CN106995643A - A kind of water paint of graphene-containing/zinc-aluminum gavite nano-complex and preparation method thereof - Google Patents
A kind of water paint of graphene-containing/zinc-aluminum gavite nano-complex and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses water paint of a kind of graphene-containing/zinc-aluminum gavite nano-complex and preparation method thereof.The water paint has following composition and matched：The mass parts of water-base resin 30~50；The mass parts of water 25~40；The mass parts of dispersant 0.1~0.5；The mass parts of wetting agent 0.1~0.5；The mass parts of defoamer 0.1~0.5；The mass parts of thickener 0.1~0.5；The mass parts of coalescents 0.1~0.5；The mass parts of curing agent 0~10；The mass parts of titanium dioxide 0~25；The mass parts of calcium carbonate 0~20；Graphene/the mass parts of zinc-aluminum gavite nano-complex 0.1~2.5.Graphene/zinc-aluminum gavite nano-complex is added in water paint by the present invention, is markedly improved the high temperature resistant of water paint, anticorrosion, anti-flammability, weatherability, impact resistance, wearability, hardness, barrier, improves the multi-efficiency of water paint.
Description
Technical field
It is to be related to a kind of graphene-containing/zinc-aluminum gavite specifically the present invention relates to a kind of coating and preparation method thereof
Water paint of nano-complex and preparation method thereof, belongs to technical field of coatings.
Background technology
Coating plays more and more important effect in people live, and has become modern social development indispensable
A kind of material.Poisonous and hazardous organic matter is greatly used in current coating as molten in coating configuration process
Have a large amount of VOC during agent and auxiliary agent, use to get into the air, the harm to environment is quite big.And as global environment is asked
Topic is increasingly protruded, and various countries' environmental regulation becomes tight, and consumer's environmental consciousness is improved, and paint industry also faces environmental protection problem
Test, Environmentally friendly coatings turn into the study hotspot of coating industry.
Water paint be it is a kind of be free of or the coating containing a small amount of solvent, with its energy-saving and environmental protection, the advantage of low stain, at present
The direction given priority to as Environmentally friendly coatings product, according to relevant data display, current water paint already takes up industry
30% or so of coating total amount.But also there is the defects such as coating variety is single, performance is dull, it is necessary to right in current powdery paints
Coating is modified to develop the Functional Powder Coating with a variety of functions.
A kind of new material for the individual layer laminated structure being made up of carbon atom of graphene, with specific surface area height, conductive performance
Quickly, high temperature resistant, anticorrosion, the performance such as antistatic effect is strong, chemical stability is excellent, are added to painting by graphene at present
To improve the relevant report of coating property in material, " the leading of being modified of a kind of graphenes of CN201510208892.9 for example, Chinese patent
The graphene that mass percent is 20~35% is added in hot coating " in coating, to improve the thermal conductivity and rub resistance of coating
Property.The graphitiferous alkenes coating mainly solvent based coating reported at present, environmental pollution is larger, because graphene is in the aqueous solution
Middle bad dispersibility, easily reunites, and the poor compatibility with matrix in water paint, stability is poor, for example Chinese patent
A kind of water is disclosed in " a kind of graphene heat conduction anticorrosion water-soluble coating of CN201610816676.7 and its preparation and application "
Property coating, mixed by components I and compositionⅱ, the weight ratio of components I and compositionⅱ is 100：58~65, components I is water-soluble
Property amine, auxiliary agent, the mixture of graphene dispersing solution and filler, 1；Compositionⅱ is bisphenol A epoxide resin emulsion.Though the water paint
So increased due to the addition anticorrosive property of graphene, but not only preparation method is complex, and product stability compared with
Difference, the coating prepared must be timely used within 6 hours, have a strong impact on its application.
In order to improve application of the graphene in water paint, it is necessary to be modified to it.Hydrotalcite-based compound
(LDHs) be novel inorganic functional material that a class has unique layer structure, with excellent lamella barrier, heat endurance,
The performances such as memory effect, fire resistance.In paint field, it has in the functional paint such as fire-retardant, anti-corrosion and high intensity
There is very big application prospect.Have at present and graphene has been modified using hydrotalcite-based compound, obtained graphene/neatly
The relevant report of stone class compound." a kind of 201410649883.9 hydrotalcites load Graphene fire retardants and its should Chinese patent
With " in by coprecipitation prepare hydrotalcite load Graphene fire retardant, but in the fire retardant be only hydrotalcite is loaded
With the surface of graphene, the modification to graphene is poor, although obtained fire retardant can be improved to height to a certain extent
The flame retardant effect of molecular material, but improve limited, and the corrosion resistance that can improve coating is not explained in detail, pass through
Cross research to find, the hydrotalcite loads Graphene fire retardant and improves also very limited to the corrosion resistance of coating, it is impossible to meet actual
Application demand, in addition, using hydrazine hydrate for reducing agent in the preparation process of the fire retardant, hydrazine hydrate is extremely toxic substance, with cause
It is carcinous, and meeting self-firing and self-explosion when being contacted with oxidant, not only pollute environment and health hazard can be caused to human body.Chinese patent
One kind graphene intercalation zinc is disclosed in " a kind of fire-retardant corrosion resistant coatings for including modified graphene of CN201610570601 "
Inorganic coating prepared by iron houghite, the invention is using sodium borohydride, triethanolamine modified graphene and by itself and zinc-iron class
Hydrotalcite intercalation, finally with zinc-aluminium solution mixing system for inorganic corrosion resistant coating.What the patent was prepared is inorganic coating, and
Poisonous and harmful substance is still used in non-aqueous coating, and preparation process, environment is polluted, although while the inorganic coating is due to stone
The addition anticorrosive property of black alkene and zinc-iron houghite somewhat increases, but overall performance is still poor, and anti-flammability
It is relatively low, it can not also meet practical application request.
It is the main pollution source in water paint due to VOC, what China promulgated in 2005《Environmental labelling product technology
It is required that --- water paint》(HJ/T201-2005) VOC is all volatilizable in unit volume coating than water defined in
Property organic compound amount, and regulation, VOC content belongs to low VOC coatings less than 30g/L coating, and VOC content then belongs to less than 1g/L
In Diamond Search coating.Therefore, water paint in the market would generally excessively pursue " Diamond Search ", " low VOC " etc., although causing
VOC content is reduced, but coating physical property also can be reduced substantially simultaneously so that VOC content and physical property can not reach
Balance.
There is presently no graphene and hydrotalcite-based compound are modified, the obtained graphene/hydrotalcite of processing is compound to be filled out
Expect, and obtained compounded mix is added to the relevant report in water paint, more graphene/hydrotalcite is combined and filled out
Material be added in water paint and meanwhile improve the high temperature resistant of water paint, it is anticorrosion, anti-flammability, weatherability, impact resistance, wear-resisting
Property, the physical property such as barrier, hardness while, it is ensured that water paint is free of VOC, and good environmental protection makes water paint
Physical property and VOC content realize balance relevant report.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide it is a kind of there is excellent high temperature resistant, it is anti-
The physical properties such as burn into anti-flammability, weatherability, impact resistance, wearability, hardness, barrier, graphene-containing/zinc-aluminium class of VOC free
Water paint of hydrotalcite nano compound and preparation method thereof, to overcome the defect of existing water paint.
For achieving the above object, the technical solution adopted by the present invention is as follows：
The water paint of a kind of graphene-containing/zinc-aluminum gavite nano-complex, with following composition and proportioning：
Water-base resin：30~50 mass parts；
Water：25~40 mass parts；
Dispersant：0.1~0.5 mass parts；
Wetting agent：0.1~0.5 mass parts；
Defoamer：0.1~0.5 mass parts；
Thickener：0.1~0.5 mass parts；
Coalescents：0.1~0.5 mass parts；
Curing agent：0~10 mass parts；
Titanium dioxide：0~25 mass parts；
Calcium carbonate：0~20 mass parts；
Graphene/zinc-aluminum gavite nano-complex：0.1~2.5 mass parts；
The graphene/zinc-aluminum gavite nano-complex be by with Sheet Graphite alkenyl body, it is former on matrix surface
Position grows zinc-aluminum gavite lamella, forms the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella
Material, then gained composite micro-nano rice material is modified processing through coupling agent and obtained.
Preferably, the water-base resin is water-based acrylic resin, aqueous epoxy resins, waterborne polyurethane resin
At least one of, solid content is 30~50%.
Preferably, the dispersant is selected from P-19 (Shanghai Wenhua Chemical Co., Ltd.), N-Aol-106 (Hefei
Bo Langde Nanosolutions GmbH) in any one, further preferred P-19 (Shanghai Wenhua Chemical Co., Ltd.).
Preferably, the wetting agent is propane diols.
Preferably, the defoamer is defoamer 202 (Shanghai Wenhua Chemical Co., Ltd.).
Preferably, the thickener (Yixing can selected from ZT-800 (Shanghai Zhi Tu Chemical Co., Ltd.s), ASE-60
Believe Chemical Co., Ltd.) in any one, further preferred ASE-60 (Yixing is credible Chemical Co., Ltd.).
Preferably, the coalescents are alcohol ester 12 (Shanghai Wenhua Chemical Co., Ltd.).
Preferably, the curing agent is epoxy curing agent NPED-508.
Preferably, the titanium dioxide is rutile or anatase titanium dioxide, further preferred rutile type titanium
White powder.
Preferably, the calcium carbonate is any one in powdered whiting, precipitated calcium carbonate, activated Calcium carbonate
Kind, further preferred precipitated calcium carbonate.
Preferably, in graphene/zinc-aluminum gavite nano-complex, the matter of graphene and zinc-aluminum gavite
Measuring ratio is：1:5~1:100.
Preferably, in graphene/zinc-aluminum gavite nano-complex, coupling agent and composite micro-nano rice material
Mass ratio is：1:1~1:10.
Preferably, the graphene is selected from sulfonated graphene, graphene oxide, fluorinated graphene, reduction-oxidation
Any one in graphene, wherein being preferred with graphene oxide.
Preferably, the coupling agent is silane coupler or titanate coupling agent.Wherein, silane coupler is selected from
3- aminopropyl triethoxysilanes (NH2 (CH2) 3Si (OC2H5) 3, KH550), 3- glycidyl ether oxygen propyl trimethoxy silicon
Alkane (CH2OCHCH2OCH2CH2CH2Si (OCH3) 3, KH560), N- (β-aminoethyl)-γ-aminopropyl front three (second) TMOS
Any one in (NH2CH2CH2NHCH2CH2CH2Si (OCH3) 3, KH792) and its derivative；Titanate coupling agent is selected from
PN-101, PN-102, PN-105, PN-201 (Nanjing Pin Ning coupling agents Co., Ltd), KR-TTS, KR-41B, KR-38S, KR-
At least one of 46 (Ken Ruiqi petrochemical industries Co., Ltds of the U.S.), TYZOR-TE (du pont company), with PN-101,
PN105, KR-46, KR-TTS are preferable.
A kind of method for the water paint for preparing graphene-containing of the present invention/zinc-aluminum gavite nano-complex,
Comprise the following steps：
The dispersant of proportional quantity, wetting agent, coalescents and water are mixed well mixed；Then the froth breaking of proportional quantity is added
Agent, graphene/zinc-aluminum gavite nano-complex, titanium dioxide and calcium carbonate, are uniformly mixed；It is eventually adding proportional quantity
Water-base resin, thickener and curing agent, are uniformly mixed, at room temperature film-forming, produce the graphene-containing/zinc-aluminium class water
The water paint of talcum nano-complex.
Preferably, the preparation of the graphene/zinc-aluminum gavite nano-complex, comprises the following steps：
1) disperse graphene in alcohol solution, obtain graphene solution；By nine water aluminum nitrates, zinc nitrate hexahydrate, urea
It is soluble in water, obtain zinc-aluminum gavite precursor solution；Coupling agent is dissolved in alcohol aqueous solvent, pH is 3.5~5.5 times hydrolysis, is obtained
Coupling agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, is anti-7~9 times in 90~100 DEG C, pH value
18~24h is answered, is reacted after terminating, product is centrifuged, washed, and obtains graphene sheet layer alternate with zinc-aluminum gavite lamella
Composite micro-nano rice material；
3) composite micro-nano rice material is scattered in progress coupling modifier processing in coupling agent hydrolyzate, after reaction terminates, mistake
Filter, obtained solid particle is scrubbed, dry, produces the graphene/zinc-aluminum gavite nano-complex.
Be used as further preferred scheme, step 1) in zinc nitrate hexahydrate, nine water aluminum nitrates, urea mass ratio be 2:1:5
~3:1:15.
Be used as further preferred scheme, step 3) in composite micro-nano rice material ultrasonic disperse in coupling agent hydrolyzate, surpass
60~480min of sound time, then in 40~60 DEG C of 4~6h of insulation reaction.
Compared with prior art, the present invention has following conspicuousness beneficial effect：
The present invention is with Sheet Graphite alkenyl body, and growth in situ goes out zinc-aluminum gavite lamella on matrix surface, forms stone
The black alkene lamella composite micro-nano rice material alternate with zinc-aluminum gavite lamella, then by gained composite micro-nano rice material through coupling agent
It is modified processing and graphene/zinc-aluminum gavite nano-complex is made, realizes the matching property of storeroom, will be obtained
Graphene/zinc-aluminum gavite nano-complex is added in water paint, overcomes the agglomeration traits of functional filler, passes through
The bridge joint effect of coupling agent, realizes the close compatibility of inorganic matrix and resin matrix, in graphene, zinc-aluminum gavite
Under synergy, can be markedly improved the high temperature resistant of water paint, anticorrosion, anti-flammability, weatherability, impact resistance, wearability,
The physical properties such as hardness, barrier, expand the use scope of water paint, extend the service life of water paint, and
The stability of coating is good, and transport can be preserved for a long time, while obtained water paint is free of VOC, formaldehyde, lead, chromium, cadmium, mercury
Deng heavy metal element, environmental protection realizes the perfectly balanced of VOC content and physical property in water paint；In addition, of the invention
Preparation technology it is economical and practical, preparation process is simple, with low cost, without using dangerous or toxic material, safety and environmental protection, nothing
Special installation and harsh conditions are needed, it is easy to accomplish large-scale production, with extremely strong practical value.
Brief description of the drawings
Fig. 1 is the Tafel curve figure of the water paint prepared in embodiment 1 and comparative example 1；
Fig. 2 be the water paint prepared in embodiment 1 and comparative example 1 coating salt spray resistance test 30 days after shape appearance figure；
Fig. 3 is the Tafel curve figure of the water paint prepared in embodiment 2 and comparative example 2；
Fig. 4 be the water paint prepared in embodiment 2 and comparative example 2 coating salt spray resistance test 30 days after shape appearance figure；
Fig. 5 is the Tafel curve figure of the water paint prepared in embodiment 3 and comparative example 3；
Fig. 6 be the water paint prepared in embodiment 3 and comparative example 3 coating salt spray resistance test 30 days after shape appearance figure.
Embodiment
Technical solution of the present invention is described in further detail and completely with reference to embodiment and comparative example.
Embodiment 1
First, the preparation of graphene/zinc-aluminum gavite nano-complex：
1) 100mg graphene oxides are scattered in glycol water (50g ethylene glycol+50g deionized waters), in 30 DEG C
Ultrasonically treated 30 minutes, obtain graphene solution；2.2g zinc nitrate hexahydrates, the water aluminum nitrates of 1.1g nine, 11.5g urea are dissolved in 20ml
In water, zinc-aluminum gavite precursor solution is obtained；1.0g coupling agents (3- aminopropyl triethoxysilanes) are dissolved in ethylene glycol water-soluble
In liquid (49.5g ethylene glycol+49.5g deionized waters), the pH of regulation solution is 4, stirs two hours, is fully hydrolyzed coupling agent,
Obtain coupling agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, time for adding is about 4 hours, Ran Hou
100 DEG C, pH value be to react 24h under conditions of 8, terminate reaction, reaction solution is centrifuged, the anhydrous second of the powder particle isolated
Alcohol and deionized water distinguish rinse 5 times, obtain the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella；
3) by 0.5g steps 2) in prepare composite micro-nano rice material ultrasonic disperse in step 1) coupling agent hydrolyzate, adjust
Save pH value of solution be 7, ultrasonic disperse 120 minutes, then in 40~60 DEG C continue react 4 hours, terminate reaction, reacting liquid filtering from
Heart processing, obtained solid particle absolute ethyl alcohol and deionized water difference rinse 5 times, is subsequently placed in thermostatic drying chamber 60
Dried 8 hours at DEG C, produce the graphene/zinc-aluminum gavite nano-complex.
2nd, the preparation of the water paint of graphene-containing/zinc-aluminum gavite nano-complex：
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.2g graphenes/zinc-aluminum gavite nano-complex, 0.1g are added
Defoamer 202,0g titanium dioxides and 0g calcium carbonate (not needing titanium dioxide and calcium carbonate), are uniformly mixed that (mixing speed is
1500r/min, mixing time is 60 minutes)；It is eventually adding 30g aqueous epoxy resins (solid contents：45%, South Asia epoxy resin：
NPEW291-W-53), 0.2g ASE-60,5g curing agent (South Asia epoxy curing agent：NPED-508), it is uniformly mixed
(mixing speed is 500r/min, and mixing time is 120 minutes), film-forming, produces the graphene-containing/zinc-aluminium class at room temperature
The water paint of hydrotalcite nano compound.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared aqueous painting
The performance test data of material is shown in Table 1；The recombination current of product coating is measured, measurement result is as shown in Figure 1；To production
Product coating carries out salt spray resistance experiment, and experimental result is as shown in Figure 2.
Comparative example 1
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g defoamers 202,0g titanium dioxides and 0g calcium carbonate, stirring are added
Well mixed (mixing speed is 1500r/min, and mixing time is 60 minutes)；Be eventually adding 30g aqueous epoxy resins (admittedly contain
Amount：45%, South Asia epoxy resin：NPEW291-W-53), 0.2g ASE-60,5g curing agent (South Asia epoxy curing agent：
NPED-508), (mixing speed is 500r/min, and mixing time is 120 minutes) is uniformly mixed, at room temperature film-forming,
Produce contrast water paint.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared contrast water
The performance test data of property coating is shown in Table 1；The recombination current of product coating is measured, measurement result is as shown in Figure 1；
Salt spray resistance experiment is carried out to product coating, experimental result is as shown in Figure 2.
The performance test data of the water paint of table 1
From table 1：The water paint of the graphene-containing that the present invention is provided/zinc-aluminum gavite nano-complex has excellent
Good impact resistance, solvent resistance, wearability, resistance to elevated temperatures, fire resistance, barrier and higher hardness.
Fig. 1 is the Tafel curve figure of the water paint prepared in embodiment 1 and comparative example 1；1a is aqueous for comparative example 1
Coating, 1b is the water paint of embodiment 1, as seen from the figure：Graphene-containing/the zinc-aluminum gavite prepared in embodiment 1 is received
The coating corrosion electric current of the water paint of rice compound is 7.333 × 10-8A/cm2；The contrast water paint prepared in comparative example 1
Coating corrosion electric current be 2.051 × 10-7A/cm2；Illustrate that the corrosion resistance of the water paint obtained in the embodiment of the present invention 1 will
Significantly larger than traditional water paint.
Shape appearance figure after the coating salt spray resistance of water paints of the Fig. 2 to be prepared in embodiment 1 and comparative example 1 is tested 30 days；
It can be seen that under the same conditions, after salt spray resistance experiment in 30 days, the graphene-containing prepared in embodiment 1/zinc-aluminium class water
The water paint of talcum nano-complex without bubbling, peel off, get rusty, cracking situation occurs, salt spray resistance is significantly larger than tradition
Water paint.
Embodiment 2
First, the preparation of graphene/zinc-aluminum gavite nano-complex：
1) 250mg graphene oxides are scattered in glycol water (50g ethylene glycol+50g deionized waters), in 30 DEG C
Ultrasonically treated 60 minutes, obtain graphene solution；2.2g zinc nitrate hexahydrates, the water aluminum nitrates of 1.1g nine, 15g urea are dissolved in 30ml water
In, obtain zinc-aluminum gavite precursor solution；1.5g coupling agents (3- aminopropyl triethoxysilanes) are dissolved in glycol water
In (49g ethylene glycol+49.5g deionized waters), the pH of regulation solution is 4, stirs two hours, is fully hydrolyzed coupling agent, obtains idol
Join agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, time for adding is about 5 hours, Ran Hou
100 DEG C, pH value be to react 24h under conditions of 8.5, terminate reaction, reaction solution is centrifuged, the powder particle isolated is with anhydrous
Ethanol and deionized water distinguish rinse 5 times, obtain the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella
Material；
3) by 0.6g steps 2) in prepare composite micro-nano rice material ultrasonic disperse in step 1) coupling agent hydrolyzate, adjust
Save pH value of solution be 7, ultrasonic disperse 240 minutes, then in 40~60 DEG C continue react 4 hours, terminate reaction, reacting liquid filtering from
Heart processing, obtained solid particle absolute ethyl alcohol and deionized water difference rinse 5 times, is subsequently placed in thermostatic drying chamber 60
Dried 8 hours at DEG C, produce the graphene/zinc-aluminum gavite nano-complex.
2nd, the preparation of the water paint of graphene-containing/zinc-aluminum gavite nano-complex：
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 30ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g graphenes/zinc-aluminum gavite nano-complex, 0.1g are added
Defoamer 202,0g titanium dioxides and 0g calcium carbonate (not needing titanium dioxide and calcium carbonate), are uniformly mixed that (mixing speed is
1500r/min, mixing time is 90 minutes)；It is eventually adding 30g aqueous epoxy resins (solid contents：45%, South Asia epoxy resin：
NPEW291-W-53), 0.2g ASE-60,5g curing agent (South Asia epoxy curing agent：NPED-508), it is uniformly mixed
(mixing speed is 500r/min, and mixing time is 120 minutes), film-forming, produces the graphene-containing/zinc-aluminium class at room temperature
The water paint of hydrotalcite nano compound.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared aqueous painting
The performance test data of material is shown in Table 2；The recombination current of product coating is measured, measurement result is as shown in Figure 3；To production
Product coating carries out salt spray resistance experiment, and experimental result is as shown in Figure 4.
Comparative example 2
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 30ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g defoamers 202,0g titanium dioxides and 0g calcium carbonate, stirring are added
Well mixed (mixing speed is 1500r/min, and mixing time is 90 minutes)；Be eventually adding 30g aqueous epoxy resins (admittedly contain
Amount：45%, South Asia epoxy resin：NPEW291-W-53), 0.2g ASE-60,5g curing agent (South Asia epoxy curing agent：
NPED-508), (mixing speed is 500r/min, and mixing time is 120 minutes) is uniformly mixed, at room temperature film-forming,
Produce contrast water paint.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared contrast water
The performance test data of property coating is shown in Table 2；The recombination current of product coating is measured, measurement result is as shown in Figure 3；
Salt spray resistance experiment is carried out to product coating, experimental result is as shown in Figure 4.
The performance test data of the water paint of table 2
From table 2：The water paint of the graphene-containing that the present invention is provided/zinc-aluminum gavite nano-complex has excellent
Good impact resistance, solvent resistance, wearability, resistance to elevated temperatures, fire resistance, barrier and higher hardness.
Fig. 3 is the Tafel curve figure of the water paint prepared in embodiment 2 and comparative example 2；2a is aqueous for comparative example 2
Coating, 2b is the water paint of embodiment 2, as seen from the figure：Graphene-containing/the zinc-aluminum gavite prepared in embodiment 2 is received
The coating corrosion electric current of the water paint of rice compound is 8.528 × 10-8A/cm2；The contrast water paint prepared in comparative example 2
Coating corrosion electric current be 2.051 × 10-7A/cm2；Illustrate that the corrosion resistance of the water paint obtained in the embodiment of the present invention 2 will
Significantly larger than traditional water paint.
Shape appearance figure after the coating salt spray resistance of water paints of the Fig. 4 to be prepared in embodiment 2 and comparative example 2 is tested 30 days；
It can be seen that under the same conditions, after salt spray resistance experiment in 30 days, the graphene-containing prepared in embodiment 2/zinc-aluminium class water
The water paint of talcum nano-complex without bubbling, peel off, get rusty, cracking situation occurs, salt spray resistance is significantly larger than tradition
Water paint.
Embodiment 3
First, the preparation of graphene/zinc-aluminum gavite nano-complex：
1) 150mg graphene oxides are scattered in glycol water (50g ethylene glycol+50g deionized waters), in 30 DEG C
Ultrasonically treated 50 minutes, obtain graphene solution；2.2g zinc nitrate hexahydrates, the water aluminum nitrates of 1.1g nine, 12.5g urea are dissolved in 30ml
In water, zinc-aluminum gavite precursor solution is obtained；1.0g coupling agents (3- aminopropyl triethoxysilanes) are dissolved in ethylene glycol water-soluble
In liquid (49.5g ethylene glycol+49.5g deionized waters), the pH of regulation solution is 4, stirs two hours, is fully hydrolyzed coupling agent,
Obtain coupling agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, time for adding is about 5 hours, Ran Hou
100 DEG C, pH value be to react 24h under conditions of 8.3, terminate reaction, reaction solution is centrifuged, the powder particle isolated is with anhydrous
Ethanol and deionized water distinguish rinse 5 times, obtain the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella
Material；
3) by 0.5g steps 2) in prepare composite micro-nano rice material ultrasonic disperse in step 1) coupling agent hydrolyzate, adjust
Save pH value of solution be 7, ultrasonic disperse 240 minutes, then in 40~60 DEG C continue react 4 hours, terminate reaction, reacting liquid filtering from
Heart processing, obtained solid particle absolute ethyl alcohol and deionized water difference rinse 5 times, is subsequently placed in thermostatic drying chamber 60
Dried 10 hours at DEG C, produce the graphene/zinc-aluminum gavite nano-complex.
2nd, the preparation of the water paint of graphene-containing/zinc-aluminum gavite nano-complex：
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 30ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g graphenes/zinc-aluminum gavite nano-complex, 0.1g are added
Defoamer 202,0g titanium dioxides and 0g calcium carbonate (not needing titanium dioxide and calcium carbonate), are uniformly mixed that (mixing speed is
1500r/min, mixing time is 90 minutes)；It is eventually adding 30g aqueous polyurethane (Bayers：2592, without curing agent), 0.2g
ASE-60, (mixing speed is 500r/min, and mixing time is 120 minutes) is uniformly mixed, film-forming, is produced at room temperature
The water paint of the graphene-containing/zinc-aluminum gavite nano-complex.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared aqueous painting
The performance test data of material is shown in Table 3；The recombination current of product coating is measured, measurement result is as shown in Figure 5；To production
Product coating carries out salt spray resistance experiment, and experimental result is as shown in Figure 6.
Comparative example 3
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g defoamers 202,0g titanium dioxides and 0g calcium carbonate, stirring are added
Well mixed (mixing speed is 1500r/min, and mixing time is 90 minutes)；It is eventually adding 30g aqueous polyurethane (Bayers：
2592, without curing agent), 0.2g ASE-60, it is uniformly mixed that (mixing speed is 500r/min, and mixing time is 120 points
Clock), film-forming, produces contrast water paint at room temperature.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, on prepared contrast water
The performance test data of property coating is shown in Table 3；The recombination current of product coating is measured, measurement result is as shown in Figure 5；
Salt spray resistance experiment is carried out to product coating, experimental result is as shown in Figure 6.
The performance test data of the water paint of table 3
From table 3：The water paint of the graphene-containing that the present invention is provided/zinc-aluminum gavite nano-complex has excellent
Good impact resistance, solvent resistance, wearability, resistance to elevated temperatures, fire resistance, barrier and higher hardness.
Fig. 5 is the Tafel curve figure of the water paint prepared in embodiment 3 and comparative example 3；3a is aqueous for comparative example 3
Coating, 3b is the water paint of embodiment 3, as seen from the figure：Graphene-containing/the zinc-aluminum gavite prepared in embodiment 3 is received
The coating corrosion electric current of the water paint of rice compound is 2.355 × 10-6A/cm2；The contrast water paint prepared in comparative example 3
Coating corrosion electric current be 1.706 × 10-5A/cm2；Illustrate that the corrosion resistance of the water paint obtained in the embodiment of the present invention 3 will
Significantly larger than traditional water paint.
Shape appearance figure after the coating salt spray resistance of water paints of the Fig. 6 to be prepared in embodiment 3 and comparative example 3 is tested 30 days；
It can be seen that under the same conditions, after salt spray resistance experiment in 30 days, the graphene-containing prepared in embodiment 3/zinc-aluminium class water
The water paint of talcum nano-complex without bubbling, peel off, get rusty, cracking situation occurs, salt spray resistance is significantly larger than tradition
Water paint.
Embodiment 4
First, the preparation of graphene/zinc-aluminum gavite nano-complex：
1) 200mg graphene oxides are scattered in glycol water (50g ethylene glycol+50g deionized waters), in 30 DEG C
Ultrasonically treated 30 minutes, obtain graphene solution；2.2g zinc nitrate hexahydrates, the water aluminum nitrates of 1.1g nine, 11.5g urea are dissolved in 20ml
In water, zinc-aluminum gavite precursor solution is obtained；By 1.0g coupling agents (PN-101) be dissolved in glycol water (49g ethylene glycol+
49g deionized waters) in, the pH of regulation solution is 4, stirs two hours, is fully hydrolyzed coupling agent, obtains coupling agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, time for adding is about 4 hours, Ran Hou
100 DEG C, pH value be to react 24h under conditions of 8, terminate reaction, reaction solution is centrifuged, the anhydrous second of the powder particle isolated
Alcohol and deionized water distinguish rinse 5 times, obtain the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella；
3) by 0.5g steps 2) in prepare composite micro-nano rice material ultrasonic disperse in step 1) coupling agent hydrolyzate, adjust
Save pH value of solution be 7, ultrasonic disperse 120 minutes, then in 40~60 DEG C continue react 4 hours, terminate reaction, reacting liquid filtering from
Heart processing, obtained solid particle absolute ethyl alcohol and deionized water difference rinse 5 times, is subsequently placed in thermostatic drying chamber 60
Dried 8 hours at DEG C, produce the graphene/zinc-aluminum gavite nano-complex.
2nd, the preparation of the water paint of graphene-containing/zinc-aluminum gavite nano-complex：
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.3g graphenes/zinc-aluminum gavite nano-complex, 0.1g are added
Defoamer 202,20g titanium dioxides and 20g calcium carbonate, are uniformly mixed that (mixing speed is 1500r/min, and mixing time is 60
Minute)；It is eventually adding 30g aqueous epoxy resins (solid contents：45%, South Asia epoxy resin：NPEW291-W-53)、0.2g
ASE-60,5g curing agent (South Asia epoxy curing agent：NPED-508), be uniformly mixed (mixing speed is 500r/min,
Mixing time is 120 minutes), film-forming, produces the water of the graphene-containing/zinc-aluminum gavite nano-complex at room temperature
Property coating.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, and product coating is combined
Electric current and salt fog resistance are measured, and the performance test data on prepared contrast water paint is shown in Table 4..
Comparative example 4
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g defoamers 202,20g titanium dioxides and 20g calcium carbonate are added, is stirred
Mix well mixed (mixing speed is 1500r/min, and mixing time is 60 minutes)；Be eventually adding 30g aqueous epoxy resins (admittedly contain
Amount：45%, South Asia epoxy resin：NPEW291-W-53), 0.2g ASE-60,5g curing agent (South Asia epoxy curing agent：
NPED-508), (mixing speed is 500r/min, and mixing time is 120 minutes) is uniformly mixed, at room temperature film-forming,
Produce contrast water paint.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, and product coating is combined
Electric current and salt fog resistance are measured, and the performance test data on prepared contrast water paint is shown in Table 4.
The performance test data of the water paint of table 4
From table 4：The water paint of the graphene-containing that the present invention is provided/zinc-aluminum gavite nano-complex has excellent
Good impact resistance, solvent resistance, wearability, resistance to elevated temperatures, fire resistance, barrier, salt fog resistance, corrosion resistance and compared with
High hardness.
Embodiment 5
First, the preparation of graphene/zinc-aluminum gavite nano-complex：
1) 250mg graphene oxides are scattered in glycol water (50g ethylene glycol+50g deionized waters), in 30 DEG C
Ultrasonically treated 50 minutes, obtain graphene solution；2.2g zinc nitrate hexahydrates, the water aluminum nitrates of 1.1g nine, 12.5g urea are dissolved in 30ml
In water, zinc-aluminum gavite precursor solution is obtained；By 2.0g coupling agents (PN-105) be dissolved in glycol water (49g ethylene glycol+
49g deionized waters) in, the pH of regulation solution is 4, stirs two hours, is fully hydrolyzed coupling agent, obtains coupling agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, time for adding is about 5 hours, Ran Hou
100 DEG C, pH value be to react 24h under conditions of 8.3, terminate reaction, reaction solution is centrifuged, the powder particle isolated is with anhydrous
Ethanol and deionized water distinguish rinse 5 times, obtain the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella
Material；
3) by 0.5g steps 2) in prepare composite micro-nano rice material ultrasonic disperse in step 1) coupling agent hydrolyzate, adjust
Save pH value of solution be 7, ultrasonic disperse 240 minutes, then in 40~60 DEG C continue react 4 hours, terminate reaction, reacting liquid filtering from
Heart processing, obtained solid particle absolute ethyl alcohol and deionized water difference rinse 5 times, is subsequently placed in thermostatic drying chamber 60
Dried 10 hours at DEG C, produce the graphene/zinc-aluminum gavite nano-complex.
2nd, the preparation of the water paint of graphene-containing/zinc-aluminum gavite nano-complex：
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 30ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.2g graphenes/zinc-aluminum gavite nano-complex, 0.1g are added
Defoamer 202,23g titanium dioxides and 18g calcium carbonate, are uniformly mixed that (mixing speed is 1500r/min, and mixing time is 90
Minute)；It is eventually adding 30g aqueous polyurethane (Bayers：2592, without curing agent), 0.2g ASE-60, it is uniformly mixed and (stirs
Speed is mixed for 500r/min, mixing time is 120 minutes), film-forming, produces the graphene-containing/zinc-aluminium class water at room temperature
The water paint of talcum nano-complex.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, and product coating is combined
Electric current and salt fog resistance are measured, and the performance test data on prepared contrast water paint is shown in Table 5.
Comparative example 5
0.2g propane diols, 0.3g P-19,0.1g alcohol ester 12 and 25ml deionized waters are uniformly mixed (stirring speed
Spend for 800r/min, mixing time is 20 minutes)；Then 0.1g defoamers 202,23g titanium dioxides and 18g calcium carbonate are added, is stirred
Mix well mixed (mixing speed is 1500r/min, and mixing time is 90 minutes)；It is eventually adding 30g aqueous polyurethane (Bayers：
2592, without curing agent), 0.2g ASE-60, it is uniformly mixed that (mixing speed is 500r/min, and mixing time is 120 points
Clock), film-forming, produces contrast water paint at room temperature.
Using GB/T 1768-2006, GB/T 23989-2009, GB/T 1732-1993, GB/T6739-2006, GB/T
1771-2007, GB/T 1735-2009, HG/T 3853-2006 carry out the performance detection of product, and product coating is combined
Electric current and salt fog resistance are measured, and the performance test data on prepared contrast water paint is shown in Table 5.
The performance test data of the water paint of table 5
From table 5：The water paint of the graphene-containing that the present invention is provided/zinc-aluminum gavite nano-complex has excellent
Good impact resistance, solvent resistance, wearability, resistance to elevated temperatures, fire resistance, barrier, salt fog resistance, corrosion resistance and compared with
High hardness.
In addition, using GB 18582-2008, GB24408-2009 to the graphitiferous that is prepared in the above embodiment of the present invention
The water paint of alkene/zinc-aluminum gavite nano-complex carries out VOC content, lead, and chromium, cadmium, mercury content, content of formaldehyde are surveyed
Examination, as a result shows, the water paint of graphene-containing/zinc-aluminum gavite nano-complex prepared by the present invention is free of VOC, first
Aldehyde, lead, chromium, cadmium, the heavy metal element such as mercury are environment friendly and pollution-free.
In summary：The present invention is with Sheet Graphite alkenyl body, and growth in situ goes out zinc-aluminum gavite piece on matrix surface
Layer, forms the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella, then by gained composite micro-nano meter material
Material is modified processing through coupling agent and graphene/zinc-aluminum gavite nano-complex is made, and realizes matching for storeroom
Property, obtained graphene/zinc-aluminum gavite nano-complex is added in water paint, the group of functional filler is overcome
Poly- problem, is acted on by the bridge joint of coupling agent, the close compatibility of inorganic matrix and resin matrix is realized, in graphene, zinc
Under the synergy of aluminium houghite, the high temperature resistant of water paint can be markedly improved, it is anticorrosion, anti-flammability, weatherability, resistance to
The physical properties such as impact, wearability, hardness, barrier, expand the use scope of water paint, extend making for water paint
With the life-span, while obtained water paint is free of VOC, formaldehyde, lead, chromium, cadmium, the heavy metal element such as mercury, environmental protection is realized
VOC content and physical property is perfectly balanced in water paint；Meanwhile, the present invention is using modified graphene/zinc-aluminium class neatly
Stone nano-complex does filler, adds the amalgamation and binding ability of organic body interface, and the usage amount of graphene is relatively low,
Reduce production cost；In addition, the preparation technology of the present invention is economical and practical, preparation process is simple, especially graphene/zinc-aluminium class
Without any poisonous and harmful substance in the preparation process of hydrotalcite nano compound, alkaline solution can be while oxygen reduction fossil
Black alkene and generation hydrotalcite, can one-step method direct in-situ generation graphene/zinc without additionally adding remaining strong reductant
Aluminium acrylic/hydrotalcite-like nano compound, nontoxic, safety and environmental protection is with low cost, without special installation and harsh conditions, it is easy to real
Existing large-scale production, with extremely strong practical value, in terms of existing technologies, achieves conspicuousness progress and unexpected
Effect.
Finally need it is pointed out here that be：It the above is only the part preferred embodiment of the present invention, it is impossible to be interpreted as to this hair
The limitation of bright protection domain, those skilled in the art according to the present invention the above make some it is nonessential improvement and
Adjustment belongs to protection scope of the present invention.
Claims (10)
1. a kind of water paint of graphene-containing/zinc-aluminum gavite nano-complex, it is characterised in that with following composition and
Proportioning：
Water-base resin：30~50 mass parts；
Water：25~40 mass parts；
Dispersant：0.1~0.5 mass parts；
Wetting agent：0.1~0.5 mass parts；
Defoamer：0.1~0.5 mass parts；
Thickener：0.1~0.5 mass parts；
Coalescents：0.1~0.5 mass parts；
Curing agent：0~10 mass parts；
Titanium dioxide：0~25 mass parts；
Calcium carbonate：0~20 mass parts；
Graphene/zinc-aluminum gavite nano-complex：0.1~2.5 mass parts；
The graphene/zinc-aluminum gavite nano-complex is by with Sheet Graphite alkenyl body, original position is raw on matrix surface
Zinc-aluminum gavite lamella is grown, the graphene sheet layer composite micro-nano rice material alternate with zinc-aluminum gavite lamella is formed, then
Gained composite micro-nano rice material is modified processing through coupling agent and obtained.
2. water paint according to claim 1, it is characterised in that：The water-base resin is water-based acrylic resin, water
Property epoxy resin, at least one of waterborne polyurethane resin, solid content is 30~50%.
3. water paint according to claim 1, it is characterised in that：In graphene/zinc-aluminum gavite nano-complex,
Graphene and the mass ratio of zinc-aluminum gavite are：1:5~1:100, coupling agent and composite micro-nano rice material mass ratio be：1:
1~1:10.
4. water paint according to claim 1, it is characterised in that：The graphene is selected from sulfonated graphene, oxidation stone
Any one in black alkene, fluorinated graphene, redox graphene.
5. water paint according to claim 1, it is characterised in that：The coupling agent is that silane coupler or titanate esters are even
Join agent.
6. water paint according to claim 5, it is characterised in that：Silane coupler is selected from 3- aminopropyl-triethoxy silicon
Alkane, 3- glycidyl ether oxygen propyl trimethoxy silicanes, N- (β-aminoethyl)-γ-aminopropyl front three (second) TMOS and its
Any one in derivative.
7. water paint according to claim 5, it is characterised in that：Titanate coupling agent be selected from PN-101, PN-102,
At least one of PN-105, PN-201, KR-TTS, KR-41B, KR-38S, KR-46, TYZOR-TE.
8. a kind of method of the water paint of the graphene-containing/zinc-aluminum gavite nano-complex prepared described in claim 1,
It is characterised in that it includes following steps：
The dispersant of proportional quantity, wetting agent, coalescents and water are mixed well mixed；Then defoamer, the stone of proportional quantity are added
Black alkene/zinc-aluminum gavite nano-complex, titanium dioxide and calcium carbonate, is uniformly mixed；It is eventually adding the aqueous of proportional quantity
Resin, thickener and curing agent, are uniformly mixed, at room temperature film-forming, produce the graphene-containing/zinc-aluminum gavite
The water paint of nano-complex.
9. method according to claim 8, it is characterised in that：The graphene/zinc-aluminum gavite nano-complex
Prepare, comprise the following steps：
1) disperse graphene in alcohol solution, obtain graphene solution；Nine water aluminum nitrates, zinc nitrate hexahydrate, urea are dissolved in
In water, zinc-aluminum gavite precursor solution is obtained；Coupling agent is dissolved in alcohol aqueous solvent, pH is 3.5~5.5 times hydrolysis, must be coupled
Agent hydrolyzate；
2) zinc-aluminum gavite precursor solution is added dropwise in graphene solution, is 7~9 times reactions 18 in 90~100 DEG C, pH value
~24h, after reaction terminates, product is centrifuged, washed, and obtains that graphene sheet layer is alternate with zinc-aluminum gavite lamella to answer
Close micro Nano material；
3) composite micro-nano rice material is scattered in progress coupling modifier processing in coupling agent hydrolyzate, after reaction terminates, filtering is obtained
The solid particle arrived is scrubbed, dry, produces the graphene/zinc-aluminum gavite nano-complex.
10. method according to claim 9, it is characterised in that：Step 1) in zinc nitrate hexahydrate, nine water aluminum nitrates, urea
Mass ratio be 2:1:5~3:1:15.
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