CN105802441A - Water-borne graphene composite coating, and water-borne graphene composite paint and preparation method thereof - Google Patents
Water-borne graphene composite coating, and water-borne graphene composite paint and preparation method thereof Download PDFInfo
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- CN105802441A CN105802441A CN201410841675.9A CN201410841675A CN105802441A CN 105802441 A CN105802441 A CN 105802441A CN 201410841675 A CN201410841675 A CN 201410841675A CN 105802441 A CN105802441 A CN 105802441A
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- watersoluble plumbago
- alkene composite
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Abstract
The invention provides a water-borne graphene composite paint. The water-borne graphene composite paint is composed of water-based resin, graphene, an aniline oligomer derivative, water and a paint additive, wherein the graphene accounts for 0.01 to 4% of the mass of the water-borne graphene composite paint and is uniformly dispersed in the water-based resin by forming phi-phi bonds with the aniline oligomer derivative. The invention also provides a preparation method for the water-borne graphene composite paint and a water-borne graphene composite coating.
Description
Technical field
The present invention relates to a kind of anticorrosive paint and corrosion-inhibiting coating, particularly relate to a kind of based on Graphene
Watersoluble plumbago alkene composite coating, watersoluble plumbago alkene composite coating and preparation method thereof.
Background technology
Anticorrosive paint, refers to play metal etc. the paint of etch-proof effect.The most several
Year, country was always in the ocean increasing dynamics of investment to the earth 7/10ths, and anticorrosive paint becomes
The important fresh combatants of paint field, anticorrosive paint plays increasing effect, before development
Scape is considerable.
Water paint refers to the water solvent as coating.In use, coating is with micel aggressiveness
Being dispersed in water, rely on micel aggressiveness mutually to draw close, interfacial molecular permeates, micel aggressiveness
Merge, after water volatilizees, ultimately form coating.Water paint owing to not using organic solvent, and
To adopt to use water as solvent, thus relatively environmental protection and favored by masses.
But, water paint is hardly formed the membrane structure of homogeneity, compact structure, thus makes
The about performance of water paint.Meanwhile, in film forming procedure, owing to the residual of hydrophilic group is made
Becoming coating hydrophilic to improve, reduce steam diffusion barrier ability, coating moisture-resisting cementitiousness drops
Low.In addition, water-base resin is difficult to the infiltration of the height to filler and granules of pigments and divides
Dissipate, cause its high-quality anticorrosive paint of difficult formation.
Summary of the invention
For the deficiencies in the prior art, present invention is primarily targeted at a kind of watersoluble plumbago of offer
Alkene composite coating, watersoluble plumbago alkene composite coating and preparation method thereof, described watersoluble plumbago alkene is multiple
Close graphene uniform in coating to be scattered in water-base resin, made watersoluble plumbago alkene composite coating with
Metallic matrix adhesion is big, organic volatile discharge is low, and obtained watersoluble plumbago alkene is compound to be coated with
Layer has good moisture penetration and salt fog resistance and stronger protective capacities, can be as weight
Anticorrosive paint is applied in the relatively harsh corrosive environment such as boats and ships, bridge.
The present invention provides a kind of watersoluble plumbago alkene composite coating, its by water-base resin, Graphene,
Oligomer of phenylamine derivant, water and coating additive composition, institute in watersoluble plumbago alkene composite coating
Stating the mass percent shared by Graphene is 0.01%～4%, and this Graphene is by oligomeric with aniline
Thing derivant forms pi-pi bond and is dispersed in water.
Wherein, described oligomer of phenylamine derivant is 1:10～10:1 with the mass ratio of Graphene.
Wherein, a diameter of 5 μm of described Graphene～50 μm.
Wherein, described oligomer of phenylamine derivant is the oligomer of phenylamine with functional group, described
Functional group includes carboxyl, alkyl, sulfonic group, phosphate, epoxide group, polyethylene group
And/or polyvinyl alcohol group, described oligomer of phenylamine be aniline trimer, Tetraaniline,
One in aniline pentamer, aniline six aggressiveness or combination.
Wherein, described water-base resin be aqueous epoxy resins, water-borne acrylic resin, aqueous gather
One in urethane resin, aqueous acrylic urethane resins and water-compatible amino resin or combination.
Wherein, described coating additive includes anti-settling agent, defoamer and levelling agent, described anti-settling agent
For the one in aerosil, polyamide wax and organobentonite or combination, described froth breaking
Agent be dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, little point
One in sub-metallorganic and silicon modified organic polymer or combination, described levelling agent is second
Glycol butyl ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, poly-two
One in methyl-monosilane, PSI and modified organic silicon compound or combination.
The present invention also provides for the preparation method of a kind of watersoluble plumbago alkene composite coating, and it includes following
Step: by the oligomer of phenylamine derivant of equimolar amounts and alkali dissolution in water, obtain mixture A；
In described mixture A, add Graphene, make oligomer of phenylamine derivant mix with Graphene
Uniformly and form pi-pi bond between oligomer of phenylamine derivant and Graphene and obtain graphene dispersion
Liquid；One water-base resin is provided, in described water-base resin, adds described graphene dispersing solution and mix
Close uniformly, obtain mixture B；In described mixture B, add coating additive, obtain aqueous
Graphene composite coating, wherein, Graphene institute described in described watersoluble plumbago alkene composite coating
The mass percent accounted for is 0.01%～4%.
Wherein, the one during described alkali is sodium hydroxide, triethylamine, potassium hydroxide and ammonia.
The present invention also provides for a kind of watersoluble plumbago alkene composite coating, its by water-base resin, Graphene,
Oligomer of phenylamine derivant and coating additive composition, stone described in watersoluble plumbago alkene composite coating
Ink mass percent shared by alkene is 0.01%～4%, and this Graphene is by spreading out with oligomer of phenylamine
Biology forms pi-pi bond and is dispersed in described water-base resin.
Wherein, mass percent shared by water-base resin described in watersoluble plumbago alkene composite coating
Being 80%～95%, the mass percent shared by described oligomer of phenylamine derivant is
0.01%～5%, the mass percent shared by described coating additive is 1%～10%.
Compared to prior art, in the watersoluble plumbago alkene composite coating that the present invention provides, by right
The surface of Graphene, through the modifying and decorating of oligomer of phenylamine derivant, greatly improves Graphene
Dispersibility and chemical stability so that described graphene uniform is scattered in described water-base resin
In, and Graphene has good hydrophobic performance, therefore in application process, can effectively suppress water
Molecule is in the surface adsorption of the watersoluble plumbago alkene composite coating formed.Meanwhile, Graphene has two
Dimension lamellar structure, it is dispersed in coating, after forming watersoluble plumbago alkene composite coating,
Graphene can be layering, the isolation layer that formation is fine and close, thus little molecule corrosive medium (moisture
Son, chloride ion etc.) it is difficult to by this layer of fine and close isolation layer, serve prominent physical isolation
Effect.That is, obtained watersoluble plumbago alkene composite coating has good resistant to water penetration and resistance to
Salt fog and stronger protective capacities, thus watersoluble plumbago alkene composite coating has the anti-of excellence
Rotten effect.Further, described watersoluble plumbago alkene composite coating does not contains organic solvent, will not bring
Machine evaporative emissions, environmental protection.The preparation of the watersoluble plumbago alkene composite coating that the present invention provides
Method, is innovated by preparation technology, can obtain the water with preferable dispersibility and chemical stability
Property Graphene composite coating, preparation technology is simple, with low cost, beneficially industrialization.
Accompanying drawing explanation
Fig. 1 is that graphene dispersing solution (right) and undressed Graphene described in embodiment 1 are through water
The photo of (left) after dispersion.
Fig. 2 is the transmission electron microscope photo of graphene dispersing solution described in embodiment 1.
The surface that Fig. 3 a is comparative example 1 aqueous epoxy resins coating after salt mist experiment 500 hours
Pattern photo.
Fig. 3 b is that the watersoluble plumbago alkene composite coating of embodiment 1 gained was through salt mist experiment 500 hours
After surface topography photo.
Fig. 4 is watersoluble plumbago alkene composite coating (corresponding b curve) and the contrast of embodiment 1 gained
Example 1 aqueous epoxy resins coating (corresponding a curve) is soaked 48 hours in 3.5wt%NaCl solution
After corrosion potential curve.
It is little that Fig. 5 a is that comparative example 1 aqueous epoxy resins coating soaks 48 in 3.5wt%NaCl solution
The impedance complex plane figure of the ac impedance spectroscopy time in.
It is little that Fig. 5 b is that comparative example 1 aqueous epoxy resins coating soaks 48 in 3.5wt%NaCl solution
The Bode diagram of the ac impedance spectroscopy time in.
Fig. 5 c is that the watersoluble plumbago alkene composite coating of embodiment 1 gained is in 3.5wt%NaCl solution
Soak the impedance complex plane figure of 48 hours interior ac impedance spectroscopies.
Fig. 5 d is that the watersoluble plumbago alkene composite coating of embodiment 1 gained is in 3.5wt%NaCl solution
Soak the Bode diagram of 48 hours interior ac impedance spectroscopies.
Fig. 6 is watersoluble plumbago alkene composite coating (corresponding solid line) and the comparative example of embodiment 1 gained
In 1 aqueous epoxy resins coating (respective dashed) is soaked 48 hours in 3.5wt%NaCl solution
Polarization curve.
Fig. 7 is watersoluble plumbago alkene composite coating (corresponding b curve) and the contrast of embodiment 1 gained
Example 1 aqueous epoxy resins coating (corresponding a curve) is soaked 48 hours in 3.5wt%NaCl solution
Interior lgQc-t1/2Curve and equation of linear regression (wherein, QcFor the electric capacity of coating, t is test
Time).
Fig. 8 a is the contact angle photo on the surface of comparative example 1 aqueous epoxy resins coating.
Fig. 8 b is that the contact angle on the surface of the watersoluble plumbago alkene composite coating of embodiment 1 gained shines
Sheet.
Detailed description of the invention
The watersoluble plumbago alkene composite coating that the present invention provided below with reference to accompanying drawing, watersoluble plumbago
Alkene composite coating and preparation method thereof is described further.
The embodiment of the present invention provides the preparation method of a kind of watersoluble plumbago alkene composite coating.The method
Comprise the steps:
Operation (1): by the oligomer of phenylamine derivant of equimolar amounts and alkali dissolution in water, obtain
Mixture A.The purpose adding alkali is to enable oligomer of phenylamine derivant to be preferably dissolved in
Water.Add equimolar amounts be make in oligomer of phenylamine derivant structure with carboxylic acid, or other
The group of acid can neutralize completely with alkali.Described alkali is sodium hydroxide, triethylamine, potassium hydroxide
With the one in ammonia.
Oligomer of phenylamine derivant and alkali are dispersed in water, make oligomer of phenylamine derivant abundant
Dissolve.Described oligomer of phenylamine derivant is for Graphene described in modification.Described aniline is low
Polymers derivant is the oligomer of phenylamine with functional group, described functional group include carboxyl, alkyl,
Sulfonic group, phosphate, epoxide group, polyethylene group and/or polyvinyl alcohol group.Excellent
Selection of land, described oligomer of phenylamine is aniline trimer, Tetraaniline, aniline pentamer, benzene
One in amine six aggressiveness or combination.
Described oligomer of phenylamine or derivatives thereof can have a following structural formula:
(M is mainly sodium ion, potassium ion, quaternary ammonium salt etc.).
Operation (2): add Graphene in described mixture A, makes oligomer of phenylamine derive
Thing is mixed homogeneously with Graphene and forms pi-pi bond between oligomer of phenylamine derivant and Graphene
Obtain graphene dispersing solution.Concrete, due to the phenyl ring in described oligomer of phenylamine derivant and
Graphene-structured is close, thus described oligomer of phenylamine derivant can and Graphene between formed
Pi-pi bond and realize mixing with graphene uniform.It is pointed out that and utilize oligomer of phenylamine to spread out
Forming pi-pi bond between biology and Graphene, this mode is different from grafting modification, and it is also
Do not destroy the structure of Graphene itself, also different from the macromolecule of physical property coated graphite alkene, its
Do not sacrifice the performance of Graphene.It is to say, it is modified by oligomer of phenylamine Derivatives Modified
Graphene, its dispersibility only making Graphene and stability are more preferable, and do not destroy Graphene
Structure, does not the most reduce the original performance of Graphene.
It is appreciated that and can pass through high-speed stirred, ultrasonic, ball milling and/or the process for dispersing of sand milling
Make graphene uniform disperse, make Graphene mix homogeneously with oligomer of phenylamine derivant further.
Described Graphene include graphene nanometer sheet, Graphene micron film, graphene nanobelt,
Few layer graphene (2-5 layer), multi-layer graphene (2-9 layer), graphene quantum dot and this
The derivant of a little graphite alkenes materials).The definition of described grapheme material can be found in document " All
in the graphene family–A recommended nomenclature for
two-dimensional carbon materials”.Described grapheme material is also selected from thickness
≤ 20nm, it is highly preferred that the material of thickness≤10nm.In the present embodiment, this Graphene
The thickness of material preferably≤3nm, grapheme material is the thinnest, and pliability is the best, is more easily worked.
Described grapheme material preparation method do not limit, use graphite well known to those skilled in the art
Prepared by alkene product or the preparation method by routine.The preferred Ningbo of grapheme material of the present invention
The graphene product that Mo Xi Science and Technology Ltd. provides.Grapheme material can be selected from chemical oxidation
Any one method system in method such as Brodie method, Hummers method or Staudenmaier method
The grapheme material that standby graphene oxide prepares through thermal expansion.Can also select mechanical stripping,
The grapheme material that liquid phase is peeled off or prepared by electrochemical stripping.Described Graphene a diameter of
5 μm～50 μm.
Described oligomer of phenylamine derivant is 1:10～10:1 with the mass ratio of Graphene.Preferably,
Described oligomer of phenylamine derivant is 2:1～1:1 with the mass ratio of Graphene.
Operation (3): provide a water-base resin, adds described Graphene in described water-base resin
Dispersion liquid mix homogeneously, obtain mixture B.Can pass through high-speed stirred, ultrasonic, ball milling and
/ or the process for dispersing of sand milling make graphene dispersing solution be dispersed in water-base resin, further
Graphene uniform is made to be scattered in water-base resin.Described water-base resin is aqueous epoxy resins, water
Property acrylic resin, waterborne polyurethane resin, aqueous acrylic urethane resins and aqueous amino
One in resin or combination.
Operation (4): add coating additive in described mixture B, obtain watersoluble plumbago alkene
Composite coating.Described coating additive includes anti-settling agent, defoamer and levelling agent.Described anti-settling agent
For the one in aerosil, polyamide wax and organobentonite or combination.Described froth breaking
Agent be dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, little point
One in sub-metallorganic and silicon modified organic polymer or combination.Described levelling agent is second
Glycol butyl ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, poly-two
One in methyl-monosilane, PSI and modified organic silicon compound or combination.
It is appreciated that described watersoluble plumbago alkene composite coating may also include firming agent.Described firming agent can
For aqueous polyamide, it is used for accelerating described watersoluble plumbago alkene composite coating solidification process.
Described in the watersoluble plumbago alkene composite coating obtained, the mass percent shared by Graphene is
0.01%～4%, it is preferably, 0.2%～1.0%.
The present invention also provides for a kind of watersoluble plumbago alkene composite coating using said method to prepare.Should
Watersoluble plumbago alkene composite coating by water-base resin, Graphene, oligomer of phenylamine derivant, water and
Coating additive forms.Percent mass shared by Graphene described in watersoluble plumbago alkene composite coating
Number is 0.01%～4%.Preferably, Graphene described in described watersoluble plumbago alkene composite coating
Shared mass percent is 0.2%～1.0%.This Graphene by with oligomer of phenylamine derivant
Form pi-pi bond and be dispersed in described water-base resin.
The present invention also provide for a kind of use prepared by above-mentioned watersoluble plumbago alkene composite coating obtain
Watersoluble plumbago alkene composite coating.Concrete, by above-mentioned watersoluble plumbago alkene composite coating by blade coating,
The means such as roller coat are coated on matrix, after the water in described watersoluble plumbago alkene composite coating volatilizees
And form watersoluble plumbago alkene composite coating.Described watersoluble plumbago alkene composite coating by water-base resin,
Graphene, oligomer of phenylamine derivant and coating additive composition.At watersoluble plumbago alkene composite coating
Described in mass percent shared by Graphene be 0.01%～4%.This Graphene by with aniline
Oligomer derivative forms pi-pi bond and is dispersed in described water-base resin.At watersoluble plumbago
Described in alkene composite coating, the mass percent shared by water-base resin is 80%～95%, described benzene
Mass percent shared by amine oligomer derivant is 0.01%～5%, shared by described coating additive
Mass percent be 1%～10%.
In the watersoluble plumbago alkene composite coating that the present invention provides, by the surface of Graphene is passed through
The modifying and decorating of oligomer of phenylamine derivant, the dispersibility and the chemistry that greatly improve Graphene are steady
Qualitative so that described graphene uniform is scattered in described water-base resin, and Graphene has good
Good hydrophobic performance, therefore in application process, can effectively suppress hydrone at the aqueous stone formed
The surface adsorption of ink alkene composite coating.Meanwhile, Graphene has two-dimensional slice structure, and it is being coated with
In material dispersed, when being formed after watersoluble plumbago alkene composite coating, Graphene can be layering,
Form fine and close isolation layer, thus little molecule corrosive medium (hydrone, chloride ion etc.) is difficult to logical
Cross this layer of fine and close isolation layer, serve prominent physical isolation effect.That is, obtained water
Property Graphene composite coating there is good resistant to water penetration and salt fog resistance and stronger anti-
Protect ability, thus watersoluble plumbago alkene composite coating has the antiseptic effect of excellence.Further, described
Watersoluble plumbago alkene composite coating does not contains organic solvent, and organic volatile will not be brought to discharge, green
Environmental protection.The preparation method of the watersoluble plumbago alkene composite coating that the present invention provides, passes through preparation technology
Innovation, can obtain the watersoluble plumbago alkene composite coating with preferable dispersibility and chemical stability,
Preparation technology is simple, with low cost, beneficially industrialization.
For further describing the present invention, it is described watersoluble plumbago alkene composite coating, aqueous stone below
The preparation method of ink alkene composite coating, the specific embodiment under different parameters:
Embodiment 1:
Weigh aniline trimer 1.24g to be dissolved in 50ml THF, add 1.04g fourth two
Anhydride, reacts 3 hours, with petroleum ether precipitation, obtains aniline trimer carboxy derivatives.
Weigh 2.0g aniline trimer carboxy derivatives and 0.33g NaOH solid is dissolved in 10mL
In water, obtain mixture A.2g Graphene is added (purchased from Ningbo in described mixture A
Mo Xi Science and Technology Ltd.), ultrasonic disperse 1 hour, obtain graphene dispersing solution.Graphene
After aniline trimer carboxy derivatives is modified, the content in water reaches 0.2g/mL.Described
Graphene dispersing solution and undressed Graphene contrast effect after water-dispersible are shown in Fig. 1.Institute
The electronic transmission electromicroscopic photograph stating graphene dispersing solution is shown in Fig. 2.From Fig. 1 and Fig. 2, stone
Ink alkene can be dispersed in water after aniline trimer carboxy derivatives is modified, described graphite
Graphene structure in the form of sheets in alkene dispersion liquid.
It is added to described graphene dispersing solution in 45g aqueous epoxy resins (collect purchased from northwest Yongxin
Company limited of group), and mix homogeneously, obtain mixture B.In described mixture B successively
Add 1g levelling agent, 2g defoamer, 2.67g anti-settling agent and 45g aqueous polyamide firming agent,
Stir, i.e. obtain watersoluble plumbago alkene composite coating.
The watersoluble plumbago alkene composite coating obtained is coated on a plain steel, treats that water volatilizees
After, obtain watersoluble plumbago alkene composite coating.
For contrast experiment's effect, also it is prepared for comparative example 1 aqueous epoxy resins coating.Contrast
Described in example 1, the preparation method of aqueous epoxy resins coating is with embodiment 1, except for the difference that, does not has
There is addition graphene dispersing solution.
Water-base epoxy tree to watersoluble plumbago alkene composite coating and comparative example 1 described in embodiment 1
Fat coating carries out the test of salt spray resistance.Concrete, by described watersoluble plumbago alkene composite coating
It is respectively placed in salt spray test chamber with comparative example 1 aqueous epoxy resins coating, takes after 500 hours
Go out, and carry out take pictures (see Fig. 3 a and Fig. 3 b) after being dried at room temperature for.By Fig. 3 a and Fig. 3 b
Visible, the surface of aqueous epoxy resins coating has obvious etch pit to occur, and watersoluble plumbago alkene
The surface of composite coating does not has obvious corrosion phenomenon to occur.
Water-base epoxy tree to watersoluble plumbago alkene composite coating and comparative example 1 described in embodiment 1
Fat coating carries out the test of antiseptic property.Concrete, by described watersoluble plumbago alkene composite coating with
The aqueous epoxy resins coating of comparative example 1 is respectively at 3.5wt%NaCl solution (with simulated seawater)
Middle immersion 8 days, then uses Shanghai China in morning CHI660E electrochemical workstation, with electricity of opening a way
It is multiple to watersoluble plumbago alkene that position, AC impedance and dynamic potential polarization curve measuring technology analyze Graphene
Close the mechanism of action of coating.Concrete, with the saturated calomel electrode with Luggin capillary for ginseng
Ratio electrode, platinum plate electrode is to electrode, and Graphene coating/carbon steel electrode is working electrode,
Simulated seawater solution soaks after making OCP (OCP) stable, disturb with sine wave under OCP
Dynamic amplitude 30mV, frequency range is that 100000Hz～0.01Hz carries out electrical impedance (EIS) and sweeps
Retouch.The scanning speed of polarization curve is 0.5mV/s, and sweep limits is-200～200mV
vs.OCP.Test OCP result is shown in that Fig. 4, results of AC impedance are shown in Fig. 5 a to Fig. 5 d, polarization
Dependence Results is shown in Fig. 6.From Fig. 4, Fig. 5 a to Fig. 5 d, Fig. 6, described watersoluble plumbago
Alkene composite coating is bigger than the impedance of epoxy coating；After soaking 48 hours, watersoluble plumbago
The corrosion current density of alkene composite coating is 130nA cm-2, and aqueous epoxy resins coating
Corrosion current density be 38nA cm-2.This explanation is through oligomer of phenylamine derivant
The Graphene of modifying and decorating can be dispersed in water-base resin, thus the watersoluble plumbago alkene obtained
The OCP of composite coating is shuffled, and impedance increases, and corrosion current density reduces, Jin Er great
Improve greatly the antiseptic property of watersoluble plumbago alkene composite coating.
To watersoluble plumbago alkene composite coating described in embodiment 1 and comparative example 1 aqueous epoxy resins
Coating carries out the test of resistant to water penetration performance.Concrete, by AC impedance is fitted,
With lgQc(Qc is coating capacitor) is to t1/2Mapping, obtains Fig. 7.By linear fit, permissible
Respectively obtain aqueous epoxy resins coating and the equation of linear regression of watersoluble plumbago alkene composite coating,
And then it is calculated aqueous epoxy resins coating and the diffusion coefficient of watersoluble plumbago alkene composite coating
It is respectively 5.56 × 10-9cm2/ h and 1.61 × 10-11cm2/h.This explanation is through oligomer of phenylamine
The Graphene of the modifying and decorating of derivant can be dispersed in water-base resin, thus slow down water
Molecule diffusion velocity in watersoluble plumbago alkene composite coating.
To watersoluble plumbago alkene composite coating described in embodiment 1 and comparative example 1 aqueous epoxy resins
Coating carries out the test (see Fig. 8) of contact angle.Result is: described watersoluble plumbago alkene is compound to be coated with
The contact angle of layer is 95.38 °；The contact angle of described aqueous epoxy resins coating is 87.32 °.This
Illustrate that the Graphene of the modifying and decorating through oligomer of phenylamine derivant can be dispersed in aqueous
In resin, so that the contact angle of described aqueous epoxy resins coating increases, and then add institute
State the hydrophobic performance of aqueous epoxy resins coating.
Embodiment 2:
Weigh the made aniline trimer carboxy derivatives of 1.5g embodiment and 0.33g NaOH is solid
Body is dissolved in 10mL water, obtains mixture A.1.5g stone is added in described mixture A
Ink alkene, ultrasonic disperse 1 hour, obtain graphene dispersing solution.Graphene is through aniline trimer carboxylic
After radical derivative modification, the content in water reaches 0.15g/mL.
Described graphene dispersing solution is added in 92g waterborne polyurethane resin (purchased from northwest Yongxin
Group Co., Ltd), and mix homogeneously, obtain mixture B.Depend in described mixture B
Secondary addition 1.67g levelling agent, 1g defoamer, 2g anti-settling agent, stir, i.e. obtain water
Property Graphene composite coating.
Embodiment 3:
Weigh the made aniline trimer carboxy derivatives of 2g embodiment 1 and 0.33g NaOH is solid
Body is dissolved in 10mL water, obtains mixture A.2g graphite is added in described mixture A
Alkene, ultrasonic disperse 1 hour, obtain graphene dispersing solution.Graphene is through aniline trimer carboxyl
After Derivatives Modified, the content in water reaches 0.2g/mL.
Described graphene dispersing solution is added in 91g water-borne acrylic resin (purchased from Weifang, Shandong
Fuller new material company limited), and mix homogeneously, obtain mixture B.To described mixture B
In be sequentially added into 1.67g levelling agent, 2g defoamer, 2g anti-settling agent, stir, i.e. arrive
Watersoluble plumbago alkene composite coating.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.Multiple amendment to these embodiments
It is apparent from for those skilled in the art, as defined herein the most former
Reason can realize the most in other embodiments.
Therefore, the present invention is not intended to be limited to the embodiments shown herein, and be to fit to
Principles disclosed herein and the consistent the widest scope of features of novelty.
Claims (10)
1. a watersoluble plumbago alkene composite coating, it is characterised in that its by water-base resin, Graphene,
Oligomer of phenylamine derivant, water and coating additive composition, institute in watersoluble plumbago alkene composite coating
Stating the mass percent shared by Graphene is 0.01%～4%, and this Graphene is by oligomeric with aniline
Thing derivant forms pi-pi bond and is dispersed in water.
Watersoluble plumbago alkene composite coating the most according to claim 1, it is characterised in that described benzene
Amine oligomer derivant is 1:10～10:1 with the mass ratio of Graphene.
Watersoluble plumbago alkene composite coating the most according to claim 1, it is characterised in that described stone
A diameter of 5 μm of ink alkene～50 μm.
Watersoluble plumbago alkene composite coating the most according to claim 1, it is characterised in that described benzene
Amine oligomer derivant is the oligomer of phenylamine with functional group, described functional group include carboxyl,
Alkyl, sulfonic group, phosphate, epoxide group, polyethylene group and/or PVA-based
Group, described oligomer of phenylamine is aniline trimer, Tetraaniline, aniline pentamer, aniline
One in six aggressiveness or combination.
Watersoluble plumbago alkene composite coating the most according to claim 1, it is characterised in that described water
Property resin is aqueous epoxy resins, water-borne acrylic resin, waterborne polyurethane resin, aqueous third
One in olefin(e) acid polyurethane resin and water-compatible amino resin or combination.
Watersoluble plumbago alkene composite coating the most according to claim 1, it is characterised in that described painting
Material auxiliary agent include anti-settling agent, defoamer and levelling agent, described anti-settling agent be aerosil,
One in polyamide wax and organobentonite or combination, described defoamer be dimethicone,
Ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, little molecular metal Organic substance and change
Property organosilicon polymer in one or combination, described levelling agent is that butyl glycol ether, vinegar fourth are fine
Dimension element, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane, poly-methyl
One in phenyl siloxane and modified organic silicon compound or combination.
7. a preparation method for watersoluble plumbago alkene composite coating, it comprises the following steps:
By the oligomer of phenylamine derivant of equimolar amounts and alkali dissolution in water, obtain mixture A；
In described mixture A, add Graphene, make oligomer of phenylamine derivant and Graphene
Mix homogeneously and between oligomer of phenylamine derivant and Graphene formed pi-pi bond obtain Graphene
Dispersion liquid；
One water-base resin is provided, in described water-base resin, adds described graphene dispersing solution and mix
Close uniformly, obtain mixture B；
In described mixture B, add coating additive, obtain watersoluble plumbago alkene composite coating,
Wherein, percent mass shared by Graphene described in described watersoluble plumbago alkene composite coating
Number is 0.01%～4%.
The most according to claim 7, the preparation method of watersoluble plumbago alkene composite coating, its feature exists
In, described alkali is the one in sodium hydroxide, triethylamine, potassium hydroxide and ammonia.
9. a watersoluble plumbago alkene composite coating, it is characterised in that its by water-base resin, Graphene,
Oligomer of phenylamine derivant and coating additive composition, stone described in watersoluble plumbago alkene composite coating
Ink mass percent shared by alkene is 0.01%～4%, and this Graphene is by spreading out with oligomer of phenylamine
Biology forms pi-pi bond and is dispersed in described water-base resin.
Watersoluble plumbago alkene composite coating the most according to claim 9, it is characterised in that in aqueous
Described in Graphene composite coating, the mass percent shared by water-base resin is 80%～95%, institute
Stating the mass percent shared by oligomer of phenylamine derivant is 0.01%～5%, described coating additive
Shared mass percent is 1%～10%.
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| CN201410841675.9A CN105802441B (en) | 2014-12-30 | 2014-12-30 | A kind of watersoluble plumbago alkene composite coating, watersoluble plumbago alkene composite coating and preparation method thereof |
| EP15865917.7A EP3228592A4 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| PCT/CN2015/095742 WO2016086796A1 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| TW104139658A TWI602611B (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and its application |
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