Even dispersion, so that coating has better electric conductivity and other coating properties.
The present invention provides a kind of waterborne conductive coatings, including water-base resin, highly conductive graphene slurry and auxiliary agent.
Preferably, the phosphorus content of the highly conductive graphene is more than or equal to 98%；
The conductivity of the highly conductive graphene is more than or equal to 40000S/m.
Preferably, the highly conductive graphene slurry includes highly conductive graphene, mixes slurry auxiliary agent and water；
The slurry auxiliary agent of mixing includes one of defoaming agent, levelling agent, rheological modifier and wetting agent or a variety of；
The water-base resin include water soluble acrylic acid, aqueous alkide resin, aqueous epoxy resins, aqueous polyanion resin,
One of water-based fluorocarbon resin and aqueous superchlorinated polyvinyl chloride resin are a variety of；
The auxiliary agent includes anti-flash rusting agent and/or coalescing agent.
Preferably, by the waterborne conductive coating integrally based on,
The water-base resin is 20~80 parts by weight；
The highly conductive graphene is 1~30 parts by weight；
The slurry auxiliary agent of mixing is 0.5~8 parts by weight；
The water is 10~30 parts by weight；
The auxiliary agent is 0.5~4 parts by weight.
Preferably, by the waterborne conductive coating integrally based on,
The defoaming agent is 0.1~2 parts by weight；
The levelling agent is 0.1~2.5 parts by weight；
The rheology modifier is 0.1~2.5 parts by weight；
The wetting agent is 0.1~2 parts by weight；
The anti-flash rusting agent is 0.5~3.5 parts by weight；
The coalescing agent is 0.2~2 parts by weight.
Preferably, the defoaming agent includes the one of tego902w, tego901, BYK-24, tego1488 and KOOLY-3150
Kind is a variety of；
The levelling agent include silok8244, silok315, silok23, silok8066 and silok333 one kind or
It is a variety of；
The rheology modifier includes the one or more of RM-8W, RM-2020n and RM-12w；
The wetting agent includes one kind of tego twin 4100, Surfynol 104A, silok8030 and silok8008
Or it is a variety of；
The anti-flash rusting agent includes one kind or more of sodium nitrite in aqueous solution, NALZIN FA 179, CH07A and R-760F
Kind；
The coalescing agent includes the one or more of texanol, DPnB, DPnP, TPnB and DPM.
The present invention also provides a kind of preparation methods of waterborne conductive coating, comprising the following steps:
1) by highly conductive graphene, mix slurry auxiliary agent and water and ground after mixing for the first time, obtain highly conductive graphene
Slurry；
2) highly conductive graphene slurry, water-base resin and the auxiliary agent obtained above-mentioned steps carries out after mixing again, stands,
Obtain waterborne conductive coating.
Preferably, the highly conductive graphene obtains after being prepared by following methods:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps obtains expanded graphite after high-temperature expansion；
C) expanded graphite for obtaining above-mentioned steps is removed in stripping media, obtains graphene.
Preferably, the mass ratio of the graphite and small molecule intercalator is 1:(1~5)；
The mass ratio of the graphite and the stripping media is 1:(50~300)；
The time of the reaction is 10~30 hours；The temperature of the reaction is 0~40 DEG C；
The mode of the removing includes one of ultrasound removing, sand milling removing, ball milling removing and shearing removing or a variety of.
Preferably, the step 2) specifically:
21) water-base resin and auxiliary agent are obtained into mixture after mixing；
22) mixture that above-mentioned steps obtain is added in highly conductive graphene slurry after being mixed again, stands, obtains
To waterborne conductive coating；
The time mixed again is 15~60min；The revolving speed of mixing again is 300~700r/min；
The time of the standing is 15~45min.
The present invention provides a kind of waterborne conductive coatings, including water-base resin, highly conductive graphene slurry and auxiliary agent.With it is existing
There is technology to compare, the present invention there are aqueous coating adhesive force is low, is easy to fall off for existing water paint electric conductivity；Silver system
Electrical Conductivity of Conductive Coating can be good, but is easy to appear the phenomenon that silver migrates；Copper- based conductive paint is oxidized easily the defects of equal,
Modified material using graphene as waterborne conductive coating；Have and water paint is added as filler for existing graphene
In, easy to reunite, effect is undesirable, and adds the mode of different types of dispersing agent or modification, and it is miscellaneous to additionally introduce other
The problems such as matter etc..
The invention selects graphene raw material, is added using highly conductive graphene, and aqueous
In the auxiliary agent of coating, specific type has been selected as slurry auxiliary agent and highly conductive graphene is mixed and has formed slurry, then as whole
Body is mixed with other compositions, enables graphene evenly dispersed in coating, so that it is excellent to have obtained various aspects of performance
The conductive water paint of special type, show higher electric conductivity and electromagnetic shielding performance, but also have that hardness is high, adhesive force
Other characteristics such as good, corrosion resistance and good, pollution-free can adapt to various market-oriented demands.Preparation method technique simultaneously
Simply, mild condition, safety and environmental protection, are more suitable technology mass production.
Preparation method provided by the invention is at low cost, can solve graphene mixed in aqueous coating system it is uneven easy
The disadvantage of reunion can guarantee the evenly dispersed of graphite alkenes material, have preferable tiled state, less fold；And
The coating electric conductivity and electromagnetic shielding performance of preparation are high, also have good hardness height, adhesive force, corrosion resistance and good and environment friend
The features such as good.
The experimental results showed that the waterborne conductive coating prepared by the present invention containing highly conductive graphene, resistivity are minimum 1
Ω m, hardness of paint film is in 2H, and adhesion 1 grade, the neutral salt spray time is in 600h or more.
Detailed description of the invention
Fig. 1 is the atomic force microscopy of highly conductive graphene prepared by the embodiment of the present invention 1；
Fig. 2 is that the thickness data that highly conductive graphene prepared by the embodiment of the present invention 1 is measured by atomic force microscope is bent
Line；
Fig. 3 is the process flow diagram that the present invention prepares composite water soluble acrylic acid conductive coating；
Fig. 4 is the scanning electron microscope (SEM) photograph of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2；
Fig. 5 is the paint film adhesion test chart of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2；
Fig. 6 is the paint film shock resistance test chart of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, multiple present invention preferably employs pure or water paint is analyzed
The conventional purity that condensation material field uses.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of waterborne conductive coatings, including water-base resin, highly conductive graphene slurry and auxiliary agent.
The water-base resin is not particularly limited in the present invention, with water-base resin type well known to those skilled in the art and
Model, those skilled in the art can select and adjust according to practical situations, product requirement and quality requirement
Whole, water-base resin of the present invention preferably includes water soluble acrylic acid, aqueous alkide resin, aqueous epoxy resins, aqueous polyanion
One of resin, water-based fluorocarbon resin and aqueous superchlorinated polyvinyl chloride resin are a variety of, more preferably water soluble acrylic acid, water alcohol acid
Resin, aqueous epoxy resins, aqueous polyanion resin, water-based fluorocarbon resin or aqueous superchlorinated polyvinyl chloride resin, it is most preferably aqueous
Acrylic acid and/or aqueous alkide resin.
The other parameters of the water-base resin are not particularly limited in the present invention, with routine well known to those skilled in the art
The parameter of water-base resin, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment.
The additional amount of the water-base resin is not particularly limited in the present invention, aqueous is led with well known to those skilled in the art
The proportion of the standard aqueous resin of electrocoating paint, those skilled in the art can according to practical situations, product requirement with
And quality requirement is selected and is adjusted, the additional amount of water-base resin of the present invention is preferably 20~80 parts by weight, more preferably
For 30~70 parts by weight, more preferably 40~60 parts by weight.
The present invention is to improve the practicability of waterborne conductive coating, widens application field, also wraps in the waterborne conductive coating
Include auxiliary agent.
The additional amount of the auxiliary agent is not particularly limited in the present invention, with water paint well known to those skilled in the art
The proportion of conven-tional adjuvants, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment, the additional amount of auxiliary agent of the present invention is preferably 0.5~4 parts by weight, more preferably 1~3.5 parts by weight, more
Preferably 1.5~3.0 parts by weight, more preferably 2.0~2.5 parts by weight.
The type of the auxiliary agent is not particularly limited in the present invention, with aqueous paint additive well known to those skilled in the art
, those skilled in the art can select and adjust according to practical situations, product requirement and quality requirement, this
It invents the auxiliary agent and preferably includes anti-flash rusting agent and/or coalescing agent, more preferably include anti-flash rusting agent and coalescing agent.
The additional amount of the anti-flash rusting agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
The proportion of the anti-flash rusting agent of the routine of material, those skilled in the art can be according to practical situations, product requirement and matter
Amount requires to be selected and adjusted, and the additional amount of anti-flash rusting agent of the present invention is preferably 0.5~3.5 parts by weight, more preferably 1
~3 parts by weight, more preferably 1.5~2.5 parts by weight.
The specific choice of the anti-flash rusting agent is not particularly limited in the present invention, with well known to those skilled in the art aqueous
The anti-flash rusting agent of coating, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment, anti-flash rusting agent of the present invention preferably include sodium nitrite in aqueous solution, NALZIN FA 179, CH07A and R-
760F's is one or more, more preferably sodium nitrite in aqueous solution, NALZIN FA 179, CH07A or R-760F.
The additional amount of the coalescing agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
The proportion of the conventional coalescing agent of material, those skilled in the art can be according to practical situations, product requirement and matter
Amount requires to be selected and adjusted, and the additional amount of coalescing agent of the present invention is preferably 0.2~2 parts by weight, more preferably 0.5
~1.7 parts by weight, more preferably 0.8~1.4 parts by weight.
The specific choice of the coalescing agent is not particularly limited in the present invention, with well known to those skilled in the art aqueous
Coating coalescing agent, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment, coalescing agent of the present invention preferably include one kind or more of texanol, DPnB, DPnP, TPnB and DPM
Kind, more preferably texanol, DPnB, DPnP, TPnB or DPM.
The definition of the graphene in the highly conductive graphene slurry is not particularly limited in the present invention, with art technology
The definition of graphene known to personnel, those skilled in the art can be according to practical situations, product requirement and matter
Amount requires to be selected and adjusted, and graphene of the present invention is preferably the graphene of broad sense, i.e. graphite alkenes material, is preferably wrapped
Include one of graphene, graphene oxide, redox graphene and modified graphene or a variety of, more preferably graphene,
Graphene oxide, redox graphene or modified graphene, most preferably graphene.
The definition of the highly conductive graphene in the highly conductive graphene slurry and parameter is not particularly limited in the present invention,
With the definition and parameter of highly conductive graphene well known to those skilled in the art, those skilled in the art can be according to reality
Applicable cases, product requirement and quality requirement are selected and are adjusted, and the present invention is to further increase waterborne conductive coating
The phosphorus content of performance, the highly conductive graphene is preferably greater than or equal to 98%, is more preferably greater than equal to 98.5%, more preferably greater than
Equal to 99%.The conductivity of the highly conductive graphene is preferably greater than or equal to 40000S/m, is more preferably greater than equal to 45000S/m,
More preferably greater than it is equal to 55000S/m, is more preferably greater than equal to 60000S/m.
The structure of the highly conductive graphene is not particularly limited in the present invention, with graphite well known to those skilled in the art
The structure of alkene, those skilled in the art can select according to practical situations, product requirement and quality requirement
And adjustment, highly conductive graphene of the present invention is flaky, and thickness is preferably no greater than 100nm, more preferably no more than 50nm,
Particularly preferably it is not more than 30nm.
The concrete composition of the highly conductive graphene slurry is not particularly limited in the present invention, and those skilled in the art can be with
It is selected and is adjusted according to practical situations, product requirement and quality requirement, the present invention is to further increase aqueous lead
The performance of electrocoating paint, improves dispersibility of the highly conductive graphene in water paint, and the highly conductive graphene slurry preferably wraps
It includes highly conductive graphene, mix slurry auxiliary agent and water.
The additional amount of the highly conductive graphene is not particularly limited in the present invention, with water well known to those skilled in the art
Conventional proportions in property coating, those skilled in the art can be according to practical situations, product requirement and quality requirement
It is selected and is adjusted, the additional amount of highly conductive graphene of the present invention is preferably 1~30 parts by weight, more preferably 5~25
Parts by weight, more preferably 10~20 parts by weight.
The additional amount for mixing slurry auxiliary agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
The proportion of conven-tional adjuvants in material, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the additional amount of the present invention for mixing slurry auxiliary agent is preferably 0.5~8 parts by weight, more preferably 1.5~7
Parts by weight, more preferably 2.5~6 parts by weight, more preferably 3.5~5 parts by weight.
The additional amount of the water is not particularly limited in the present invention, with normal in water paint well known to those skilled in the art
The proportion of solvent is advised, those skilled in the art can carry out according to practical situations, product requirement and quality requirement
Selection and adjustment, the additional amount of water of the present invention is preferably 10~30 parts by weight, more preferably 12~28 parts by weight, more preferably
For 15~25 parts by weight, more preferably 18~22 parts by weight.
The type for mixing slurry auxiliary agent is not particularly limited in the present invention, with water paint well known to those skilled in the art
Auxiliary agent, those skilled in the art can select and adjust according to practical situations, product requirement and quality requirement
Whole, the present invention further increases the performance of waterborne conductive coating, improves dispersibility of the highly conductive graphene in water paint, institute
Stating and mixing slurry auxiliary agent particularly preferably includes one of defoaming agent, levelling agent, rheological modifier and wetting agent or a variety of, more preferably
Two or more in defoaming agent, levelling agent, rheological modifier and wetting agent, more preferably defoaming agent, levelling agent, levelling are modified
Agent and wetting agent.
The present invention has carried out creative selection in the auxiliary agent of waterborne conductive coating, and is used for and highly conductive graphite
Alkene is first mixed, to effectively raise dispersibility of the graphene in coating, substantially increases the performance of water paint.
The additional amount of the defoaming agent is not particularly limited in the present invention, with water paint well known to those skilled in the art
Conventional antifoam proportion, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the additional amount of defoaming agent of the present invention is preferably 0.1~2 parts by weight, more preferably 0.3~1.8
Parts by weight, more preferably 0.5~1.5 parts by weight, more preferably 0.8~1.2 parts by weight.
The specific choice of the defoaming agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
Expect defoaming agent, those skilled in the art can select according to practical situations, product requirement and quality requirement
And adjustment, defoaming agent of the present invention preferably include tego902w, tego901, BYK-24, tego1488 and KOOLY-3150
It is one or more, more preferably tego902w, tego901, BYK-24, tego1488 or KOOLY-3150.
The additional amount of the levelling agent is not particularly limited in the present invention, with water paint well known to those skilled in the art
Conventional levelling agent proportion, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the additional amount of levelling agent of the present invention is preferably 0.1~2.5 parts by weight, more preferably 0.5~
2.0 parts by weight, more preferably 1~1.5 parts by weight.
The specific choice of the levelling agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
Expect levelling agent, those skilled in the art can select according to practical situations, product requirement and quality requirement
And adjustment, levelling agent of the present invention preferably include silok8244, silok315, silok23, silok8066 and silok333
One or more, more preferably silok8244, silok315, silok23, silok8066 or silok333.
The additional amount of the rheological modifier is not particularly limited in the present invention, with well known to those skilled in the art aqueous
The proportion of the conventional rheological modifier of coating, those skilled in the art can according to practical situations, product requirement with
And quality requirement is selected and is adjusted, the additional amount of rheological modifier of the present invention is preferably 0.1~2.5 parts by weight, more
Preferably 0.5~2.0 parts by weight, more preferably 1~1.5 parts by weight.
The specific choice of the rheological modifier is not particularly limited in the present invention, with water well known to those skilled in the art
Property coating rheological modifier, those skilled in the art can be according to practical situations, product requirement and quality requirement
It is selected and is adjusted, rheological modifier of the present invention preferably includes one kind or more of RM-8W, RM-2020n and RM-12w
Kind, more preferably RM-8W, RM-2020n or RM-12w.
The additional amount of the wetting agent is not particularly limited in the present invention, with water paint well known to those skilled in the art
Conventional wetting agents proportion, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the additional amount of wetting agent of the present invention is preferably 0.1~2 parts by weight, more preferably 0.3~1.8
Parts by weight, more preferably 0.5~1.5 parts by weight, more preferably 0.8~1.2 parts by weight.
The specific choice of the wetting agent is not particularly limited in the present invention, with aqueous painting well known to those skilled in the art
Material wetting agent, those skilled in the art can select according to practical situations, product requirement and quality requirement
Select and adjust, wetting agent of the present invention preferably include tego twin 4100, Surfynol 104A, silok8030 and
Silok8008's is one or more, more preferably tego twin 4100, Surfynol 104A, silok8030 or
silok8008。
The source of the highly conductive graphene is not particularly limited in the present invention, with routine well known to those skilled in the art
Source, commercially available purchase can also be prepared voluntarily, and those skilled in the art can be according to practical situations, product
It is required that and quality requirement selected and adjusted, the present invention further increases the performance of waterborne conductive coating, improves highly conductive
Dispersibility of the graphene in water paint, the highly conductive graphene are preferably prepared by following methods:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps obtains expanded graphite after high-temperature expansion；
C) expanded graphite for obtaining above-mentioned steps is removed in stripping media, obtains graphene.
After the present invention first reacts graphite and small molecule intercalator, intercalated graphite is obtained.
The selection of the graphite is not particularly limited in the present invention, is with graphite material well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright graphite preferably includes one of graphite powder, crystalline flake graphite, artificial graphite, expansible graphite and expanded graphite or more
Kind, more preferably graphite powder, crystalline flake graphite, artificial graphite, expansible graphite or expanded graphite.
The granularity of the graphite powder is not particularly limited in the present invention, with the grain of graphite powder well known to those skilled in the art
Diameter, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The granularity of graphite of the present invention is preferably 50~10000 mesh, more preferably 100~5000 mesh, more preferably 500~3000
Mesh, most preferably 1000~2000 mesh.
The carbon content of the graphite is not particularly limited in the present invention, with the carbon of graphite powder well known to those skilled in the art
Content, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the carbon content of graphite of the present invention is preferably greater than or equal to 70%, is more preferably greater than equal to 80%, is most preferably more than or equal to
90%, it is specifically as follows 70%~95%, or 75%~90%, or be 78%~93%.
The selection of the small molecule intercalator is not particularly limited in the present invention, with small point well known to those skilled in the art
Sub- intercalator, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the present invention are to improve the performance of final products, the small molecule intercalator is preferably that small molecule high temperature can decompose chemical combination
Object, more preferably include sulfuric acid, nitric acid, urea, sodium bicarbonate, carbonic acid sodium dihydrogen, disodium bicarbonate, oxalic acid, phosphoric acid, perchloric acid,
One of periodic acid and trifluoromethanesulfonic acid are a variety of, more preferably sulfuric acid, nitric acid, urea, sodium bicarbonate, carbonic acid sodium dihydrogen,
Disodium bicarbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid or trifluoromethanesulfonic acid.More preferably sulfuric acid, nitric acid, urea, bicarbonate
Sodium, carbonic acid sodium dihydrogen, disodium bicarbonate, oxalic acid or phosphoric acid.
The dosage of the small molecule intercalator is not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, product requirement and quality requirement are selected and are adjusted, and the present invention is to improve the performance of final products, the stone
Ink and the mass ratio of small molecule intercalator are preferably 1:(1~5), more preferably 1:(1.5~4.5), more preferably 1:(2~4),
Most preferably 1:(2.5~3.5).
The temperature of the reaction is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the present invention is to improve the performance and liquid phase separation method of final products
Advantage, reaction temperature is particularly maintained into room temperature, i.e., the temperature of the described reaction is preferably 0~40 DEG C, more preferably 5~35
DEG C, more preferably 10~30 DEG C, more preferably 15~25 DEG C.
The time of the reaction is not particularly limited in the present invention, with liquid phase separation method well known to those skilled in the art
Conventional intercalation time, those skilled in the art can be according to practical condition, product requirement and quality requirements
It being selected and is adjusted, the time of reaction of the present invention is preferably 10~30h, more preferably 12~28h, more preferably 15~
25h, more preferably 17~for 24 hours, it is specifically as follows 10h, 15h, 20h or 30h.
The present invention can decompose intercalator using small molecule high temperature and carry out intercalation, small molecule high temperature decomposable compound to graphite
It can be realized small molecule and enter interlayer, reduce graphite reaction, keep the complete structure of graphite flake layer；And also avoid high temperature height
The reaction condition of pressure has further lowered the temperature of intercalation, can be mild under the conditions of lower temperature and common room temperature etc.
Condition realizes effective intercalation of graphite, obtains graphite intercalation compound, reduces the loss and energy consumption of preparation process, green ring
It protects.
The present invention is to improve the practicability of preparation method, and complete process route, it is also preferable to include post-processings after the reaction
Step.The specific steps of the post-processing are not particularly limited in the present invention, with post-processing well known to those skilled in the art step
Rapid, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
Post-processing of the present invention is preferably included to wash and be separated, more specific to be preferably washed to neutral and centrifuge separation.
Then intercalated graphite that the present invention obtains above-mentioned steps obtains expanded graphite after high-temperature expansion.
The temperature of the high-temperature expansion is not particularly limited in the present invention, with such expansion well known to those skilled in the art
Temperature, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the present invention are to improve the advantage of the performance and liquid phase separation method of final products, and the temperature of the high-temperature expansion is preferably 500
~1200 DEG C, more preferably 600~1100 DEG C, more preferably 700~1000 DEG C, more preferably 800~900 DEG C.
The time of the high-temperature expansion is not particularly limited in the present invention, with high-temperature expansion well known to those skilled in the art
Time, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the time of high-temperature expansion of the present invention is preferably 5~60 seconds, more preferably 10~55 seconds, more preferably 15~50 seconds,
More preferably 25~40 seconds, it is specifically as follows 5 seconds, 10 seconds, 30 seconds or 60 seconds.
The expanded graphite that the present invention finally obtains above-mentioned steps is removed in stripping media, obtains graphene.
Stripping media of the present invention is it can be appreciated that dispersed phase, i.e., by the expanded graphite dispersing agent after expansion process
It is removed after being diluted.
The selection of the stripping media is not particularly limited in the present invention, with stripping media well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention is to improve the performance of final products, and the stripping media preferably includes water, aqueous solution of urea, neopelex water
Solution, ethanol water, N-Methyl pyrrolidone, N, N- dimethyl imide, tetrabutylammonium, dodecyl sodium sulfate
Aqueous solution, lauryl sodium sulfate aqueous solution, Tween 80, cetyl trimethylammonium bromide, nonyl phenol polyethers, P-123 and
One of Dev2043 or a variety of, more preferably water, aqueous solution of urea, sodium dodecyl benzene sulfonate aqueous solution, ethyl alcohol are water-soluble
Liquid, N-Methyl pyrrolidone, N, N- dimethyl imide, tetrabutylammonium, sodium dodecyl sulfate aqueous solution, dodecane
Base aqueous sodium persulfate solution, Tween 80, cetyl trimethylammonium bromide, nonyl phenol polyethers, P-123 or Dev2043, specifically can be with
For aqueous solution of urea, sodium dodecyl benzene sulfonate aqueous solution, ethanol water, N-Methyl pyrrolidone or N, N- dimethyl Asia acyl
Amine, or the aqueous solution of water or organic matter.
The dosage of the stripping media is not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, product requirement and quality requirement are selected and are adjusted, the present invention be improve final products performance, the graphite with
The mass ratio of the stripping media is preferably 1:(50~300), more preferably 1:(100~250), more preferably 1:(150~
200)。
The temperature of the removing is not particularly limited in the present invention, with the temperature of such removing well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The present invention is to improve the advantage of the performance and liquid phase separation method of final products, and the temperature of the removing is preferably room temperature, i.e., preferably
It is 0~40 DEG C, more preferably 5~35 DEG C, more preferably 10~30 DEG C, more preferably 15~25 DEG C.
The time of the removing is not particularly limited in the present invention, and the time with removing well known to those skilled in the art is
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The time of the bright removing is preferably 3~24 hours, more preferably 6~20 hours, more preferable 10~16 hours, is specifically as follows
3 hours, 6 hours, 9 hours, 24 hours.
The mode of the removing is not particularly limited in the present invention, with the side of such removing well known to those skilled in the art
Formula, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The present invention be improve final products performance, the mode of the removing preferably include ultrasound removing, be sanded removing, ball milling removing and
One of shearing removing is a variety of, more preferably ultrasound removing, sand milling removing, ball milling removing or shearing removing, most preferably
Ball milling ultrasound removing simultaneously.
The present invention is to improve the practicability of preparation method, and complete process route, it is also preferable to include post-processings after the removing
Step.The specific steps of the post-processing are not particularly limited in the present invention, with post-processing well known to those skilled in the art step
Rapid, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
Post-processing of the present invention preferably includes washing and/or drying.
The specific steps and condition of the washing are not particularly limited in the present invention, are washed with well known to those skilled in the art
The specific steps and condition washed, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, the mode of washing of the present invention is preferably washed.The standard of washing of the present invention is preferably washed
It is 6~7.5 to pH value, that is, the pH value of water is preferably 6~7.5 after washing, and more preferably 6.5~7.
The specific steps and condition of the drying are not particularly limited in the present invention, with well known to those skilled in the art dry
Dry specific steps and condition, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, the mode of drying of the present invention is preferably dried in vacuo.The temperature of drying of the present invention is preferred
It is 60~100 DEG C, more preferably 70~90 DEG C, more preferably 75~85 DEG C.The time of the drying is preferably 6~for 24 hours, it is more excellent
It is selected as 10~20h, more preferably 12~18h.
The process route combination that the present invention especially uses small molecule intercalation-high-temperature expansion-ultrasound ball milling to remove, can be mild
Under the conditions of quickly, prepare graphene at low cost.And graphene prepared by the present invention have complete lamellar structure, not into
Row surface modification keeps the intrinsic feature of two-dimensional slice,
The invention selects graphene raw material, and the height of further preferred particular step or parameter is led
Graphene is added, and in the auxiliary agent of water paint, has selected specific type as mixing slurry auxiliary agent and highly conductive stone
Black alkene is initially formed slurry, then is mixed as entirety with other compositions, finally have also combined specific auxiliary agent and it is each at
/ ratio combination, enable graphene evenly dispersed in coating, to obtain the excellent spy of various aspects of performance
The conductive water paint of kind, shows higher electric conductivity and electromagnetic shielding performance, but also has hardness height, adhesive force good, resistance to
Corrosive nature is good, other characteristics such as pollution-free, can adapt to various market-oriented demands.
The present invention also provides a kind of preparation methods of waterborne conductive coating, comprising the following steps:
1) by highly conductive graphene, mix slurry auxiliary agent and water and ground after mixing for the first time, obtain highly conductive graphene
Slurry；
2) highly conductive graphene slurry, water-base resin and the auxiliary agent obtained above-mentioned steps carries out after mixing again, stands,
Obtain waterborne conductive coating.
The present invention is and aforementioned to the selection of required raw material in above-mentioned preparation process and composition and corresponding optimum principle
The selection of corresponding raw material and composition in waterborne conductive coating, and corresponding optimum principle can be corresponded to, herein not
It repeats one by one again.
The present invention first by highly conductive graphene, mix slurry auxiliary agent and water and ground after mixing for the first time, obtain height and lead
Graphene slurry.
The design parameter of the highly conductive graphene is not particularly limited in the present invention, with well known to those skilled in the art
The parameter of conventional graphite alkenes material, those skilled in the art can according to practical situations, product requirement and
Quality requirement is selected and is adjusted, in highly conductive graphene of the present invention, the accounting of graphene of the lamella less than or equal to 5 layers
Preferably greater than or equal to 80%, more preferably higher than it is equal to 85%, is more preferably higher than equal to 90%.
The mode mixed for the first time is not particularly limited in the present invention, with hybrid mode well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The first mixing is invented to preferably include to be stirred.
The time mixed for the first time is not particularly limited in the present invention, with incorporation time well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Inventing the time mixed for the first time is preferably 15~60min, more preferably 25~50min, more preferably 35~50min.
The revolving speed mixed for the first time is not particularly limited in the present invention, with mixing revolving speed well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Inventing the revolving speed mixed for the first time is preferably 300~700r/min, more preferably 350~650r/min, more preferably 400~
600r/min, more preferably 450~550r/min.
The mode of the grinding is not particularly limited in the present invention, is with lapping mode well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright grinding preferably includes wet grinding, more preferably wet ball grinding.
The time of the grinding is not particularly limited in the present invention, is with milling time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The time of the bright grinding is preferably 20~80min, more preferably 30~70min, more preferably 40~60min.
The revolving speed of the grinding is not particularly limited in the present invention, is with grinding revolving speed well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The revolving speed of the bright grinding is preferably 200~800r/min, more preferably 300~700r/min, more preferably 400~600r/
min。
Highly conductive graphene slurry, water-base resin and the auxiliary agent that the present invention then obtains above-mentioned steps are mixed again
Afterwards, it stands, obtains waterborne conductive coating.
The present invention further increases the performance of waterborne conductive coating, improves dispersion of the highly conductive graphene in water paint
Property, optimize and complete process route, the step 2) be particularly preferred as:
21) water-base resin and auxiliary agent are obtained into mixture after mixing；
22) mixture that above-mentioned steps obtain is added in highly conductive graphene slurry after being mixed again, stands, obtains
To waterborne conductive coating；
The present invention obtains mixture first by water-base resin and auxiliary agent after mixing.
The mixed mode and parameter is not particularly limited in the present invention, with mixing well known to those skilled in the art
Mode and parameter, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, mixing of the present invention preferably includes to be stirred.
Mixture that above-mentioned steps obtain is added in highly conductive graphene slurry again by the present invention mixed again after, it is quiet
It sets, obtains waterborne conductive coating.
The mode mixed again is not particularly limited in the present invention, with hybrid mode well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The invention mixing again preferably includes to be stirred and/or ultrasonic disperse, is stirred simultaneously when more preferably ultrasonic.
The time mixed again is not particularly limited in the present invention, with incorporation time well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The invention time mixed again is preferably 15~60min, more preferably 25~50min, more preferably 35~50min.
The revolving speed mixed again is not particularly limited in the present invention, with mixing revolving speed well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The invention revolving speed mixed again is preferably 300~700r/min, more preferably 350~650r/min, more preferably 400~
600r/min, more preferably 450~550r/min.
The time of the standing is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the time of standing of the present invention is preferably 15~45min, more
Preferably 20~40min, more preferably 25~35min.
Above-mentioned steps of the present invention provide a kind of waterborne conductive coating containing highly conductive graphene, the invention
Graphene raw material is selected, the highly conductive graphene of particular step or parameter is selected, especially uses small molecule intercalation-high temperature
The process route combination of expansion-ultrasound ball milling removing, can in a mild condition quickly, prepare graphene at low cost；And it makes
Standby graphene has complete lamellar structure, is not surface modified, keeps the intrinsic feature of two-dimensional slice.The present invention is also
Further in the auxiliary agent of water paint, select specific type as mixing slurry auxiliary agent and highly conductive graphene is initially formed slurry
Body, then mixed as entirety with other compositions, finally have also combined the ratio between specific auxiliary agent and each ingredient
Combination, enables graphene evenly dispersed in coating, to obtain the conductive aqueous painting of the excellent special type of various aspects of performance
Material, shows higher electric conductivity and electromagnetic shielding performance, but also has that hardness is high, adhesive force is good, corrosion resistance and good, nothing
Other characteristics such as pollution can adapt to various market-oriented demands.
Preparation method provided by the invention is at low cost, can solve graphene mixed in aqueous coating system it is uneven easy
The disadvantage of reunion can guarantee the evenly dispersed of graphite alkenes material, have preferable tiled state, less fold；And
The coating electric conductivity and electromagnetic shielding performance of preparation are high, also have good hardness height, adhesive force, corrosion resistance and good and environment friend
The features such as good.
The experimental results showed that the waterborne conductive coating prepared by the present invention containing highly conductive graphene, resistivity are minimum 1
Ω m, hardness of paint film is in 2H, and adhesion 1 grade, the neutral salt spray time is in 600h or more.
In order to further illustrate the present invention, with reference to embodiments to a kind of system of waterborne conductive coating provided by the invention
Preparation Method is described in detail, but it is to be understood that these embodiments are to carry out under the premise of the technical scheme of the present invention in fact
It applies, the detailed implementation method and specific operation process are given, only to further illustrate the features and advantages of the present invention, and
It is not limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
Highly conductive graphene
Raw material are 1000 mesh natural graphites (Qingdao Dong Kai graphite Co., Ltd).By 10g graphite and 50g carbonic acid sodium dihydrogen
Mixing is scattered in 100g water, and mixed liquor mechanical stirring is reacted 20 hours at room temperature, is added the dilution of 400g water, is centrifuged
To intercalated graphite.Intercalated graphite is placed in 1000 DEG C of Muffle furnace, expands 30s.Graphite dispersion after 5g expansion is in 5LN- first
In base pyrrolidones, 800W ultrasound removes 8h, 300rmp ball milling 2h, is centrifuged washing and drying, obtains highly conductive graphene.
The highly conductive graphene prepared to the embodiment of the present invention 1 characterizes.
Referring to Fig. 1, Fig. 1 is the atomic force microscopy of highly conductive graphene prepared by the embodiment of the present invention 1.
It is shown by the atomic force microscopy of Fig. 1, graphene sheet layer has smooth lamellar structure, and planar dimension is in 6 μ
M or so is not surface modified, and keeps the intrinsic feature of two-dimensional slice, thus has preferable electric conductivity.
Thickness sensitivity is carried out to highly conductive graphene prepared by the embodiment of the present invention 1.
Test method: graphene sample thickness is tested to obtain by PARK NX-10 atomic force microscope.
Referring to fig. 2, the thickness that the highly conductive graphene that Fig. 2 is prepared for the embodiment of the present invention 1 is measured by atomic force microscope
Spend data and curves.
It can be obtained by the data analysis in Fig. 2, graphene thickness is in 3nm hereinafter, the number of plies is within 10 layers.
Elemental analysis is carried out to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the elemental analysis of graphene sample is tested to obtain by ELEMENTAR elemental analyser.
Referring to table 1, table 1 is the Elemental analysis data of the highly conductive graphene of preparation of the embodiment of the present invention.
Table 1
As shown in Table 1, the carbon content for the highly conductive graphene that prepared by the embodiment of the present invention 1 has reached 99.414%.
Conductivity is measured using four probe conduction rate methods of testing to the highly conductive graphene of preparation of the embodiment of the present invention.
Test method: the conductivity of graphene sample is by being pressed into the disk that diameter is 10mm for sample, by Suzhou crystalline substance
Four probe conduction rate tester of lattice is tested to obtain.
The conductivity of highly conductive graphene prepared by the embodiment of the present invention 1 has reached 51000S/m.
Embodiment 2
Weigh highly conductive graphene dry powder, the 10g deionized water, 0.1g defoaming agent, 0.1g levelling of the preparation of 1.0g embodiment 1
Agent, 0.1g wetting agent, 0.5g rheology modifier agent are tentatively uniformly mixed in specified containers；The material tentatively mixed is added
1h or so is ground in ball mill, keeps material grinding abundant.50g water-based acrylic resin is weighed, anti-flash rusting agent 0.2g, 0.5g is added
Coalescing agent, being sufficiently stirred makes to be uniformly mixed.Ground slurry and the water-based acrylic resin that specified auxiliary agent is added are mixed
It is added in specified containers afterwards, compound 1.5h or so under conditions of ultrasonic 20kHz mechanical stirring 200r/min；It then will be compound good
Water paint be stored at room temperature 30min or so, obtain composite water soluble acrylic acid conductive coating.
Referring to Fig. 3, Fig. 3 is the process flow diagram that the present invention prepares composite water soluble acrylic acid conductive coating.
The paint film of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2 is characterized.
Referring to fig. 4, Fig. 4 is the scanning electron microscope (SEM) photograph of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2.
As shown in Figure 4, graphene is uniformly mixed in aqueous coating system, is not reunited, and evenly dispersed, is had preferable
Tiled state, less fold.
Adhesive force is carried out using scratch to the paint film of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2
Detection.
It is surveyed referring to the paint film adhesion that Fig. 5, Fig. 5 are composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2
Attempt.
As shown in Figure 5, the paint film adhesion of composite water soluble acrylic acid conductive coating prepared by the present invention is 1 grade.
Shock resistance detection is carried out to the paint film of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2.
It is surveyed referring to the paint film shock resistance that Fig. 6, Fig. 6 are composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 2
Attempt.
It will be appreciated from fig. 6 that the paint film shock resistance of composite water soluble acrylic acid conductive coating prepared by the present invention is 70 or more.
Specific detection method and standard are referring to method corresponding in national standard and standard.
Referring to table 2, table 2 is the paint film property data of the composite water soluble conductive coating of preparation of the embodiment of the present invention.
Table 2
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Paint film appearance | It is flat and smooth | It is flat and smooth | It is flat and smooth |
| Water resistance | Paint film is normal | Paint film is normal | Paint film is normal |
| Adhesive force | 1 grade | 1 grade | 1 grade |
| Shock resistance cm | 70 | 70 | 50 |
| Hardness | H | H | H |
| Flexibility mm | 1 | 1 | 1 |
| Salt spray resistance 120h | Paint film is normal | Paint film is normal | Paint film is normal |
| Resistivity | 200Ω/m | 5Ω/m | 20Ω/m |
Embodiment 3
Weigh highly conductive graphene dry powder, 100g deionized water, 0.8g defoaming agent, the 0.8g stream of the preparation of 10.0g embodiment 1
Flat agent, 1.2g wetting agent, 3.5g rheology modifier agent are tentatively uniformly mixed in specified containers；The material tentatively mixed is added
Enter and grind 1h or so in ball mill, keeps material grinding abundant.Weigh 50g water-based acrylic resin, be added anti-flash rusting agent 0.8g,
2.5g coalescing agent, being sufficiently stirred makes to be uniformly mixed.By the water-based acrylic resin of ground slurry and the specified auxiliary agent of addition
It is added in specified containers after mixing, compound 2.0h or so under conditions of ultrasonic 20kHz mechanical stirring 200r/min；Then it will answer
The water paint got togather is stored at room temperature 30min or so, obtains composite water soluble acrylic acid conductive coating.
The paint film of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 3 is detected.
Specific examination criteria is referring to corresponding standard in national standard.
Referring to table 2, table 2 is the paint film property data of the composite water soluble conductive coating of preparation of the embodiment of the present invention.
Embodiment 4
The commercially available phosphorus content of 3.0g is weighed more than or equal to 98%, conductivity is more than or equal to the highly conductive graphene of 45000S/m
Dry powder, 25g deionized water, 0.2g defoaming agent, 0.3g levelling agent, 0.2g wetting agent, 1.2g rheology modifier agent are in specified containers
In tentatively be uniformly mixed；The material tentatively mixed is added in ball mill and grinds 1h or so, keeps material grinding abundant.It weighs
Anti- flash rusting agent 0.4g, 1.0g coalescing agent is added in 50g aqueous alkide resin, and being sufficiently stirred makes to be uniformly mixed.By ground slurry
Material and the water-based acrylic resin that specified auxiliary agent is added are added in specified containers after mixing, in ultrasonic 20kHz mechanical stirring 200r/
Compound 1.5h or so under conditions of min；Then compound good water paint is stored at room temperature 30min or so, obtains composite water soluble
Acrylic acid conductive coating.
The paint film of composite water soluble acrylic acid conductive coating prepared by the embodiment of the present invention 4 is detected.
Specific examination criteria is referring to corresponding standard in national standard.
Referring to table 2, table 2 is the paint film property data of the composite water soluble conductive coating of preparation of the embodiment of the present invention.
A kind of waterborne conductive coating containing highly conductive graphene provided by the invention and preparation method thereof is carried out above
Detailed introduction, used herein a specific example illustrates the principle and implementation of the invention, above implementation
The explanation of example is merely used to help understand method and its core concept of the invention, including best mode, and but also ability
Any technical staff in domain can practice the present invention, including any device or system of manufacture and use, and implement any combination
Method.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
Can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the protection scope of the claims in the present invention
It is interior.The range of the invention patent protection is defined by the claims, and may include those skilled in the art it is conceivable that its
His embodiment.If these other embodiments, which have, is not different from the structural element of claim character express, or if
They include the equivalent structural elements with the character express of claim without essence difference, then these other embodiments should also wrap
Containing within the scope of the claims.
Claims (10)
1. a kind of waterborne conductive coating, which is characterized in that including water-base resin, highly conductive graphene slurry and auxiliary agent.
2. waterborne conductive coating according to claim 1, which is characterized in that the phosphorus content of the highly conductive graphene is greater than
Equal to 98%；
The conductivity of the highly conductive graphene is more than or equal to 40000S/m.
3. waterborne conductive coating according to claim 1, which is characterized in that the highly conductive graphene slurry is led including height
Graphene mixes slurry auxiliary agent and water；
The slurry auxiliary agent of mixing includes one of defoaming agent, levelling agent, rheological modifier and wetting agent or a variety of；
The water-base resin includes water soluble acrylic acid, aqueous alkide resin, aqueous epoxy resins, aqueous polyanion resin, aqueous
One of fluorocarbon resin and aqueous superchlorinated polyvinyl chloride resin are a variety of；
The auxiliary agent includes anti-flash rusting agent and/or coalescing agent.
4. waterborne conductive coating according to claim 3, which is characterized in that by the waterborne conductive coating integrally based on,
The water-base resin is 20~80 parts by weight；
The highly conductive graphene is 1~30 parts by weight；
The slurry auxiliary agent of mixing is 0.5~8 parts by weight；
The water is 10~30 parts by weight；
The auxiliary agent is 0.5~4 parts by weight.
5. waterborne conductive coating according to claim 3, which is characterized in that by the waterborne conductive coating integrally based on,
The defoaming agent is 0.1~2 parts by weight；
The levelling agent is 0.1~2.5 parts by weight；
The rheology modifier is 0.1~2.5 parts by weight；
The wetting agent is 0.1~2 parts by weight；
The anti-flash rusting agent is 0.5~3.5 parts by weight；
The coalescing agent is 0.2~2 parts by weight.
6. waterborne conductive coating according to claim 1, which is characterized in that the defoaming agent include tego902w,
Tego901, BYK-24, tego1488 and KOOLY-3150's is one or more；
The levelling agent includes the one or more of silok8244, silok315, silok23, silok8066 and silok333；
The rheology modifier includes the one or more of RM-8W, RM-2020n and RM-12w；
The wetting agent includes one kind or more of tego twin 4100, Surfynol 104A, silok8030 and silok8008
Kind；
The anti-flash rusting agent includes the one or more of sodium nitrite in aqueous solution, NALZIN FA 179, CH07A and R-760F；
The coalescing agent includes the one or more of texanol, DPnB, DPnP, TPnB and DPM.
7. a kind of preparation method of waterborne conductive coating, which comprises the following steps:
1) by highly conductive graphene, mix slurry auxiliary agent and water and ground after mixing for the first time, obtain highly conductive graphene slurry；
2) highly conductive graphene slurry, water-base resin and the auxiliary agent obtained above-mentioned steps carries out after mixing again, stands, obtains
Waterborne conductive coating.
8. preparation method according to claim 7, which is characterized in that after the highly conductive graphene is prepared by following methods
It obtains:
A after) being reacted graphite and small molecule intercalator, intercalated graphite is obtained；
B) intercalated graphite for obtaining above-mentioned steps obtains expanded graphite after high-temperature expansion；
C) expanded graphite for obtaining above-mentioned steps is removed in stripping media, obtains graphene.
9. preparation method according to claim 8, which is characterized in that the mass ratio of the graphite and small molecule intercalator is
1:(1~5)；
The mass ratio of the graphite and the stripping media is 1:(50~300)；
The time of the reaction is 10~30 hours；The temperature of the reaction is 0~40 DEG C；
The mode of the removing includes one of ultrasound removing, sand milling removing, ball milling removing and shearing removing or a variety of.
10. preparation method according to claim 7, which is characterized in that the step 2) specifically:
21) water-base resin and auxiliary agent are obtained into mixture after mixing；
22) mixture that above-mentioned steps obtain is added in highly conductive graphene slurry after being mixed again, stands, obtains water
Property conductive coating；
The time mixed again is 15~60min；The revolving speed of mixing again is 300~700r/min；
The time of the standing is 15~45min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128913A (en) * | 2019-05-27 | 2019-08-16 | 长沙如洋环保科技有限公司 | A kind of painting dressing automobiles paint |
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| CN115298273A (en) * | 2020-01-03 | 2022-11-04 | 纳米技术能源公司 | Electromagnetic interference shielding material, device and method for manufacturing the same |
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