CN115160878A - Anticorrosive paint for building exterior wall and preparation method and application thereof - Google Patents

Anticorrosive paint for building exterior wall and preparation method and application thereof Download PDF

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Publication number
CN115160878A
CN115160878A CN202210900228.0A CN202210900228A CN115160878A CN 115160878 A CN115160878 A CN 115160878A CN 202210900228 A CN202210900228 A CN 202210900228A CN 115160878 A CN115160878 A CN 115160878A
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Prior art keywords
parts
zinc oxide
modified
fly ash
graphene oxide
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Inventor
罗宇文
高毅
周洪坤
刘冲
王剑锋
刘健
郑明贵
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Ganzhou Nankang District Tuokang Engineering Project Construction Co ltd
Jiangxi University of Science and Technology
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Ganzhou Nankang District Tuokang Engineering Project Construction Co ltd
Jiangxi University of Science and Technology
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Priority to CN202210900228.0A priority Critical patent/CN115160878A/en
Publication of CN115160878A publication Critical patent/CN115160878A/en
Pending legal-status Critical Current

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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
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D5/004—Reflecting paints; Signal paints
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention belongs to the technical field of anticorrosive coatings, and discloses an anticorrosive coating for an exterior wall of a building, and a preparation method and application thereof; the anticorrosive paint for the building outer wall mainly comprises the following raw materials in parts by weight: 10-35 parts of graphene oxide powder, 1-5 parts of nano zinc oxide, 20-60 parts of film-forming agent, 5-10 parts of fly ash, 0.1-2 parts of aluminum silicate and 2-20 parts of silane coupling agent; the film forming agent is a copolymer emulsion prepared from methyl methacrylate and ethyl acrylate in any proportion. The anticorrosive coating prepared by the invention can realize heat preservation of a wall body, has good hydrophobic and anticorrosive effects, can effectively protect the outer wall of a house in a humid area, especially in a humid area with acid rain weather, and is low in price and easy to obtain raw materials for preparing the anticorrosive coating, thereby being beneficial to popularization and use.

Description

Anticorrosive paint for building exterior wall and preparation method and application thereof
Technical Field
The invention relates to the technical field of anticorrosive coatings, in particular to an anticorrosive coating for an exterior wall of a building, and a preparation method and application thereof.
Background
In the use process of buildings such as houses and the like, because the outer wall of the buildings is exposed for a long time, the service life of the buildings is greatly influenced by external factors such as ultraviolet rays and rainwater, and in order to prolong the service life of the outer wall, the technicians in the field usually adopt the coating to coat the surface of the outer wall for defense. The coating for the outer wall in the prior art is mainly a heat insulation coating, and the coating mainly solves the problems of coating aging, color change and the like caused by wind, sunshine and the like so as to realize the purpose of protecting the outer wall of the building.
However, in south areas such as the west and the river, due to the fact that air is humid, particularly rainwater is abundant in summer and autumn, and rainwater has a certain acid rain frequency, in recent years, although the situation that the west and the river are affected by acid rain is improved gradually, the corrosion of the outer wall of a house is still affected, and therefore, the provision of the anticorrosive paint for the outer wall is particularly important.
However, the anticorrosive coating in the prior art is mainly used for corrosion prevention of a metal matrix or a wood matrix, and is rarely used as an anticorrosive coating for an exterior wall of a building, and due to the difference between matrix materials, the combination between the matrix materials and the coating is different, so that the protection effect of the coating on the matrix materials is influenced, and the protection of the exterior wall cannot be effectively realized by the existing anticorrosive coating.
Therefore, the invention provides an anticorrosive paint for building exterior walls and a preparation method and application thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides an anticorrosive coating for an exterior wall of a building, and a preparation method and application thereof.
The invention relates to an anticorrosive paint for building exterior walls, a preparation method and application thereof, which are realized by the following technical scheme:
the invention aims to provide an anticorrosive paint for building exterior walls, which is prepared from the following main raw materials in parts by weight:
10-35 parts of graphene oxide powder, 1-5 parts of nano zinc oxide, 20-60 parts of film forming agent, 5-10 parts of fly ash, 0.1-2 parts of aluminum silicate and 2-20 parts of silane coupling agent;
the film forming agent is a copolymer emulsion prepared from methyl methacrylate and ethyl acrylate in any proportion.
Further, the silane coupling agent is one or more of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and gamma-aminopropyltriethoxysilane.
Further, the particle size of the fly ash is 5-50 nm.
The second purpose of the invention is to provide a preparation method of the anticorrosive paint for the building exterior wall, which comprises the following steps:
step 1, weighing each preparation raw material with corresponding mass according to the proportioning relation of each preparation raw material for later use;
step 2, carrying out first modification treatment on the nano zinc oxide and the fly ash by using a silane coupling agent to obtain modified nano zinc oxide and modified fly ash;
step 3, carrying out secondary modification treatment on the graphene oxide by using the modified nano zinc oxide and the modified fly ash to obtain modified graphene oxide;
and 4, uniformly dispersing the modified graphene oxide in a film forming agent, and then adding aluminum silicate and uniformly mixing to obtain the anticorrosive paint for the building exterior wall.
Further, in step 2, the specific steps of the first modification treatment are as follows:
uniformly dispersing the nano zinc oxide and the fly ash in a solvent A together or respectively, then adding a silane coupling agent, uniformly mixing, stirring at the temperature of 40-70 ℃ for 2-8 h, carrying out solid-liquid separation, and drying to obtain the modified nano zinc oxide and the modified fly ash.
Further, the solvent A is ethanol or water.
Furthermore, the dosage ratio of the solvent A to the nano zinc oxide is 10-20mL.
Further, in step 2, the specific steps of the second modification treatment are as follows:
uniformly dispersing graphene oxide in a solvent B, adjusting the pH value to 3-5, then adding modified nano zinc oxide and modified fly ash, uniformly dispersing by ultrasonic, then reacting at 78-87 ℃ for 0.5-1.5 h, carrying out solid-liquid separation, and drying to obtain the modified graphene oxide.
Further, the dosage ratio of the graphene oxide to the solvent B is 1-7mg.
Further, the solvent B is ethanol or water.
The third purpose of the invention is to provide the application of the anticorrosive paint for the exterior wall of the building in the protection of the exterior wall of the cement-based building.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the silane coupling agent is used for modifying the nano zinc oxide and the fly ash to make the nano zinc oxide and the fly ash aminated, so that the nano zinc oxide is prevented from self-agglomeration, and the compatibility of the nano zinc oxide, the fly ash and a solvent is improved; and then, under an acidic condition, fully contacting and colliding aminated modified nano zinc oxide and modified fly ash with graphene oxide under the action of ultrasonic waves, so that hydroxyl on the surface of the modified nano zinc oxide, amino grafted to the surface of the modified nano zinc oxide and amino grafted to the surface of the fly ash can be fully bonded with carboxyl on the surface of the graphene oxide, the modification of the graphene oxide by the modified nano zinc oxide and the modified fly ash is realized, the surface energy of the graphene oxide is reduced, the self-aggregation of the graphene oxide is avoided, and the compactness of a two-dimensional network structure of the graphene oxide is improved, so that the isolation effect of the coating on the building outer wall and acidic harmful substances in rainwater is improved, the corrosion resistance of the coating is improved, and the protection effect of the coating on the building outer wall is improved.
The total dosage of the nano zinc oxide and the fly ash is less than that of the graphene oxide, so that the surface of the graphene oxide still has non-bonded carboxyl, and after the coating is coated on the outer wall of the cement-based building, the non-bonded carboxyl on the surface of the graphene oxide in the coating can be mixed with Ca (OH) in the cement-based material along with the fact that the coating is deeply inserted into the outer wall of the cement-based building 2 The reaction occurs to form a stronger covalent bond, which not only can optimize the microstructure of the coating and improve the compactness of the coating, but also can increase the adhesive force between the coating and the cement-based matrix.
The nano zinc oxide has extremely high chemical activity, excellent catalytic activity and photocatalytic activity, has the functions of resisting infrared rays and ultraviolet radiation and sterilizing, can improve the anticorrosion effect of the coating, can simultaneously act synergistically with hollow microsphere components in the fly ash, particularly with floating beads with small density in the fly ash, can effectively reflect light and heat radiation, and improves the heat insulation effect of the coating.
According to the invention, the modified graphene oxide has good solvent compatibility and fluidity, and meanwhile, a plurality of polar oxygen-containing functional groups (such as hydroxyl, epoxy and the like) are also arranged on the graphene oxide, and after the graphene oxide is dispersed in the film forming agent, the polar oxygen-containing functional groups can be grafted on components in the film forming agent, so that the agglomeration of the graphene oxide can be further avoided, the combination among the components in the coating is improved, the uniformity of the coating components is improved, and the anticorrosive coating with stable effect is further obtained.
The aluminum silicate disclosed by the invention can realize a thickening effect, improves the suspension property of the coating components, further can prevent the coating components from settling and improve the uniformity of the coating components; and silicate ions can be dissolved out in the stirring process of the aluminum silicate, so that the silicate ions can perform chemical reaction with calcium ions in the cement-based outer wall, calcium silicate hydrate (dendritic crystals) of water is formed in a network structure, the combination of the coating and the cement-based outer wall is further improved, a dense coating with high adhesive force is formed on the surface of the outer wall, and the protection of the outer wall is further improved.
The anticorrosive coating prepared by the invention can realize heat preservation of a wall body, has good hydrophobic and anticorrosive effects, can effectively protect the outer wall of a house in a humid area, especially in a humid area with acid rain weather, and is low in price and easy to obtain raw materials for preparing the anticorrosive coating, thereby being beneficial to popularization and use.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
Example 1
The embodiment provides an anticorrosive paint for building exterior walls, and the preparation method comprises the following steps:
step 1, weighing preparation raw materials with corresponding mass according to the following mixture ratio for later use;
20 parts of graphene oxide powder, 3 parts of nano zinc oxide, 40 parts of a film forming agent, 8 parts of fly ash, 1 part of aluminum silicate and 10 parts of a silane coupling agent;
the graphene oxide of the present invention is prepared by a modified Hummers method, and the obtained graphene oxide is mechanically ground to pass through a 80-mesh sieve, thereby obtaining a graphene oxide powder having a large number of carboxyl groups attached to the surface. The preparation method of the improved Hummers method is as follows: under the condition of ice bath at 0 ℃, 1g of natural graphite is added into a 500mL three-necked bottle, then 90 to 85mL of concentrated sulfuric acid and 20 to 25mL of concentrated nitric acid are slowly added and continuously stirred for 20 to 60min, and then 6g of KMnO is added 4 Slowly adding the mixture into the solution, and reacting for 40-60 min at the constant temperature of 35 ℃; then, heating to 85 ℃, keeping the temperature for 20-40 min, then dropwise adding 90-85 mL of deionized water within 20-40 min, and then continuously keeping the temperature of 85 ℃ for reaction for 20-4And 0min, gradually changing the color of the solution from dark brown to bright yellow in the process, then cooling the solution to room temperature, dropwise adding 8-12mL of 30% hydrogen peroxide to obtain orange suspension, repeatedly and centrifugally washing the orange suspension by using dilute hydrochloric acid and deionized water until the solution is neutral (the PH is 6.8-7.2), and freezing and drying to obtain the used GO.
Step 2, carrying out first modification treatment on the nano zinc oxide and the fly ash by using a silane coupling agent to obtain modified nano zinc oxide and modified fly ash;
it should be noted that the invention is not limited to the specific components of the silane coupling agent, as long as the amination modification treatment of the nano zinc oxide and the fly ash can be realized. In this example, gamma-aminopropyltriethoxysilane was optionally used as a silane coupling agent.
In this example, zinc oxide nanoflower was used as the nano zinc oxide of this example in order to improve the effect of modifying the amination of the nano zinc oxide. And the present invention is not limited to a specific method for obtaining zinc oxide nanoflower as long as the zinc oxide nanoflower can be obtained. The invention can be selected, and the zinc oxide nano-rice is prepared by the following steps: taking zinc acetate as a zinc source, respectively weighing corresponding mass of zinc acetate, trisodium citrate, sodium hydroxide and polyethylene glycol according to a mass ratio of 4-6:5-7 of 1.
The invention does not limit the specific specification of the fly ash, and the C-grade fly ash with the particle size of 5-50 nm can be selected to prepare the anticorrosive paint.
It should be noted that the invention is not limited to the specific modification mode of the nano zinc oxide and the fly ash, as long as the aminated modified nano zinc oxide and the modified fly ash can be obtained. In this embodiment, the following process is adopted:
according to the dosage ratio of 10-20mL of ethanol to 1g of nano zinc oxide, weighing ethanol with a corresponding volume, uniformly dispersing the weighed nano zinc oxide and fly ash into the ethanol, then adding the weighed silane coupling agent, uniformly mixing, stirring at the temperature of 40-70 ℃ at the speed of 250-350 r/min for 2-8 h, carrying out solid-liquid separation, and drying to obtain a mixture of the modified nano zinc oxide and the modified fly ash.
The specific manner of solid-liquid separation is not limited in step 2 of the present invention, as long as the liquid component can be removed and the solid component can be obtained. In this embodiment, solid-liquid separation may be optionally performed by suction filtration, and the solid product is washed with ethanol and water at least 3 times to remove impurities on the surface of the solid product.
In step 2 of the present invention, the specific drying manner is not limited as long as the excessive solvent on the surface of the solid product can be removed, and in this embodiment, the mixture of the modified nano zinc oxide and the modified fly ash can be obtained by optionally drying in an oven at 50-70 ℃ for 2-6 hours.
Step 3, carrying out secondary modification treatment on the graphene oxide by using the modified nano zinc oxide and the modified fly ash to obtain modified graphene oxide;
the invention is not limited to the specific mode of the second modification treatment, as long as the hydroxyl on the surface of the nano zinc oxide, the amino grafted on the surface of the nano zinc oxide, and the amino grafted on the surface of the fly ash are bonded with the carboxyl on the surface of the graphene oxide, so as to modify the graphene oxide. This embodiment is optional, and the modified graphene oxide is obtained by the following steps:
weighing ethanol with corresponding volume according to the dosage ratio of 1-7 mL of ethanol to 1-7 mL of graphene oxide, subjecting the graphene oxide to ultrasonic treatment with the power of 300-450W for 10-30 min to uniformly disperse the graphene oxide in the ethanol, adjusting the pH value to 3-5, adding the modified nano zinc oxide and the modified fly ash obtained in the step 2, subjecting the graphene oxide to ultrasonic treatment with the power of 300-450W for 10-30 min to uniformly disperse the graphene oxide and the modified fly ash, reacting at the temperature of 78-87 ℃ for 0.5-1.5 h, and performing solid-liquid separation and drying to obtain the modified graphene oxide.
The specific mode of solid-liquid separation is not limited in step 3 of the present invention, as long as the liquid component can be removed to obtain the solid component. In this embodiment, solid-liquid separation may be optionally performed by suction filtration, and the solid product is washed with ethanol and water at least 3 times to remove impurities on the surface of the solid product.
In step 3 of the present invention, the specific drying manner is not limited as long as the excessive solvent on the surface of the solid product can be removed, and in this embodiment, the mixture of the modified nano zinc oxide and the modified fly ash can be obtained by optionally drying in an oven at 50-70 ℃ for 2-6 hours.
Step 4, uniformly dispersing the modified graphene oxide in a film forming agent, then adding aluminum silicate and uniformly mixing to obtain the anticorrosive paint for the building outer wall;
it should be noted that the specific manner of the modified graphene oxide in the film forming agent is not limited in the present invention, as long as the modified graphene oxide can be uniformly dispersed in the film forming agent. In this embodiment, a mode of ultrasonic wave combined with stirring may be optionally used for the dispersion. In the embodiment, methyl methacrylate and ethyl acrylate with equal mass are stirred at the speed of 1500-2500 r/min for 5-10 min, then the modified graphene oxide is added and continuously stirred, and ultrasonic treatment is combined for 5-10 min, so that the modified graphene oxide is uniformly dispersed in the film forming agent.
It should be noted that the invention does not limit the specific manner of mixing the aluminum silicate, as long as the aluminum silicate can be uniformly dispersed in the mixed solution of the modified graphene oxide and the film forming agent. In this embodiment, the dispersion may be performed by stirring. In this embodiment, the stirring is performed at a speed of 100 to 250r/min for 10 to 60min.
Example 2
The embodiment provides an anticorrosive paint for building exterior walls, and the preparation method of the anticorrosive paint is different from that of the embodiment 1 as follows:
in step 1 of this embodiment, each preparation raw material with corresponding mass is weighed for use according to the following ratio;
10 parts of graphene oxide powder, 1 part of nano zinc oxide, 20 parts of a film forming agent, 5 parts of fly ash, 0.1 part of aluminum silicate and 2 parts of a silane coupling agent;
the graphene oxide of the present example was prepared by a modified Hummers method, and the obtained graphene oxide was mechanically ground to pass through a 100-mesh sieve.
This example, step 2, uses N- (. Beta. -aminoethyl) -gamma. -aminopropyltrimethoxysilane as the silane coupling agent.
The C-grade fly ash with the particle size of 5nm is adopted to prepare the anticorrosive paint.
In this example, the following process was used for the first modification treatment:
weighing ethanol with corresponding volume according to the dosage ratio of ethanol to 10mL of nano zinc oxide to 1g of nano zinc oxide, uniformly dispersing the weighed nano zinc oxide and fly ash into the ethanol, then adding the weighed silane coupling agent, uniformly mixing, stirring at the temperature of 40 ℃ at the speed of 250r/min for 8 hours, centrifuging, and drying in a 50 ℃ oven for 6 hours to obtain a mixture of the modified nano zinc oxide and the modified fly ash.
In step 3 of this embodiment, modified graphene oxide is obtained by the following steps:
weighing ethanol with corresponding volume according to the dosage ratio of the ethanol to the graphene oxide 1g in the volume of 1mL, subjecting the graphene oxide to ultrasonic treatment with the power of 300W for 30min to uniformly disperse the graphene oxide in the ethanol, adjusting the pH value to 3, adding the modified nano zinc oxide and the modified fly ash obtained in the step 2, subjecting the graphene oxide to ultrasonic treatment with the power of 300W for 30min to uniformly disperse the graphene oxide and the modified fly ash, reacting at the temperature of 78 ℃ for 1.5h, centrifuging, and drying in an oven at the temperature of 50 ℃ for 6h to obtain a mixture of the modified nano zinc oxide and the modified fly ash.
In step 4 of this example, a film forming agent (a copolymer emulsion prepared by mixing methyl methacrylate and ethyl acrylate at a mass ratio of 1.5.
Example 3
The embodiment provides an anticorrosive paint for building exterior walls, and the preparation method of the anticorrosive paint is different from that of the embodiment 1 as follows:
in step 1 of this embodiment, each preparation raw material with a corresponding mass is weighed for use according to the following ratio;
35 parts of graphene oxide powder, 5 parts of nano zinc oxide, 60 parts of a film forming agent, 5 parts of fly ash, 2 parts of aluminum silicate and 20 parts of a silane coupling agent;
the graphene oxide of the present example is prepared by a modified Hummers method, and the obtained graphene oxide is mechanically ground to pass through a 60-mesh sieve.
This example, step 2, uses N- (. Beta. -aminoethyl) -gamma. -aminopropyltrimethoxysilane as the silane coupling agent.
The C-grade fly ash with the particle size of 50nm is adopted to prepare the anticorrosive paint.
In this example, the following process was used for the first modification treatment:
weighing ethanol with corresponding volume according to the dosage ratio of the ethanol to the nano zinc oxide of 20mL of 1g, uniformly dispersing the weighed nano zinc oxide and the fly ash into the ethanol, adding the weighed silane coupling agent, uniformly mixing, stirring at the temperature of 70 ℃ at the speed of 350r/min for 8 hours, centrifuging, and drying in an oven at the temperature of 70 ℃ for 2 hours to obtain a mixture of the modified nano zinc oxide and the modified fly ash.
In step 3 of this embodiment, modified graphene oxide is obtained by the following steps:
weighing ethanol with corresponding volume according to the dosage ratio of the ethanol to the graphene oxide of 1g/7mL, subjecting the graphene oxide to ultrasonic treatment with power of 450W for 10min to uniformly disperse the graphene oxide in the ethanol, adjusting the pH value to 5, adding the modified nano zinc oxide and the modified fly ash obtained in the step 2, subjecting the graphene oxide to ultrasonic treatment with power of 450W for 10min to uniformly disperse the graphene oxide, reacting at 87 ℃ for 1.5h, centrifuging, and drying in an oven at 70 ℃ for 2h to obtain a mixture of the modified nano zinc oxide and the modified fly ash.
In step 4 of this example, a film forming agent (a copolymer emulsion prepared by mixing methyl methacrylate and ethyl acrylate at a mass ratio of 1.5) was stirred at a speed of 2500r/min for 5min, then modified graphene oxide was added and stirring was continued while applying ultrasonic treatment at a power of 450W for 5min, then aluminum silicate was added and stirring was performed at a speed of 250r/min for 10min.
Comparative example 1
The comparative example provides an anticorrosive paint for building exterior walls, and the comparative example is different from example 1 only in that: this comparative example does not contain nano-zinc oxide.
Comparative example 2
The comparative example provides an anticorrosive paint for building exterior walls, and the comparative example is different from example 1 only in that: this comparative example contained no fly ash.
Comparative example 3
The comparative example provides an anticorrosive paint for building exterior walls, and the comparative example is different from example 1 only in that: this comparative example contained no aluminum silicate.
Comparative example 4
The comparative example provides an anticorrosive paint for building exterior walls, and the comparative example is different from example 1 only in that: the present comparative example does not contain graphene oxide.
Test section
(I) adhesion test
The anticorrosive coatings of examples 1 to 3 and comparative examples 1 to 4 are used as examples, and the test and evaluation are carried out according to the method of GB/T1720-79 (89) coating adhesion determination method (circled method), and the test results are shown in Table 1.
As can be seen from the data in Table 1, the adhesion ratings of examples 1-3 and comparative examples 1-2 are all 1, while the adhesion ratings of comparative examples 3-4 are all 2, which shows that the aluminum silicate and the graphene oxide in the present invention have a significant effect on the adhesion of the coating of the present invention, and also shows that the good adhesion of the present invention is achieved by the synergistic effect of the components, especially the aluminum silicate and the graphene oxide.
(II) Water resistance
The anticorrosive coatings of examples 1 to 3 and comparative examples 1 to 4 were tested for water resistance (test was stopped at 720 h) and evaluated according to the method described in GB/T1733-1993, and the test results are shown in Table 1.
As can be seen from the data in table 1: the appearances of examples 1-3 and comparative example 3 were not obviously abnormal, while the paint films of comparative example 1, comparative example 2 and comparative example 4 were abnormal to different degrees, which shows that nano zinc oxide and graphene oxide have obvious influence on the water resistance of the paint, and aluminum silicate has certain influence on the water resistance of the paint, and shows that the good water resistance of the invention is achieved by the synergistic effect of the components, especially nano zinc oxide, aluminum silicate and graphene oxide.
(III) acid resistance
The anticorrosive coatings of examples 1-3 and comparative examples 1-4 were tested for acid resistance according to the method for testing the chemical resistance of paint films of GB1763-89, and the test results are shown in Table 1.
The specific test is as follows: soaking 2/3 of the coating plate in a sulfuric acid solution with the temperature of 25 ℃ and the mass fraction of 4.5% respectively, taking out every 24 hours, cleaning the coating plate with water, wiping the surface with absorbent paper, and checking whether the surface of a paint film has the conditions of discoloration, light loss, bubbles, spots, falling off and the like.
As can be seen from the data in table 1: the acid resistance of examples 1-3 was not much different and was significantly better than that of comparative examples 1-4. Moreover, the acid resistance of the paint films of comparative examples 1 and 4 is not only obviously lower than that of examples 1-3, but also obviously lower than that of comparative examples 2 and 3, which shows that the nano zinc oxide and the graphene oxide have obvious influence on the alkali resistance and the acidity of the paint, and also shows that the good acid resistance of the paint is realized by the synergistic action of the components, especially the nano zinc oxide and the graphene oxide.
(IV) alkali resistance
The alkali resistance of the anticorrosive coatings of examples 1-3 and comparative examples 1-4 is tested according to the method for testing the chemical reagent resistance of the paint film of GB1763-89, and the test results are shown in Table 1.
The specific test is as follows: and respectively soaking 2/3 of the coating plate in sodium hydroxide solution with the temperature of 25 ℃ and the mass fraction of 4.5%, taking out every 24 hours, cleaning the coating plate with water, wiping the surface with moisture absorption paper, and checking whether the surface of the paint film has the conditions of discoloration, light loss, bubbles, spots, falling and the like.
As can be seen from the data in table 1: the results of the alkali resistance test were similar to those of the acid resistance test, and the alkali resistance of examples 1 to 3 was not greatly different and was significantly superior to that of comparative examples 1 to 4. Moreover, the alkali resistance of the paint films of comparative examples 1 and 4 is not only obviously lower than that of examples 1-3, but also obviously lower than that of comparative examples 2 and 3, which shows that the nano zinc oxide and the graphene oxide have obvious influence on the alkali resistance of the paint, and also shows that the good alkali resistance of the paint is realized by the synergistic action of the components, especially the nano zinc oxide and the graphene oxide.
(V) resistance to moist Heat
The invention tests the wet heat resistance of the anticorrosive coatings of examples 1-3 and comparative examples 1-4 according to the method for measuring the wet heat resistance of paint films of GB/T1740-2007, and the test results are shown in Table 1.
As can be seen from the test results of table 1: the influence of the nano zinc oxide and the graphene oxide on the moisture and heat resistance of the paint is the largest, and the influence of the fly ash and the aluminum silicate is the second, which shows that the good moisture and heat resistance of the paint is realized by the synergy of all the components.
TABLE 1 Performance test results for coatings
Figure BDA0003770663550000131
Figure BDA0003770663550000141
In conclusion, the anticorrosive coating for the exterior wall of the building, prepared by the invention, has good hydrophobicity, corrosion resistance, good adhesion effect on a cement-based matrix and good moist heat resistance, and can be used for protecting the exterior wall of the cement-based building.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. The anticorrosive paint for the building outer wall is characterized by mainly comprising the following preparation raw materials in parts by weight:
10-35 parts of graphene oxide powder, 1-5 parts of nano zinc oxide, 20-60 parts of film forming agent, 5-10 parts of fly ash, 0.1-2 parts of aluminum silicate and 2-20 parts of silane coupling agent;
the film forming agent is a copolymer emulsion prepared from methyl methacrylate and ethyl acrylate in any proportion.
2. The anticorrosive paint for exterior walls of buildings according to claim 1, wherein the silane coupling agent is one or more of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and gamma-aminopropyltriethoxysilane.
3. The anticorrosive paint for exterior walls of buildings according to claim 1, wherein the particle size of the fly ash is 5-50 nm.
4. A method for preparing the anticorrosive paint for the exterior wall of the building according to any one of claims 1 to 3, characterized by comprising the following steps:
step 1, weighing each preparation raw material with corresponding mass according to the proportion relation of each preparation raw material for later use;
step 2, carrying out first modification treatment on the nano zinc oxide and the fly ash by using a silane coupling agent to obtain modified nano zinc oxide and modified fly ash;
step 3, carrying out secondary modification treatment on the graphene oxide by using the modified nano zinc oxide and the modified fly ash to obtain modified graphene oxide;
and 4, uniformly dispersing the modified graphene oxide in a film forming agent, and then adding aluminum silicate and uniformly mixing to obtain the anticorrosive paint for the building exterior wall.
5. The preparation method according to claim 4, wherein in the step 2, the specific steps of the first modification treatment are as follows:
uniformly dispersing the nano zinc oxide and the fly ash in a solvent A together or respectively, then adding a silane coupling agent, uniformly mixing, stirring at the temperature of 40-70 ℃ for 2-8 h, carrying out solid-liquid separation, and drying to obtain the modified nano zinc oxide and the modified fly ash.
6. The method according to claim 5, wherein the solvent A is ethanol or water.
7. The preparation method according to claim 5, wherein the ratio of the solvent A to the nano zinc oxide is 10 to 20mL.
8. The preparation method according to claim 4, wherein in the step 2, the second modification treatment comprises the following specific steps:
uniformly dispersing graphene oxide in a solvent B, adjusting the pH value to 3-5, then adding modified nano zinc oxide and modified fly ash, uniformly dispersing by ultrasonic, then reacting at 78-87 ℃ for 0.5-1.5 h, carrying out solid-liquid separation, and drying to obtain the modified graphene oxide.
9. The preparation method according to claim 8, wherein the amount ratio of the graphene oxide to the volatile solvent B is 1 to 7 mg;
the solvent B is ethanol or water.
10. Use of the anticorrosive coating for exterior walls of buildings according to any one of claims 1 to 3 in the protection of exterior walls of cement-based buildings.
CN202210900228.0A 2022-07-28 2022-07-28 Anticorrosive paint for building exterior wall and preparation method and application thereof Pending CN115160878A (en)

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