CN108314946A - A kind of composite aqueous paint - Google Patents

A kind of composite aqueous paint Download PDF

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Publication number
CN108314946A
CN108314946A CN201810127071.6A CN201810127071A CN108314946A CN 108314946 A CN108314946 A CN 108314946A CN 201810127071 A CN201810127071 A CN 201810127071A CN 108314946 A CN108314946 A CN 108314946A
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added
graphene
acrylic resin
water
modified graphene
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曹月琴
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Chengdu China Technology Co Ltd
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Chengdu China Technology Co Ltd
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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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a kind of composite aqueous paints, it is related to environment-friendly materials field, it is poor to solve existing water soluble acrylic acid anticorrosive paint water resistance, the technical issues of easily dodging erosion, it includes acrylic resin, modified graphene, filler and auxiliary agent, it is characterized in that, the acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent mass percent be:30% 60%, 1.5% 12%, 10%, 10% 15%, 10% 15%, 2% 3%；The composite aqueous paint of the present invention, have the characteristics that safety and environmental protection, anti-corrosion resistance to ag(e)ing is excellent, alkali resistance is good, synthesis processing is simple, modified graphene is introduced with blend method, with water resistance outstanding and salt fog resistance, anti-corrosion effect is substantially better than the water paint of other carbon-based materials filling；Oxidation processes of the graphene through potassium permanganate, the concentrated sulfuric acid, obtained modified graphene have the physical and chemical performance of graphene oxide, are obviously improved the performances such as permeability resistance, tensile strength and the elongation at break of composite coating with metal packing compatibility.

Description

A kind of composite aqueous paint
Technical field
The present invention relates to environment-friendly materials fields, more particularly to a kind of composite aqueous paint.
Background technology
Water paint is the new coating that development is encouraged in countries in the world, water paint in the industrial coating that the U.S. produces now 25% is accounted for, and the research and development of the water paint in China are started late, major product is the emulsion paint produced as means using emulsion polymerization, by The limitation of cost performance can't contend on the market with traditional solvent-borne coating, improve overall performance, the drop of water paint as early as possible Low production cost be China's industrial circle promote the use of water paint there is an urgent need to.
Graphene oxide is a kind of derivative of graphene, is by graphite oxide is peeling-off and is formed single-layer or multi-layer Lamella has typical accurate two bit space structures.Graphene oxide has high-ratio surface energy and mechanical performance, and containing abundant Oxygen-containing functional group is used widely in fields such as optics, catalysis, charge storage and electrode materials.In recent years, because of oxidation Graphene have can dispersion and the easily compound advantage with other polymers well in most polar solvents, so with It replaces graphene to be used for corrosion-inhibiting coating, can overcome graphene difficulty and metal base, polymeric substrate interaction and Yi Fu Close the problem of reuniting in object.By graphene oxide, ultrasonic disperse obtains homogeneous solution to Prabakar etc. in ethanol, is spin-coated on lithium Drying prepares GO coatings on ion battery afflux aluminium sheet, plays good anti-corrosion effect.Krishnamoorthy etc. is to aoxidize stone Black alkene is filler, and using ball-milling method by itself and alkyd resin mixing, the corrosion potential that GO/ alkyd resin composite coatings are made is more naked The reduction of galvanized iron sheet, corrosion current reduce 1.5 orders of magnitude.Ramezanzadeh etc. is by graphene oxide, polyamides The graphene oxide of imines graft modification is added in polyurethane coating, improve to some extent coating ion barrier ability can and Antiseptic property.Ke Qiang et al. is prepared for graphene/Pt/Polypyrrole composite material (RGOs/PPy) using emulsion polymerization, to enhance Epoxy resin, when RGOs/PPy additions are 1%, the purer poly epoxy resin of impact resistance of composite coating increases 267%, And anti-corrosion effect is best.
Invention content
It is an object of the invention to：There is provided a kind of has that safety and environmental protection, anti-corrosion resistance to ag(e)ing is excellent, alkali resistance is good, synthesis Process the composite aqueous paint of the features such as simple.
The present invention specifically uses following technical scheme to achieve the goals above：
A kind of composite aqueous paint, including acrylic resin, modified graphene, filler and auxiliary agent, which is characterized in that described Acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent mass percent be:30%-60%, 1.5%- 12%, 10%, 10%-15%, 10%-15%, 2%-3%；The preparation method of the acrylic resin is：
1) by methyl methacrylate, the 20-23 by volume of butyl acrylate, chlorine:25-30:95-110 is mixed：It will Methyl methacrylate and butyl acrylate pour into four-hole boiling flask in proportion, then are passed through the chlorine of respective volume, obtain methyl The mixing liquid of methyl acrylate, butyl acrylate and chlorine；
2) mixing liquid of methyl methacrylate, butyl acrylate and chlorine and acrylic acid by volume 6:1 is mixed in Four-hole boiling flask is added dropwise n-butanol stirring, is reacted 2-4 hours after being warming up to 80 DEG C -90 DEG C, be cooled to room temperature and subtract after reaction Pressure distillation is added after a small amount of dispersant solution dilution and adjusts pH value to 6.5-7.5 with triethylamine, stirs to get acrylic resin.
The preparation method of the crosslinking agent is：
1) formalin that mass fraction is 90%-95% is added to melamine in three-necked flask, and in water It is stirred at reflux in bath, is heated to 75 DEG C -90 DEG C and reacts 3-4 hours, until there is the precipitation of white crystalline solid substance；
2) methanol solution is added, is stirred to react and is all dissolved to material and discharge to obtain high etherified melamine amine formaldehyde tree Fat.The preparation method of the modified graphene is：
1) configuration quality score is the liquor potassic permanganate of 2.5%-3.5%；
2) liquor potassic permanganate of 2.5%-3.5%, graphene and the concentrated sulfuric acid are pressed into 200ml：1g：The ratio of 100ml is set Simultaneously ultrasonic disperse is uniformly mixed in beaker；
3) beaker for containing mixed solution is put into heating stirring in water-bath, filters out after graphene is washed till neutrality and dries To modified graphene.
The preparation method of the composite aqueous paint is：
1) auxiliary rheological agents are added in deionized water, are stirring evenly and then adding into dispersant, antifoaming agent, cosolvent stirring 20min-30min obtains the deionized water solution of auxiliary agent；
2) modified graphene, titanium dioxide, trbasic zinc phosphate, zinc oxide, iron oxide red, sulfuric acid are added in the adjuvant water solution 1) obtained Barium, silica and talcum powder, then ultrasonic disperse 20min-30min；
3) high etherified melamine amine-formaldehyde resins and antifoaming agent is added in the mixing liquid obtained in 2), then ultrasound point Dissipate 5min-10min；
4) 3) acrylic resin, pH adjusting agent, levelling agent, emulsifier, activity will be added in the mixing liquid obtained to dilute Agent and coalescents are uniformly mixed and with strainer filterings more than 200 mesh, obtain composite aqueous paint.
The mass ratio of the zinc oxide and trbasic zinc phosphate is 1:2 to 3:1.
The mass ratio of the zinc oxide and trbasic zinc phosphate and high etherified melamine amine-formaldehyde resins is 3:5 to 3:1, and zinc oxide It is 1 with the mass ratio of trbasic zinc phosphate and acrylic resin:5 to 1:2.
Beneficial effects of the present invention are as follows：
In general, composite aqueous paint of the invention, have safety and environmental protection, anti-corrosion resistance to ag(e)ing is excellent, alkali resistance is good, The features such as synthesis processing is simple introduces modified graphene with blend method, with water resistance outstanding and salt fog resistance, Anti-corrosion effect is substantially better than the water paint of other carbon-based materials filling；And impact strength, wear-resistant amount also increase；And And coating is environmentally friendly, pollution-free.Oxidation processes of the graphene through potassium permanganate, the concentrated sulfuric acid, obtain modified graphene, exist The physical and chemical performance of graphene oxide, can in coating well dispersion, with the compound advantage of other polymers, with metal base, Polymeric substrate interaction is reunited.The performances such as permeability resistance, tensile strength and the elongation at break of composite coating are made to obtain It is obviously improved.
Specific implementation mode
In order to which those skilled in the art are better understood from the present invention, the present invention is made into one with reference to following embodiment Step detailed description.
Embodiment 1
The present invention provides a kind of composite aqueous paint, including acrylic resin, modified graphene, crosslinking agent, filler and helps Agent, which is characterized in that the acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent mass percent be: 50%, 12%, 10%, 12%, 14%, 2%；The preparation method of the acrylic resin is：
1) by methyl methacrylate, butyl acrylate, chlorine by volume 21:26:97 mixing：By methacrylic acid Methyl esters and butyl acrylate pour into four-hole boiling flask in proportion, then are passed through the chlorine of respective volume, obtain methyl methacrylate, The mixing liquid of butyl acrylate and chlorine；
2) mixing liquid of methyl methacrylate, butyl acrylate and chlorine and acrylic acid by volume 6:1 is mixed in Four-hole boiling flask is added dropwise n-butanol stirring, is reacted 2.5 hours after being warming up to 85 DEG C, be cooled to room temperature after reaction and depressurize steaming It evaporates, is added after a small amount of dispersant solution dilution and adjusts pH value to 7 with triethylamine, stir to get acrylic resin.
The preparation method of the crosslinking agent is：
1) formalin that mass fraction is 93% is added to melamine in three-necked flask, and in water-bath It is stirred at reflux, is heated to 80 DEG C and reacts 3 hours, until there is the precipitation of white crystalline solid substance；
2) methanol solution is added, is stirred to react and is all dissolved to material and discharge to obtain high etherified melamine amine formaldehyde tree Fat.
The preparation method of the modified graphene is：
1) liquor potassic permanganate that configuration quality score is 2.5%；
2) 2.5% liquor potassic permanganate, graphene and the concentrated sulfuric acid are pressed into 200ml：1g：The ratio of 100ml is placed in beaker In be uniformly mixed and ultrasonic disperse；
3) beaker for containing mixed solution is put into heating stirring in water-bath, filters out after graphene is washed till neutrality and dries To modified graphene.
The preparation method of the composite aqueous paint is：
1) auxiliary rheological agents are added in deionized water, are stirring evenly and then adding into dispersant, antifoaming agent, cosolvent stirring 22min obtains the deionized water solution of auxiliary agent；
2) modified graphene, titanium dioxide, trbasic zinc phosphate, zinc oxide, iron oxide red, sulfuric acid are added in the adjuvant water solution 1) obtained Barium, silica and talcum powder, then ultrasonic disperse 25min；
3) high etherified melamine amine-formaldehyde resins and antifoaming agent is added in the mixing liquid obtained in 2), then ultrasound point Dissipate 5min；
4) 3) acrylic resin, pH adjusting agent, levelling agent, emulsifier, activity will be added in the mixing liquid obtained to dilute Agent and coalescents are uniformly mixed and with strainer filterings more than 200 mesh, obtain composite aqueous paint.
The mass ratio of the zinc oxide and trbasic zinc phosphate is 2:5.
The mass ratio of the zinc oxide and trbasic zinc phosphate and high etherified melamine amine-formaldehyde resins is 2:1, and zinc oxide and phosphorus The mass ratio of sour zinc and acrylic resin is 1:3.
Embodiment 2
The present invention provides a kind of composite aqueous paint, including acrylic resin, modified graphene, crosslinking agent, filler and helps Agent, which is characterized in that the acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent mass percent be: 50%, 7%, 10%, 15%, 15%, 3%；The preparation method of the acrylic resin is：
1) by methyl methacrylate, butyl acrylate, chlorine by volume 22:28:98 mixing：By methacrylic acid Methyl esters and butyl acrylate pour into four-hole boiling flask in proportion, then are passed through the chlorine of respective volume, obtain methyl methacrylate, The mixing liquid of butyl acrylate and chlorine；
2) mixing liquid of methyl methacrylate, butyl acrylate and chlorine and acrylic acid by volume 6:1 is mixed in Four-hole boiling flask is added dropwise n-butanol stirring, is reacted 2.5 hours after being warming up to 86 DEG C, be cooled to room temperature after reaction and depressurize steaming It evaporates, is added after a small amount of dispersant solution dilution and adjusts pH value to 6.8 with triethylamine, stir to get acrylic resin.
The preparation method of the crosslinking agent is：
1) formalin that mass fraction is 95% is added to melamine in three-necked flask, and in water-bath It is stirred at reflux, is heated to 85 DEG C and reacts 3 hours, until there is the precipitation of white crystalline solid substance；
2) methanol solution is added, is stirred to react and is all dissolved to material and discharge to obtain high etherified melamine amine formaldehyde tree Fat.
The preparation method of the modified graphene is：
1) liquor potassic permanganate that configuration quality score is 3%；
2) 35% liquor potassic permanganate, graphene and the concentrated sulfuric acid are pressed into 200ml：1g：The ratio of 100ml is placed in beaker It is uniformly mixed simultaneously ultrasonic disperse；
3) beaker for containing mixed solution is put into heating stirring in water-bath, filters out after graphene is washed till neutrality and dries To modified graphene.
The preparation method of the composite aqueous paint is：
1) auxiliary rheological agents are added in deionized water, are stirring evenly and then adding into dispersant, antifoaming agent, cosolvent stirring 20min-30min obtains the deionized water solution of auxiliary agent；
2) modified graphene, titanium dioxide, trbasic zinc phosphate, zinc oxide, iron oxide red, sulfuric acid are added in the adjuvant water solution 1) obtained Barium, silica and talcum powder, then ultrasonic disperse 25min；
3) high etherified melamine amine-formaldehyde resins and antifoaming agent is added in the mixing liquid obtained in 2), then ultrasound point Dissipate 10min；
4) 3) acrylic resin, pH adjusting agent, levelling agent, emulsifier, activity will be added in the mixing liquid obtained to dilute Agent and coalescents are uniformly mixed and with strainer filterings more than 200 mesh, obtain composite aqueous paint.
The mass ratio of the zinc oxide and trbasic zinc phosphate is 1:1.
The mass ratio of the zinc oxide and trbasic zinc phosphate and high etherified melamine amine-formaldehyde resins is 1:1, and zinc oxide and phosphorus The mass ratio of sour zinc and acrylic resin is 4:5.
Embodiment 3
The present invention provides a kind of composite aqueous paint, including acrylic resin, modified graphene, crosslinking agent, filler and helps Agent, which is characterized in that the acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent mass percent be: 60%, 2%, 10%, 10%, 15%, 3%；The preparation method of the acrylic resin is：
1) by methyl methacrylate, butyl acrylate, chlorine by volume 23:30:105 mixing：By metering system Sour methyl esters and butyl acrylate pour into four-hole boiling flask in proportion, then are passed through the chlorine of respective volume, obtain methyl methacrylate The mixing liquid of ester, butyl acrylate and chlorine；
2) mixing liquid of methyl methacrylate, butyl acrylate and chlorine and acrylic acid by volume 6:1 is mixed in Four-hole boiling flask is added dropwise n-butanol stirring, is reacted 2 hours after being warming up to 90 DEG C, be cooled to room temperature and be evaporated under reduced pressure after reaction, It is added after a small amount of dispersant solution dilution and adjusts pH value to 7.5 with triethylamine, stir to get acrylic resin.
The preparation method of the crosslinking agent is：
1) formalin that mass fraction is 90% is added to melamine in three-necked flask, and in water-bath It is stirred at reflux, is heated to 90 DEG C and reacts 3 hours, until there is the precipitation of white crystalline solid substance；
2) methanol solution is added, is stirred to react and is all dissolved to material and discharge to obtain high etherified melamine amine formaldehyde tree Fat.
The preparation method of the modified graphene is：
1) liquor potassic permanganate that configuration quality score is 3.5%；
2) 3.5% liquor potassic permanganate, graphene and the concentrated sulfuric acid are pressed into 200ml：1g：The ratio of 100ml is placed in beaker In be uniformly mixed and ultrasonic disperse；
3) beaker for containing mixed solution is put into heating stirring in water-bath, filters out after graphene is washed till neutrality and dries To modified graphene.
The preparation method of the composite aqueous paint is：
1) auxiliary rheological agents are added in deionized water, are stirring evenly and then adding into dispersant, antifoaming agent, cosolvent stirring 20min obtains the deionized water solution of auxiliary agent；
2) modified graphene, titanium dioxide, trbasic zinc phosphate, zinc oxide, iron oxide red, sulfuric acid are added in the adjuvant water solution 1) obtained Barium, silica and talcum powder, then ultrasonic disperse 20min；
3) high etherified melamine amine-formaldehyde resins and antifoaming agent is added in the mixing liquid obtained in 2), then ultrasound point Dissipate 5min；
4) 3) acrylic resin, pH adjusting agent, levelling agent, emulsifier, activity will be added in the mixing liquid obtained to dilute Agent and coalescents are uniformly mixed and with strainer filterings more than 200 mesh, obtain composite aqueous paint.
The mass ratio of the zinc oxide and trbasic zinc phosphate is 2:5.
The mass ratio of the zinc oxide and trbasic zinc phosphate and high etherified melamine amine-formaldehyde resins is 3:5 to 3:1, and zinc oxide It is 1 with the mass ratio of trbasic zinc phosphate and acrylic resin:3.
The above, only presently preferred embodiments of the present invention, are not intended to limit the invention, patent protection model of the invention It encloses and is subject to claims, equivalent variations made by every specification and embodiment content with the present invention similarly should all It is included within the scope of the present invention.

Claims (3)

1. a kind of composite aqueous paint, including acrylic resin, modified graphene, crosslinking agent, filler and auxiliary agent, feature exist It is in the mass percent of, the acrylic resin, modified graphene, crosslinking agent, filler, water and auxiliary agent:30%-60%, 1.5%-12%, 10%, 10%-15%, 10%-15%, 2%-3%；The preparation method of the acrylic resin is：
1) by methyl methacrylate, the 20-23 by volume of butyl acrylate, chlorine:25-30:95-110 is mixed：By methyl Methyl acrylate and butyl acrylate pour into four-hole boiling flask in proportion, then are passed through the chlorine of respective volume, obtain metering system The mixing liquid of sour methyl esters, butyl acrylate and chlorine；
2) mixing liquid of methyl methacrylate, butyl acrylate and chlorine and acrylic acid by volume 6:1 is mixed in four mouthfuls Flask is added dropwise n-butanol stirring, is reacted 2-4 hours after being warming up to 80 DEG C -90 DEG C, be cooled to room temperature after reaction and depressurize steaming It evaporates, is added after a small amount of dispersant solution dilution and adjusts pH value to 6.5-7.5 with triethylamine, stir to get acrylic resin.
The preparation method of the crosslinking agent is：
1) formalin that mass fraction is 90%-95% is added to melamine in three-necked flask, and in water-bath In be stirred at reflux, be heated to 75 DEG C -90 DEG C react 3-4 hour, until have white crystalline solid substance be precipitated；
2) methanol solution is added, is stirred to react and is all dissolved to material and discharge to obtain high etherified melamine amine-formaldehyde resins.
The preparation method of the modified graphene is：
1) configuration quality score is the liquor potassic permanganate of 2.5%-3.5%；
2) liquor potassic permanganate of 2.5%-3.5%, graphene and the concentrated sulfuric acid are pressed into 200ml：1g：The ratio of 100ml is placed in burning Simultaneously ultrasonic disperse is uniformly mixed in cup；
3) beaker for containing mixed solution is put into heating stirring in water-bath, filters out graphene and be washed till after neutrality to dry and is changed Property graphene.
The preparation method of the composite aqueous paint is：
1) auxiliary rheological agents are added in deionized water, are stirring evenly and then adding into dispersant, antifoaming agent, cosolvent stirring 20min- 30min obtains the deionized water solution of auxiliary agent；
2) in the adjuvant water solution 1) obtained be added modified graphene, titanium dioxide, trbasic zinc phosphate, zinc oxide, iron oxide red, barium sulfate, Silica and talcum powder, then ultrasonic disperse 20min-30min；
3) high etherified melamine amine-formaldehyde resins and antifoaming agent is added in the mixing liquid obtained in 2), then ultrasonic disperse 5min-10min；
4) will in the mixing liquid 3) obtained be added acrylic resin, pH adjusting agent, levelling agent, emulsifier, reactive diluent and Coalescents are uniformly mixed and with strainer filterings more than 200 mesh, obtain composite aqueous paint.
2. composite aqueous paint according to claim 1, which is characterized in that the mass ratio of the zinc oxide and trbasic zinc phosphate is 1:2 to 3:1.
3. composite aqueous paint according to claim 1, which is characterized in that the zinc oxide and trbasic zinc phosphate and high etherificate three The mass ratio of melamine-formaldehyde resin is 3:5 to 3:1, and the mass ratio of zinc oxide and trbasic zinc phosphate and acrylic resin is 1:5 arrive 1:2。
CN201810127071.6A 2018-02-08 2018-02-08 A kind of composite aqueous paint Pending CN108314946A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109504216A (en) * 2018-12-04 2019-03-22 浙江为华新材料有限公司 A kind of graphene modified aqueous acrylic acid coating and preparation method thereof
CN113045976A (en) * 2021-03-16 2021-06-29 广东绿色大地化工有限公司 Nano ceramic anticorrosive water-based paint
CN115029039A (en) * 2022-07-26 2022-09-09 安徽理工大学 Modified anticorrosive paint and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109504216A (en) * 2018-12-04 2019-03-22 浙江为华新材料有限公司 A kind of graphene modified aqueous acrylic acid coating and preparation method thereof
CN113045976A (en) * 2021-03-16 2021-06-29 广东绿色大地化工有限公司 Nano ceramic anticorrosive water-based paint
CN115029039A (en) * 2022-07-26 2022-09-09 安徽理工大学 Modified anticorrosive paint and preparation method thereof

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