CN110484064B - Aluminum paste fluorocarbon coating and preparation method thereof - Google Patents

Aluminum paste fluorocarbon coating and preparation method thereof Download PDF

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CN110484064B
CN110484064B CN201910809300.7A CN201910809300A CN110484064B CN 110484064 B CN110484064 B CN 110484064B CN 201910809300 A CN201910809300 A CN 201910809300A CN 110484064 B CN110484064 B CN 110484064B
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aluminum paste
parts
micro powder
opal shale
agent
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CN110484064A (en
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王军胜
常好亮
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SHENZHEN DIANJING PRECIOUS METALS REFINE 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses an aluminum paste fluorocarbon coating, which comprises the following components in parts by weight: 18-35 parts of waterborne fluorocarbon resin, 13-24 parts of polyurethane resin, 0.5-1 part of titanate modified graphene, 0.2-1 part of silane coupling agent, 6-23 parts of waterborne aluminum paste, 1-3 parts of opal shale micro powder and opal shale micro powder loaded TiO22-5 parts of ethylene glycol, 5-9 parts of dispersing agent, 0.1-1.5 parts of flatting agent, 0.1-1.5 parts of defoaming agent, 0.1-0.6 part of pH regulator and 15-28 parts of deionized water. According to the invention, the aqueous fluorocarbon resin and the polyurethane resin are mixed in proportion to be used as the matrix material, so that the coating has good comprehensive performance, and the opal shale micro powder, the titanate modified graphene, the silane coupling agent and the polyethylene glycol are used for promoting the directional arrangement of aluminum paste, so that the coating has high metallic luster.

Description

Aluminum paste fluorocarbon coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, in particular to an aluminum paste fluorocarbon coating and a preparation method thereof.
Background
The aluminum paste is a pasty metal pigment treated by a certain process, the aluminum has a snowflake shape, a fish scale shape and a silver element shape, and the aluminum paste is characterized in that the surface of an aluminum sheet is smooth and flat, the particle size distribution is concentrated, the shape is regular, the aluminum paste has excellent light reflection capability and metal luster, the aluminum paste is mixed with a transparent pigment for use, a paint film has an obvious angle-dependent heterochromatic effect, the decorative effect is gorgeous and beautiful, and the aluminum paste is mainly used for automobile paints, plastic paints, metal industrial paints, ship paints, heat-resistant paints, roof paints and the like.
The fluorocarbon coating has the advantages of water resistance, solvent resistance, pollution resistance, high hardness, weather resistance, durability and the like. However, the existing fluorocarbon coating mainly adopts a solvent type and contains high VOC, the solvent is directly volatilized into the air during construction and cannot be recycled, so that resource waste is caused, the environment is polluted, and certain toxicity is caused to constructors.
Chinese patent document CN107033710A discloses a preparation method of a breathable environment-friendly fluorocarbon coating, which comprises the steps of immersing a carbon nano tube in 1-hexyl-3-methylimidazolium tetrafluoroborate, drying, heating and preserving heat to obtain a first prefabricated material; uniformly mixing talcum powder, titanium nitrate, saturated ammonia water and water, carrying out hydrothermal reaction, and drying to obtain a second prefabricated material; adding a second prefabricated material, chlorosulfonated polyethylene and a titanate coupling agent into the first prefabricated material, heating and drying to obtain a first material; sequentially adding cocamidopropyl betaine and polyvinyl alcohol into water, uniformly stirring, continuously adding a pH regulator, a defoaming agent, a first material, fumed silica, carbon fibers, aqueous aluminum paste and a film-forming aid, and uniformly stirring to obtain a second material; and adding the fluorine modified acrylate emulsion, the epoxy resin emulsion, the preservative and the mildew preventive into the second material, stirring, continuously adding the xanthan gum, the polyether polyester modified organosiloxane and the adhesion promoter, and uniformly stirring to obtain the breathable environment-friendly fluorocarbon coating. The coating has the advantages of high tensile strength and impact strength, difficulty in cracking, good thermal stability, excellent aging resistance and corrosion resistance, but has the problems of low glossiness, VOC release amount only meeting the standard and less than 50g/L, environmental protection property to be improved, complex preparation steps, more raw material types and high cost.
The existing aluminum paste fluorocarbon coating has the problems of low gloss, poor adhesive force, low corrosion resistance, easiness in foaming and the like caused by overhigh VOC and poor directional arrangement of aluminum paste. Therefore, the research and development of the water-based aluminum paste fluorocarbon coating with low VOC, strong gloss sense, strong adhesive force and good corrosion resistance is of great significance.
Disclosure of Invention
The invention provides the environment-friendly aluminum paste fluorocarbon coating which has high glossiness, high water resistance and corrosion resistance, is simple to prepare and low in cost and can be produced in batch and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the aluminum paste fluorocarbon coating comprises the following components in parts by weight: 18-35 parts of waterborne fluorocarbon resin, 13-24 parts of polyurethane resin, 0.5-1 part of titanate modified graphene, 0.2-1 part of silane coupling agent, 6-23 parts of waterborne aluminum paste, 1-3 parts of opal shale micro powder and opal shale micro powder loaded TiO22 to 5 portions of glycol, 5 to 9 portions of glycol, 0.1 to 1.5 portions of dispersant, 0.1 to 1.5 portions of flatting agent, 0.3 to 1.5 portions of defoaming agent and pH regulator0.1-0.6 part and 15-28 parts of deionized water.
Further, the preparation method of the titanate modified graphene comprises the following steps: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
Further, in the preparation method of the titanate modified graphene, the mass ratio of the graphene oxide to the titanate coupling agent TM-200S is 1: 7.
Further, the aqueous aluminum silver paste is a double-layer coated aluminum silver paste, and the preparation method comprises the following steps: dispersing the silicon dioxide coated aluminum paste in ethanol, sequentially adding a methyl methacrylate monomer, a butyl acrylate monomer, a hexafluorobutyl methacrylate monomer and an acrylic acid monomer, then adding an initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated with the fluorine-containing acrylate and the silicon dioxide in double layers.
Further, the particle size of the opal shale micro powder is 10-20 μm.
Further, the opal shale micro powder loads TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, stopping dropwise adding after the pH value is measured to be 10, continuing the water bath reaction for 1h, filtering, drying the obtained filter residue in an oven for 2h at the drying temperature of 120 ℃, and finally taking out and grinding to obtain the compound.
Further, the polyethylene glycol has an average molecular weight of 4000.
Further, the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
A preparation method of aluminum paste fluorocarbon coating comprises the following steps:
adding part of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest part of deionized water into a blending tank, and then adding aqueous fluorocarbon resin, polyurethane resin, ethylene glycol and opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
Further, the power of ultrasonic treatment in the step one is 200W, and the time is 40-60 min.
According to the invention, the waterborne fluorocarbon resin and polyurethane resin are adopted as the coating matrix material, the waterborne fluorocarbon resin has high crosslinking density and good weather resistance, the waterborne polyester resin has good oil resistance, toughness and wear resistance, the titanate modified graphene can be coupled with the resin, the graphene has excellent characteristics of high mechanical strength, high temperature resistance and corrosion resistance, the combination of the graphene and the resin matrix can improve the comprehensive performance of the coating, meanwhile, PEG-4000 added in the preparation process can be used as a carrier of a solid dispersing agent in cooperation with opal shale to achieve the purpose of promoting solid dispersion, and after coating construction, the two can adjust the volatilization rate of a solvent to ensure that aluminum paste is directionally arranged, so that the metallic luster of the coating is improved; in addition, the cracking and bubbling of the coating can be effectively prevented through the porous nano structure of the opal nano micro powder combined by the silane coupling agent and the matrix material.
According to the preparation method of the water-based aluminum silver paste, silicon dioxide coated aluminum silver paste is used as a raw material and is mixed with four monomers for reaction, wherein methyl methacrylate endows the coating layer with hardness; the hexafluorobutyl methacrylate ensures that the coating layer has good adhesive force on the surface of the silicon dioxide aluminum paste, and simultaneously improves the aging resistance of the coating layer; butyl acrylate makes the coating layer flexible; the acrylic acid endows the coating layer with good mechanical stability, and is further optimized, and the water-based aluminum silver paste has optimal hydrophobicity, acid and alkali resistance, aging resistance and soluble salt resistance when the proportion of the methyl methacrylate monomer, the butyl acrylate monomer, the hexafluorobutyl methacrylate monomer and the acrylic acid monomer is 2:4:3: 6.
The method firstly activates the opal shale micro powder by two steps of high-temperature calcination and phosphoric acid treatment to increase the specific surface area, and adopts TiO only2The active material does not have visible light catalytic activity, and good anatase titanium dioxide is obtained after the active material is loaded on the activated opal shale micro powder by a hydrolytic precipitation method, and simultaneously, the residual phosphorus and sulfur elements in the opal shale dope titanium dioxide crystals, so that the opal shale micro powder is loaded with TiO2The visible light catalytic efficiency can reach 90%.
According to the invention, firstly, the waterborne aluminum paste is pre-dispersed in deionized water, the opal shale micro powder, the titanate modified graphene and the silane coupling agent are added, under the ultrasonic action, the silane coupling agent and the titanate modified graphene can be combined with the opal shale micro powder to form a continuous network structure, the uniform dispersion of the waterborne aluminum paste is promoted, the directional arrangement of aluminum powder in a coating is facilitated, and the silane coupling agent contains a crosslinkable curing group-OCH3After the second step is mixed with the resin component, crosslinking and curing can be carried out, so that the mechanical strength and the hardness of the coating are improved; the titanate modified graphene can be coupled with surface groups of opal shale and aqueous aluminum paste, so that the dispersion uniformity and the fluidity of the pre-dispersion liquid of the aluminum paste are improved, and the generation of mottling on a coating can be avoided.
The opal shale micro powder of the invention loads TiO2The catalyst is loaded with TiO in situ through activated opal micro powder with large specific surface area2Not only effectively avoids the phenomenon that titanium dioxide nano particles directly added into the coating are easy to agglomerate and inactivate, but also ensures thatTo obtain TiO2The catalyst has high photocatalytic activity, can be uniformly distributed with aluminum paste in the coating under the action of a silane coupling agent, and is firmly combined with the coating matrix due to the good compatibility between the opal shale micro powder and the matrix resin, so that catalyst particles are not easy to lose in the using process of the coating; because the opal shale has good adsorption performance, the opal shale can adsorb gas organic pollutants, provides higher reactant concentration for photocatalytic reaction, further improves the photocatalytic degradation rate, and greatly reduces the VOC of the coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the aluminum paste fluorocarbon coating provided by the invention, the water-based aluminum paste is coated by two layers, so that the luster is strong, the opal shale micro powder, the titanate modified graphene and the silane coupling agent are added, cellulose acetate butyrate is not required, the directional arrangement of the aluminum paste in the coating can be promoted, the luster can reach over 90, the coating cost is reduced, the aluminum paste has good water resistance, wear resistance and corrosion resistance, and the luster is not reduced after long-term use;
(2) according to the aluminum paste fluorocarbon coating provided by the invention, the aqueous fluorocarbon resin and the polyurethane resin are mixed in proportion to serve as the matrix material, the excellent characteristics of the aqueous fluorocarbon resin and the polyurethane resin can be integrated, so that the coating has good impact strength, tensile strength, wear resistance and weather resistance, the titanate modified graphene can be coupled with the resin matrix, the strength and corrosion resistance of the coating are further improved, compared with other inorganic fillers, the opal shale micropowder is light in weight, so that the coating is easy to disperse and does not settle, the solid dispersibility of the coating is improved together with PEG-4000, and the directional arrangement of aluminum paste is promoted;
(3) the opal shale micro powder added in the aluminum paste fluorocarbon coating provided by the invention is loaded with TiO2Not only can absorb ultraviolet rays, but also can reflect and scatter the ultraviolet rays, greatly improves the ultraviolet ray aging resistance of the coating, has very high photocatalytic activity, can quickly decompose and mineralize organic pollutants absorbed by the opal shale, and meanwhile, the opal shale micro powder can also release negative ions to purifyAir.
(4) The aluminum paste fluorocarbon coating provided by the invention is simple in preparation method, low in cost, good in adhesive force to metal, plastic and concrete base materials and wide in application range.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following detailed description is given with reference to specific embodiments.
Example 1
The aluminum paste fluorocarbon coating comprises the following components in parts by weight: 18 parts of waterborne fluorocarbon resin, 13 parts of polyurethane resin, 0.5 part of titanate modified graphene, 0.2 part of silane coupling agent, 6 parts of waterborne aluminum paste, 1 part of opal shale micro powder and TiO loaded on the opal shale micro powder22 parts of ethylene glycol, 5 parts of dispersing agent, 0.1 part of flatting agent, 0.3 part of defoaming agent, 0.1 part of pH regulator and 15 parts of deionized water.
Further, the preparation method of the titanate modified graphene comprises the following steps: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
Further, in the preparation method of the titanate modified graphene, the mass ratio of the graphene oxide to the titanate coupling agent TM-200S is 1: 7.
Further, the aqueous aluminum silver paste is a double-layer coated aluminum silver paste, and the preparation method comprises the following steps: dispersing the silicon dioxide coated aluminum paste in ethanol, sequentially adding a methyl methacrylate monomer, a butyl acrylate monomer, a hexafluorobutyl methacrylate monomer and an acrylic acid monomer, then adding an initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated with the fluorine-containing acrylate and the silicon dioxide in double layers.
Further, the particle size of the opal shale micro powder is 10-20 μm.
Further, the opal shale micro powderSupported TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, stopping dropwise adding after the pH value is measured to be 10, continuing the water bath reaction for 1h, filtering, drying the obtained filter residue in an oven for 2h at the drying temperature of 120 ℃, and finally taking out and grinding to obtain the compound.
Further, the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
A preparation method of aluminum paste fluorocarbon coating comprises the following steps:
adding 5 parts of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest 10 parts of deionized water into a blending tank, and then adding aqueous fluorocarbon resin, polyurethane resin, ethylene glycol and opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
Further, the power of the ultrasonic treatment in the step one is 200W, and the time is 40 min.
Example 2
The aluminum paste fluorocarbon coating comprises the following components in parts by weight: 22 parts of waterborne fluorocarbon resin, 15 parts of polyurethane resin, 0.6 part of titanate modified graphene and 0.3 part of silane coupling agent8 parts of water-based aluminum paste, 1.5 parts of opal shale micro powder and TiO loaded opal shale micro powder23 parts, 6 parts of ethylene glycol, 0.5 part of dispersing agent, 0.5 part of flatting agent, 0.6 part of defoaming agent, 0.2 part of pH regulator and 17 parts of deionized water.
Further, the preparation method of the titanate modified graphene comprises the following steps: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
Further, in the preparation method of the titanate modified graphene, the mass ratio of the graphene oxide to the titanate coupling agent TM-200S is 1: 7.
Further, the aqueous aluminum silver paste is a double-layer coated aluminum silver paste, and the preparation method comprises the following steps: dispersing the silicon dioxide coated aluminum paste in ethanol, sequentially adding a methyl methacrylate monomer, a butyl acrylate monomer, a hexafluorobutyl methacrylate monomer and an acrylic acid monomer, then adding an initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated with the fluorine-containing acrylate and the silicon dioxide in double layers.
Further, the particle size of the opal shale micro powder is 10-20 μm.
Further, the opal shale micro powder loads TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, stopping dropwise adding after the pH value is measured to be 10, continuing the water bath reaction for 1h, filtering, drying the obtained filter residue in an oven for 2h at the drying temperature of 120 ℃, and finally taking out and grinding to obtain the compound.
Further, the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
A preparation method of aluminum paste fluorocarbon coating comprises the following steps:
adding 6 parts of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest 11 parts of deionized water into a blending tank, and then adding aqueous fluorocarbon resin, polyurethane resin, ethylene glycol and opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
Further, the power of the ultrasonic treatment in the step one is 200W, and the time is 45 min.
Example 3
The aluminum paste fluorocarbon coating comprises the following components in parts by weight: 30 parts of waterborne fluorocarbon resin, 20 parts of polyurethane resin, 0.8 part of titanate modified graphene, 0.9 part of silane coupling agent, 19 parts of waterborne aluminum paste, 2 parts of opal shale micro powder and TiO loaded on the opal shale micro powder24 parts of ethylene glycol, 8 parts of dispersing agent, 1 part of flatting agent, 1 part of defoaming agent, 0.5 part of pH regulator and 23 parts of deionized water.
Further, the preparation method of the titanate modified graphene comprises the following steps: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
Further, in the preparation method of the titanate modified graphene, the mass ratio of the graphene oxide to the titanate coupling agent TM-200S is 1: 7.
Further, the aqueous aluminum silver paste is a double-layer coated aluminum silver paste, and the preparation method comprises the following steps: dispersing the silicon dioxide coated aluminum paste in ethanol, sequentially adding a methyl methacrylate monomer, a butyl acrylate monomer, a hexafluorobutyl methacrylate monomer and an acrylic acid monomer, then adding an initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated with the fluorine-containing acrylate and the silicon dioxide in double layers.
Further, the particle size of the opal shale micro powder is 10-20 μm.
Further, the opal shale micro powder loads TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, stopping dropwise adding after the pH value is measured to be 10, continuing the water bath reaction for 1h, filtering, drying the obtained filter residue in an oven for 2h at the drying temperature of 120 ℃, and finally taking out and grinding to obtain the compound.
Further, the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
A preparation method of aluminum paste fluorocarbon coating comprises the following steps:
adding 8 parts of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest 15 parts of deionized water into a blending tank, and then adding the waterborne fluorocarbon resin, the polyurethane resin, the ethylene glycol,Opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
Further, the power of the ultrasonic treatment in the step one is 200W, and the time is 50 min.
Example 4
The aluminum paste fluorocarbon coating comprises the following components in parts by weight: 35 parts of waterborne fluorocarbon resin, 24 parts of polyurethane resin, 1 part of titanate modified graphene, 1 part of silane coupling agent, 23 parts of waterborne aluminum paste, 3 parts of opal shale micro powder, and opal shale micro powder loaded TiO25 parts of ethylene glycol 9 parts, 1.5 parts of dispersing agent, 1.5 parts of flatting agent, 1.5 parts of defoaming agent, 0.6 part of pH regulator and 28 parts of deionized water.
Further, the preparation method of the titanate modified graphene comprises the following steps: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
Further, in the preparation method of the titanate modified graphene, the mass ratio of the graphene oxide to the titanate coupling agent TM-200S is 1: 7.
Further, the aqueous aluminum silver paste is a double-layer coated aluminum silver paste, and the preparation method comprises the following steps: dispersing the silicon dioxide coated aluminum paste in ethanol, sequentially adding a methyl methacrylate monomer, a butyl acrylate monomer, a hexafluorobutyl methacrylate monomer and an acrylic acid monomer, then adding an initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated with the fluorine-containing acrylate and the silicon dioxide in double layers.
Further, the particle size of the opal shale micro powder is 10-20 μm.
Further, the opal shale micro powder loads TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, stopping dropwise adding after the pH value is measured to be 10, continuing the water bath reaction for 1h, filtering, drying the obtained filter residue in an oven for 2h at the drying temperature of 120 ℃, and finally taking out and grinding to obtain the compound.
Further, the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
A preparation method of aluminum paste fluorocarbon coating comprises the following steps:
adding 10 parts of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest 18 parts of deionized water into a blending tank, and then adding aqueous fluorocarbon resin, polyurethane resin, ethylene glycol and opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
Further, the power of the ultrasonic treatment in the step one is 200W, and the time is 60 min.
Comparative example 1
The same as in example 3 was performed, except that the titanate-modified graphene was replaced with graphene oxide.
Comparative example 2
The procedure of example 3 was followed except that the aqueous aluminum paste was replaced with a silica-coated aluminum paste.
Comparative example 3
The procedure of example 3 was repeated except that the aqueous aluminum paste, which was a double-layer aluminum paste containing fluoroacrylate and silica, was replaced with an acrylic ester-and silica-coated aluminum paste.
Comparative example 4
Not containing opal shale micro powder, and loading the opal shale micro powder with TiO2Replaced by supported TiO2Equal mass of TiO2The procedure of example 3 was repeated except for using nanoparticles.
Comparative example 5
The same procedure as in example 3 was conducted except that the opal shale fine powder was replaced with the opal shale which was not subjected to the activation treatment.
Comparative example 6
The procedure is as in example 3 except that no polyethylene glycol is included.
Comparative example 7
The procedure of example 3 was followed except that the components other than the auxiliary agent were added to the preparation tank without predispersion of aluminum paste.
Performance testing
And (3) selecting a tinplate substrate treated in the same way, painting the products obtained in the examples 1-4 and the comparative examples 1-7 on the surface of the substrate, spraying the products with the painting thickness of 30 mu m, standing or air-drying for 5-10 minutes, naturally drying to obtain the aluminum silver paste fluorocarbon coating, and performing solid drying at normal temperature for 24 hours and complete drying for 7 days.
And (3) testing acid resistance: the coating is at 0.05mol/L H2SO4Soaking in the solution for 1 day;
alkali resistance test: soaking the coating in 0.1mol/L NaOH solution for 1 day;
and other performance tests were performed on the coatings according to the relevant standards, and the results are shown in table 1.
TABLE 1 test results of the coating sample performance of examples 1-4 and comparative examples 1-6
Figure BDA0002184603560000091
Figure BDA0002184603560000101
The test results in table 1 show that the aluminum paste fluorocarbon coating provided by the invention has the advantages of low VOC (volatile organic compounds) release amount, high gloss, high pollution resistance, good mechanical property, strong water resistance, strong acid-base corrosion resistance and excellent aging resistance. The comparative example 1 replaces titanate modified graphene with graphene oxide, the graphene oxide and a resin matrix have no coupling effect, the bonding firmness is weakened, the mechanical strength of the coating is reduced, the directional arrangement of aluminum paste is also influenced, the glossiness, the hardness and the wear resistance of the coating are reduced, and the acid and alkali resistance of the coating is inferior to that of the example 3; the comparative example 2 replaces the waterborne aluminum paste with silicon dioxide coated aluminum paste, the wear resistance, acid and alkali resistance and aging resistance of the coating are obviously reduced, and the gloss and impact resistance are also slightly reduced, which shows that the fluorine-containing acrylate on the outer layer of the aluminum paste can play the effects of resisting wear, isolating acid and alkali and protecting the gloss of the aluminum paste from being reduced. Comparative example 3 the aluminum paste coated by the fluorine-containing acrylate and the silicon dioxide double layer is replaced by the aluminum paste coated by the acrylate and the silicon dioxide, the gloss of the coating is slightly reduced, and the aging resistance is also obviously reduced, because the fluorine-containing acrylate has the advantages of compact film forming and good weather resistance, the coating can play a better protection role for the aluminum paste, the film forming property of the acrylate is not as good as that of the fluorine-containing acrylate, the aluminum paste can contact oxygen and water in the preparation and coating processes, so the gloss is not as good as that of the embodiment, and the aging resistance of the aluminum paste is poorer than that of the fluorine-containing acrylate, so the aging resistance is reduced. Comparative example 4 contains no opal shale micropowder, has a VOC emission more than twice that of the example, TiO2The coating is directly added in a non-load mode, so that the luster, hardness and adhesive force of the coating are obviously reduced, the impact resistance and elongation at break are also greatly reduced, the water resistance and acid and alkali resistance are deteriorated, and the foaming phenomenon, cracks, discoloration and light loss appear in an aging resistance test, thereby showing that the opal shale is a key component for ensuring the comprehensive performance of the coating, and the absorption function of the opal shaleThe VOC of the coating is greatly reduced, the coating can be cooperated with titanate modified graphene, so that the coating has high impact strength, tensile strength and tear strength, the water resistance and corrosion resistance of the coating can be optimized, the porous structure of the coating can relieve the stress of the coating, cracks are prevented, and TiO added in a non-load mode2The ultraviolet aging resistance is far inferior to that of opal shale loaded TiO2. Comparative example 5 adopts the opal shale which is not activated, the specific surface area of the opal shale is greatly reduced compared with the activated opal shale, the adsorption rate and the capacity to harmful gases are not as good as the activated opal shale, therefore, the VOC release amount of the coating of comparative example 5 is far higher than that of example 3, the binding sites with titanate modified graphene and a coating resin matrix are relatively reduced, and the loaded TiO is2The amount decreased, making each of the comparative examples 4 inferior to the examples. Comparative example 6 does not contain polyethylene glycol, the mobility of pre-dispersion liquid of the aluminum paste is weakened, the gloss of the coating is obviously inferior to that of example 3, the dispersion uniformity of the coating in the preparation and storage processes is reduced, the hardness, the adhesive force, the water resistance and the acid and alkali resistance are obviously reduced, and the phenomena of foaming, peeling and light loss appear in an aging resistance test, probably because the polyethylene glycol and opal shale have the effect of synergistically promoting the directional arrangement of the aluminum paste, the structuring capacity among the coating components can be enhanced in the preparation process of the coating. The coating of comparative example 7 has reduced glossiness, greatly reduced wear resistance, poor acid and alkali resistance, and foaming, cracking, discoloration and light loss in an aging resistance test, because pre-dispersion is not carried out, the bonding force between the aluminum silver paste and the opal shale micro powder, the silane coupling agent and the titanate modified graphene is weak, the continuity of the formed network structure is poor, and the synergistic effect is weakened, so a series of performance reduction occurs.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and other modifications or equivalent substitutions made by the technical solution of the present invention by the ordinary skilled in the art should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The aluminum paste fluorocarbon coating is characterized by comprising the following components in parts by weight: 18-35 parts of waterborne fluorocarbon resin, 13-24 parts of polyurethane resin, 0.5-1 part of titanate modified graphene, 0.2-1 part of silane coupling agent, 6-23 parts of waterborne aluminum paste, 1-3 parts of opal shale micro powder and opal shale micro powder loaded TiO22-5 parts of ethylene glycol, 5-9 parts of dispersing agent, 0.1-1.5 parts of flatting agent, 0.1-1.5 parts of defoaming agent, 0.1-0.6 part of pH regulator and 15-28 parts of deionized water; the particle size of the opal shale micro powder is 10-20 μm;
the water-based aluminum paste is double-layer coated aluminum paste, and the preparation method comprises the following steps: dispersing silicon dioxide coated aluminum paste in ethanol, sequentially adding methyl methacrylate monomer, butyl acrylate monomer, hexafluorobutyl methacrylate monomer and acrylic acid monomer, then adding initiator azobisisobutyronitrile, stirring uniformly at room temperature, heating to 70 ℃, reacting at constant temperature for 5 hours, and performing suction filtration to obtain the aluminum paste coated by the fluorine-containing acrylate and the silicon dioxide in double layers;
the opal shale micro powder loads TiO2The preparation method comprises the following steps: (1) calcining the opal shale micro powder in a muffle furnace at 300 ℃ for 3h, then soaking the calcined opal shale micro powder in a phosphoric acid solution with the mass concentration of 15% for 24h, filtering and washing to be neutral for later use; (2) adding titanyl sulfate into distilled water, heating and stirring until the titanyl sulfate is completely dissolved, filtering, taking filtrate, and adding the opal shale micro powder prepared in the step (1) into the filtrate; (3) heating the mixed filtrate to 75 ℃ in a water bath, dropwise adding a precipitator diluted ammonia water, measuring the pH =10, stopping dropwise adding, continuing the water bath reaction for 1h, filtering, placing the obtained filter residue in a drying oven for drying for 2h, wherein the drying temperature is 120 ℃, and finally taking out and grinding to obtain the compound.
2. The aluminum paste fluorocarbon coating of claim 1, wherein the preparation method of the titanate modified graphene comprises: putting graphite oxide into a reactor, carrying out ultrasonic treatment, adjusting the pH value to 9-10 after the graphite oxide is completely dispersed, keeping the temperature at 80 ℃, then adding hydrazine hydrate and titanate coupling agent TM-200S, reacting for 8h, filtering while hot, and repeatedly washing until the filtrate is neutral, thus obtaining titanate modified graphene.
3. The aluminum paste fluorocarbon coating according to claim 2, characterized in that the mass ratio of graphene oxide to titanate coupling agent TM-200S in the preparation method of titanate modified graphene is 1: 7.
4. The aluminum paste fluorocarbon coating of claim 1, wherein the dispersant is a sodium polycarboxylate dispersant; the leveling agent is a hyperbranched organic silicon leveling agent; the defoaming agent is a polyether modified polysiloxane defoaming agent.
5. The preparation method of the aluminum paste fluorocarbon coating according to any one of claims 1 to 4, characterized by comprising the following steps:
adding part of deionized water into a feeding kettle, sequentially adding aqueous aluminum paste, opal shale micro powder, titanate modified graphene and a silane coupling agent, uniformly stirring, and performing ultrasonic treatment to obtain an aluminum paste pre-dispersion liquid;
step two, adding the rest part of deionized water into a blending tank, and then adding aqueous fluorocarbon resin, polyurethane resin, ethylene glycol and opal shale micro powder loaded TiO2After uniformly stirring, adding the pre-dispersion liquid of the aluminum paste obtained in the step one into a blending tank, continuously stirring, adding a dispersing agent, a leveling agent, a defoaming agent and a pH regulator, and continuously stirring to obtain a blending liquid;
and step three, sieving the uniformly stirred blending liquid with a 200-mesh sieve to obtain the aluminum paste fluorocarbon coating.
6. The preparation method of the aluminum paste fluorocarbon coating according to claim 5, wherein the power of the ultrasonic treatment in the first step is 200W, and the time is 40-60 min.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101322944A (en) * 2008-07-28 2008-12-17 吉林大学 Composite photocatalyst prepared from stephanoporate mineral and method thereof
KR20120139959A (en) * 2011-06-20 2012-12-28 이재환 High density nano coating compositions
CN103319916A (en) * 2013-06-19 2013-09-25 中南大学 Preparation method of inorganic-organic double-layer coated type aluminum paste
CN103342904A (en) * 2013-07-29 2013-10-09 上海理工大学 Method for preparing water-soluble graphene by titanate coupling agent modification process
CN107163710A (en) * 2017-06-19 2017-09-15 中国航发北京航空材料研究院 A kind of graphene fluorine carbon metal paint and preparation method thereof
CN109082168A (en) * 2018-07-12 2018-12-25 山东佳星环保科技有限公司 A kind of graphene fluorine carbon metal paint and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101322944A (en) * 2008-07-28 2008-12-17 吉林大学 Composite photocatalyst prepared from stephanoporate mineral and method thereof
KR20120139959A (en) * 2011-06-20 2012-12-28 이재환 High density nano coating compositions
CN103319916A (en) * 2013-06-19 2013-09-25 中南大学 Preparation method of inorganic-organic double-layer coated type aluminum paste
CN103342904A (en) * 2013-07-29 2013-10-09 上海理工大学 Method for preparing water-soluble graphene by titanate coupling agent modification process
CN107163710A (en) * 2017-06-19 2017-09-15 中国航发北京航空材料研究院 A kind of graphene fluorine carbon metal paint and preparation method thereof
CN109082168A (en) * 2018-07-12 2018-12-25 山东佳星环保科技有限公司 A kind of graphene fluorine carbon metal paint and preparation method thereof

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