CN115304963B - Initial high-adhesion water-resistant environment-friendly metal coating - Google Patents

Initial high-adhesion water-resistant environment-friendly metal coating Download PDF

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CN115304963B
CN115304963B CN202211030571.0A CN202211030571A CN115304963B CN 115304963 B CN115304963 B CN 115304963B CN 202211030571 A CN202211030571 A CN 202211030571A CN 115304963 B CN115304963 B CN 115304963B
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parts
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stirring
emulsion
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CN115304963A (en
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吕书魁
刘金明
崔沙沙
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Hebei Haoze Chemical 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Abstract

The invention discloses an initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials in parts by weight: 55-65 parts of environment-friendly acrylic emulsion, 14-15 parts of water, 0.1-0.3 part of wetting agent, 0.3-0.5 part of dispersing agent, 8-12 parts of titanium pigment, 4-6 parts of precipitated barium sulfate, 4-6 parts of zinc phosphate, 0.4-0.6 part of color paste, 0.05-0.15 part of defoaming agent, 2-4 parts of film forming auxiliary agent, 0.05-0.15 part of defoaming agent, 0.2-0.4 part of buffering agent, 0.5-0.7 part of anti-flash rust agent, 0.1-0.3 part of leveling agent and 0.1-0.3 part of thickening agent. The invention has the advantages of low VOC, green environmental protection and no toxicity, and simultaneously has simple and easy preparation process and low cost, and is suitable for general water-based metallic paint and metallic paint with outdoor changeable weather. The initial water resistance and the adhesive force of the paint are superior to those of common metallic paint emulsion, the paint is suitable for construction in outdoor changeable environments, the market competitiveness of the paint is greatly improved, and the construction requirements of customers are better met.

Description

Initial high-adhesion water-resistant environment-friendly metal coating
Technical Field
The invention relates to the technical field of environment-friendly water-based metallic paint emulsion, in particular to an initial-stage high-adhesion water-resistant environment-friendly metallic paint.
Background
The traditional solvent type resin which is widely popularized and applied at present has high content of organic volatile matters (VOC), so that the industrial production and resin application workshops have irritant poisonous gas, the health condition of workers can be influenced when the concentration is high, and a large amount of organic volatile matters are emitted into the atmosphere, so that the atmospheric environment is also greatly polluted.
The environment-friendly water-based metallic paint emulsion is more and more popular because of the characteristics of environmental friendliness, low VOC, easy cleaning, low odor, small damage to human bodies and the like. With the layering of various novel emulsifying agents, monomers and functional monomers, various performances of the water-based metallic paint, such as glossiness, adhesive force, hardness, salt spray resistance, water resistance, weather resistance and the like, are greatly improved.
With the expansion of market demands and the vigorous market competition, the application adaptability and the construction performance of the water-based metallic paint are more required. For example, in the outdoor construction process, the water-based metallic paint encounters severe weather (raining, snowing, etc.), so that requirements are made on the initial water resistance and adhesion, and the paint film is required to be dried and formed into a film in a short time (especially half an hour to one hour) and has high water resistance and adhesion so as to cope with variable weather.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides an initial high-adhesion water-resistant environment-friendly metal coating.
The initial high-adhesion water-resistant environment-friendly metal coating comprises the following raw materials in parts by weight:
environment-friendly acrylic emulsion 55-65 parts of a compound of a metal,
water and its preparation method 14-15 parts of a compound containing,
wetting agent 0.1 to 0.3 part of a compound,
dispersing agent 0.3 to 0.5 part of a compound,
titanium white powder 8-12 parts of a water-soluble polymer,
precipitated barium sulfate 4-6 parts of a compound containing, by weight,
zinc phosphate 4-6 parts of a compound containing, by weight,
color paste 0.4 to 0.6 part of a compound,
defoaming agent 0.05 to 0.15 part of a compound,
film forming aid 2-4 parts of a compound, wherein the compound comprises,
defoaming agent 0.05 to 0.15 part of a compound,
buffering agents 0.2 to 0.4 part of a compound,
flash rust inhibitor 0.5 to 0.7 part of a compound,
leveling agent 0.1 to 0.3 part of a compound,
thickening agent 0.1-0.3 parts.
Preferably, the initial high-adhesion water-resistant environment-friendly metal coating comprises the following raw materials in parts by weight:
environment-friendly acrylic emulsion 60 parts of a powder of a mixture of components,
water and its preparation method 14.5 parts of a powder of a mixture of two or more,
wetting agent 0.2 part of the total weight of the mixture,
dispersing agent 0.4 part of the total weight of the mixture,
titanium white powder 10 parts of a powder for injection,
precipitated barium sulfate 5 parts of the components in parts by weight,
zinc phosphate 5 parts of the components in parts by weight,
color paste 0.5 part of the total weight of the mixture,
defoaming agent 0.1 part of the total weight of the composition,
film forming aid 3 parts of the components in parts by weight,
defoaming agent 0.1 part of the total weight of the composition,
buffering agents 0.3 part of the total weight of the mixture,
flash rust inhibitor 0.6 part of the total weight of the mixture,
leveling agent 0.2 part of the total weight of the mixture,
thickening agent 0.2 parts.
Aiming at the defects of poor initial water resistance, poor initial adhesive force, high cost and the like of the common water-based metal coating, the prepared metal coating has high gloss, high corrosion resistance, excellent weather resistance, good water resistance and excellent adhesive force, and has the advantages of good initial water resistance, high drying speed and excellent initial adhesive force.
Preferably, the environment-friendly acrylic emulsion comprises the following raw materials in parts by weight:
styrene 10-20 parts of a compound, wherein the compound comprises,
isooctyl acrylate 10-20 parts of a compound, wherein the compound comprises,
methyl methacrylate 10-15 parts of a compound, wherein the compound comprises,
acrylic acid 1-3 parts of a compound, wherein,
hydroxy ethyl acrylate 0.5-6 parts of a compound,
tert-dodecyl mercaptan 0.2 to 0.5 part of a compound,
propyl trimethoxysilane [ S1 ]] 0.5 to 1 part of the total weight of the mixture,
alkylphenol polyoxyethylene sodium sulfate 0.5 to 2.5 parts of a compound,
siloxane phosphates 0.5-2 parts of a compound,
phosphoric acid alkyl acrylate 0.5-2 parts of a compound,
ammonium persulfate 0.1-1 part of the total weight of the components,
[S2] 0.05 to 1 part of the total weight of the components,
2,3,5, 6-tetrahydroxy-2-hexen-4-olide 0.05 to 1 part of the total weight of the components,
[S3] 0.1-0.7 parts.
Preferably, the raw materials further comprise organic modified graphene powder, and the mass ratio of the organic modified graphene powder to the styrene is 0-2.5:10-20 parts of a base; the organic modified graphene powder is obtained by grafting methyl acrylate and ethylenediamine serving as functional monomers on the surface of activated graphene.
Preferably, the organic modified graphene powder is prepared by the following specific steps: adding ethylene glycol into activated graphene, uniformly stirring, adding hexamethylenediamine, mixing, reacting at 180-220 ℃ for 10-15h under high pressure, cooling, washing until filtrate is neutral, drying, adding methanol, uniformly dispersing, adding methyl acrylate, stirring at 70-90 ℃ for 10-20h under nitrogen protection, adding ethylenediamine, continuously stirring for 5-10h, centrifuging, washing, and drying to obtain the organic modified graphene powder.
Preferably, the mass ratio of the graphene to the hexamethylenediamine to the methyl acrylate to the ethylenediamine after activation is 4-8:0.01-0.1:0.1-1:0.1-1.
Preferably, the activated graphene is obtained by heat treatment of graphene powder with concentrated acid.
According to the invention, the graphene is activated by adopting mixed acid, an active carboxyl is formed on the surface of the graphene, then hexamethylenediamine is used as a modifier, an active amino is formed on the graphene through a high-pressure high-temperature environment, methyl acrylate and ethylenediamine are used as functional monomers, the activated graphene is grafted into a hydrophobic long-chain structure, and then chlorohydrin is used for hydroxylation on the surface of the graphene, and the product can be combined with the monomers in the system to obtain a dendritic structure to form a crosslinked whole in the system, so that the hydrophobic performance is good, the water resistance and the adhesive force of the system can be effectively enhanced, and the product can be promoted to form a film in a short time.
Preferably, the activated graphene is prepared by the following specific steps: mixing concentrated nitric acid and concentrated sulfuric acid, cooling to room temperature, adding graphene powder, condensing and refluxing at 60-80deg.C for 2-6 hr, cooling to room temperature, standing for 10-20 hr, removing acid, washing with water until the washing liquid is neutral, and drying.
The invention adopts styrene, isooctyl acrylate, methyl methacrylate, hydroxyethyl acrylate and alkyl acrylic acid phosphate as main polymerization monomers, uses acrylic acid as a crosslinking monomer, prepares environment-friendly acrylic emulsion under the action of ammonium persulfate initiation, can use water as a continuous phase in the polymerization process, and is compounded by alkylphenol polyoxyethylene sodium sulfate and siloxane phosphate, thereby reducing the interfacial tension of two phases of water and oil, having higher polymerization reaction rate, high molecular weight and complex structure of the product, controllable viscosity, avoiding the use of Gao Angjia lattice solvent oil, and having small environmental pollution and low cost.
The alkyl phenol polyoxyethylene ether sodium sulfate and the siloxane phosphate are compounded, so that the emulsion has good chemical stability on the basis of ensuring the emulsification force, ensuring the small granularity and mechanical stability of the emulsion, avoiding the gel in the polymerization process, and simultaneously, two molecules are alternately arranged, so that the electrostatic repulsive force between the surfaces of emulsion particles caused by singly using the alkyl phenol polyoxyethylene ether sodium sulfate can be reduced, and free radicals can enter the emulsion particles to participate in the reaction more easily, thereby effectively improving the polymerization rate; by adding 3-propyl trimethoxy silane, the emulsion has lower surface energy, can be grafted in a main chain structure of emulsion particles, and silicon-containing groups tend to migrate to the surface of an emulsion film, so that a layer of protective film can be formed on the surface of the emulsion film, and the water resistance and ageing resistance of the emulsion are effectively improved. The organic modified graphene powder can be effectively dispersed into a system, so that the technical problem that the existing graphene powder is easy to agglomerate is solved, the organic modified graphene powder is added into the system, the compatibility with the polymerization monomer used in the invention is excellent, meanwhile, the hydrophobic long-chain structure of the organic modified graphene powder is fully dispersed into a latex film system, the hydrophobic and water-resistant properties of the latex can be further improved, and the initial water resistance and adhesive force of the metal coating obtained in the following process for 0.5h can be obviously enhanced.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene ether sodium sulfate into water, stirring, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic phosphate and organically modified graphene powder in a stirring state, continuing stirring for 40-50min, and adding 3-propyl trimethoxy silane before stirring is finished to obtain an emulsion;
(2) Adding the residual alkylphenol polyoxyethylene ether sodium sulfate into water, heating to 75-85 ℃, adding the emulsion and stirring to obtain a premix;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent; adding ammonium persulfate diluent into the premix, stirring at 80-90 ℃ for 10-20min, simultaneously dropwise adding the residual emulsion and the residual ammonium persulfate aqueous solution into the premix in a stirring state for 2-4h, and preserving heat at 80-90 ℃ for 0.5-1.5h after the dropwise adding is finished to obtain a prefabricated material;
(3) Cooling the prefabricated material to 70-72 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution into the prefabricated material in a stirring state, preserving heat for 40-50min after dropwise adding, cooling to 45-55 ℃, adding diluted ammonia water to adjust the pH value of the system, stirring, cooling to 30-40 ℃, and sieving with a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
Preferably, the mass ratio of the alkylphenol ethoxylate sodium sulfate used in the step (1) to the alkylphenol ethoxylate sodium sulfate used in the step (2) is 55-65:35-45.
Preferably, in the step (1), the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate to the water is 1-2:10-20.
Preferably, in the step (2), the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate to the water is 0.8-1.2:30-40.
Preferably, the mass of the emulsion used in the premix of step (2) is 3-5% of the total mass of the emulsion.
Preferably, in the step (2), the mass ratio of the first usage amount and the second usage amount of ammonium persulfate is 60-80:20-40.
Preferably, in the ammonium persulfate dilution liquid in the step (2), the mass ratio of water to ammonium persulfate is 5-9:1-2.
Preferably, in the aqueous solution of ammonium persulfate in the step (2), the mass ratio of water to ammonium persulfate is 1.4-1.8:0.08-0.12.
Preferably, the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone in the aqueous solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone of step (3) is 1:0.03-0.07.
Preferably, in the diluted ammonia water in the step (3), the mass ratio of water to ammonia water is 1:0.6-0.8.
Before ammonium persulfate is added, styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate and alkyl acrylic acid phosphate are firstly added into a part of aqueous dispersion of alkylphenol polyoxyethylene sodium sulfate to prepare emulsion, then the rest alkylphenol polyoxyethylene sodium sulfate is added into water to form a bottom material, part of emulsion is added into the bottom material to prepare seed emulsion, the system is stable, an ammonium persulfate initiator is not added at the stage, the siloxane phosphate and the alkyl phenol polyoxyethylene sodium sulfate are compounded and adsorbed on the surface layer of acrylic beads, so that acrylic acid can be suspended in a water continuous phase, then the ammonium persulfate initiator is added, the continuous phase is decomposed to start to generate emulsion particles, then the rest emulsion and ammonium persulfate are added into the emulsion, the reaction process is thorough, the solid content of the product is high and can reach 42-47%, the viscosity is controllable (< 150 cp=, the particle size is uniform (90-140 nm), meanwhile, the pH=7.5-8.5, and the Tg is 35-45 ℃.
According to the invention, the environment-friendly acrylic emulsion is added into the metal coating, and even if the environment-friendly acrylic emulsion encounters severe rainy, snowy and other weather in the outdoor construction process, the initial water resistance and the adhesive force of the environment-friendly acrylic emulsion are excellent in 0.5h, a paint film is not swelled when being soaked in water, and can be formed into a film within 30min in combination with the high hydrophobic and waterproof performances of the environment-friendly acrylic emulsion, so that the environment-friendly acrylic emulsion can cope with variable weather.
The invention has the advantages of low VOC, environmental protection and no toxicity, and simultaneously has simple and easy preparation process and low cost, is suitable for general water-based metallic paint and outdoor metallic paint with changeable weather, and has good water resistance, corrosion resistance, weather resistance, glossiness, adhesive force and hardness. The initial water resistance and the adhesive force of the paint are superior to those of common metallic paint emulsion, the paint is suitable for construction in outdoor changeable environments, the market competitiveness of the paint is greatly improved, and the construction requirements of customers are better met.
Drawings
FIG. 1 is an infrared absorption spectrum of the organically modified graphene powder of example 4 and that of the graphene powder of comparative example 4.
FIG. 2 is a graph showing contact angle measurements of acrylic emulsion coating films obtained in example 4 and comparative example 4.
FIG. 3 is a graph showing the water absorption test of the acrylic emulsion coating film obtained in example 4 and comparative example 4.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60 parts of emulsion, 14.5 parts of water, 0.2 part of wetting agent, 0.4 part of dispersing agent, 10 parts of titanium dioxide, 5 parts of precipitated barium sulfate, 5 parts of zinc phosphate, 0.5 part of color paste, 0.1 part of defoamer, 3 parts of film forming auxiliary agent, 0.1 part of defoamer, 0.3 part of buffering agent, 0.6 part of anti-flash rust agent, 0.2 part of flatting agent and 0.2 part of thickener.
The raw materials of the environment-friendly acrylic emulsion comprise: 15 parts of styrene, 13 parts of isooctyl acrylate, 13 parts of methyl methacrylate, 1 part of acrylic acid, 0.5 part of hydroxyethyl acrylate, 0.3 part of tertiary dodecyl mercaptan, 0.5 part of 3-propyl trimethoxy silane, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of siloxane phosphate, 0.5 part of alkyl acrylic phosphate, 0.25 part of ammonium persulfate, 0.05 part of hydrogen peroxide, 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone, 0.7 part of ammonia water and 55 parts of pure water.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
1. preparing an emulsion: adding 15 parts of water, stirring, adding 1.5 parts of alkylphenol polyoxyethylene sodium sulfate, dissolving, stirring for 15min, sequentially adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate and alkyl acrylic acid phosphate, and stirring for 45min; 3-propyltrimethoxysilane was added dropwise to the emulsifier for the last half hour.
2. Preparing a reaction kettle: 35 parts of water is added into a reaction kettle, stirring is started, 1 part of alkylphenol polyoxyethylene sodium sulfate is added, the temperature is raised to 80 ℃, 4% of prepared emulsion is added, 0.15 part of ammonium persulfate diluted by 0.7 part of water is added after 2min, the temperature is stabilized at 82-85 ℃, and the reaction is carried out for 15min.
3. Simultaneously, the rest emulsion and 1.6 parts of ammonium persulfate diluted by water are added dropwise for 3 hours, and the temperature is kept for 1 hour at 82-85 ℃ after the addition is finished.
4. Cooling to 70-72 ℃, dropwise adding 0.7 part of hydrogen peroxide diluted by water, dropwise adding for 5min, and stirring for 5min. Then, 1 part of water-soluble 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was added dropwise for 10 minutes. Preserving the heat for 45min.
5. Cooling to 45 ℃, adding 0.7 part of ammonia water diluted by 1 part of water to adjust Ph value, and stirring for 5min. Cooling to 40 ℃, and filtering and discharging by a 120-mesh screen.
Comparative example 1
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60 parts of emulsion, 14.5 parts of water, 0.2 part of wetting agent, 0.4 part of dispersing agent, 10 parts of titanium dioxide, 5 parts of precipitated barium sulfate, 5 parts of zinc phosphate, 0.5 part of color paste, 0.1 part of defoamer, 3 parts of film forming auxiliary agent, 0.1 part of defoamer, 0.3 part of buffering agent, 0.6 part of anti-flash rust agent, 0.2 part of flatting agent and 0.2 part of thickener.
The raw materials of the environment-friendly acrylic emulsion comprise: 15 parts of styrene, 13 parts of isooctyl acrylate, 13 parts of methyl methacrylate, 1 part of acrylic acid, 0.5 part of hydroxyethyl acrylate, 0.3 part of tertiary dodecyl mercaptan, 0.5 part of 3-propyl trimethoxy silane, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of alkyl acrylic phosphate, 0.25 part of ammonium persulfate, 0.05 part of hydrogen peroxide, 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone, 0.7 part of ammonia water and 55 parts of pure water.
1. Preparing an emulsion: 15 parts of water is added to open stirring, 1.5 parts of alkylphenol polyoxyethylene sodium sulfate is added to dissolve, stirring is carried out for 15min, styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan and siloxane phosphate are sequentially added to stir for 45min. 3-propyltrimethoxysilane was added dropwise to the emulsifier for the last half hour.
2. Preparing a reaction kettle: 35 parts of water is added into a reaction kettle, stirring is started, 1 part of alkylphenol polyoxyethylene sodium sulfate is added, the temperature is raised to 80 ℃, 4% of prepared emulsion is added, 0.15 part of ammonium persulfate diluted by 0.7 part of water is added after 2min, the temperature is stabilized at 82-85 ℃, and the reaction is carried out for 15min.
3. Simultaneously, the rest emulsion and 1.6 parts of ammonium persulfate diluted by water are added dropwise for 3 hours, and the temperature is kept for 1 hour at 82-85 ℃ after the addition is finished.
4. Cooling to 70-72 ℃, dropwise adding 0.7 part of hydrogen peroxide diluted by water, dropwise adding for 5min, and stirring for 5min. Then, 1 part of water-soluble 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was added dropwise for 10 minutes. Preserving the heat for 45min.
5. Cooling to 45 ℃, adding 0.7 part of ammonia water diluted by 1 part of water to adjust Ph value, and stirring for 5min. Cooling to 40 ℃, and filtering and discharging by a 120-mesh screen.
Comparative example 2
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60 parts of emulsion, 14.5 parts of water, 0.2 part of wetting agent, 0.4 part of dispersing agent, 10 parts of titanium dioxide, 5 parts of precipitated barium sulfate, 5 parts of zinc phosphate, 0.5 part of color paste, 0.1 part of defoamer, 3 parts of film forming auxiliary agent, 0.1 part of defoamer, 0.3 part of buffering agent, 0.6 part of anti-flash rust agent, 0.2 part of flatting agent and 0.2 part of thickener.
The raw materials of the environment-friendly acrylic emulsion comprise: 15 parts of styrene, 13 parts of isooctyl acrylate, 13 parts of methyl methacrylate, 1 part of acrylic acid, 0.5 part of hydroxyethyl acrylate, 0.3 part of tertiary dodecyl mercaptan, 0.5 part of 4-propyl trimethoxy silane, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of siloxane phosphate, 0.25 part of ammonium persulfate, 0.05 part of hydrogen peroxide, 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone, 0.7 part of ammonia water and 55 parts of pure water.
1. Preparing an emulsion: 15 parts of water is added to open stirring, 1.5 parts of alkylphenol polyoxyethylene sodium sulfate is added to dissolve, stirring is carried out for 15min, styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan and siloxane phosphate are sequentially added to stir for 45min. 3-propyltrimethoxysilane was added dropwise to the emulsifier for the last half hour.
2. Preparing a reaction kettle: 35 parts of water is added into a reaction kettle, stirring is started, 1 part of alkylphenol polyoxyethylene sodium sulfate is added, the temperature is raised to 80 ℃, 4% of prepared emulsion is added, 0.15 part of ammonium persulfate diluted by 0.7 part of water is added after 2min, the temperature is stabilized at 82-85 ℃, and the reaction is carried out for 15min.
3. Simultaneously, the rest emulsion and 1.6 parts of ammonium persulfate diluted by water are added dropwise for 3 hours, and the temperature is kept for 1 hour at 82-85 ℃ after the addition is finished.
4. Cooling to 70-72 ℃, dropwise adding 0.7 part of hydrogen peroxide diluted by water, dropwise adding for 5min, and stirring for 5min. Then, 1 part of water-soluble 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was added dropwise for 10 minutes. Preserving the heat for 45min.
5. Cooling to 45 ℃, adding 0.7 part of ammonia water diluted by 1 part of water to adjust Ph value, and stirring for 5min. Cooling to 40 ℃, and filtering and discharging by a 120-mesh screen.
Comparative example 3
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60 parts of emulsion, 14.5 parts of water, 0.2 part of wetting agent, 0.4 part of dispersing agent, 10 parts of titanium dioxide, 5 parts of precipitated barium sulfate, 5 parts of zinc phosphate, 0.5 part of color paste, 0.1 part of defoamer, 3 parts of film forming auxiliary agent, 0.1 part of defoamer, 0.3 part of buffering agent, 0.6 part of anti-flash rust agent, 0.2 part of flatting agent and 0.2 part of thickener.
The raw materials of the environment-friendly acrylic emulsion comprise: 15 parts of styrene, 13 parts of isooctyl acrylate, 13 parts of methyl methacrylate, 1 part of acrylic acid, 0.3 part of tertiary dodecyl mercaptan, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of siloxane phosphate, 0.25 part of ammonium persulfate, 0.05 part of hydrogen peroxide, 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone, 0.7 part of ammonia water and 55 parts of pure water.
1. Preparing an emulsion: 15 parts of water is added to open stirring, 1.5 parts of alkylphenol polyoxyethylene sodium sulfate is added to dissolve, stirring is carried out for 15min, styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, tertiary dodecyl mercaptan and siloxane phosphate are sequentially added to stir for 45min.
2. Preparing a reaction kettle: 35 parts of water is added into a reaction kettle, stirring is started, 1 part of alkylphenol polyoxyethylene sodium sulfate is added, the temperature is raised to 80 ℃, 4% of prepared emulsion is added, 0.15 part of ammonium persulfate diluted by 0.7 part of water is added after 2min, the temperature is stabilized at 82-85 ℃, and the reaction is carried out for 15min.
3. Simultaneously, the rest emulsion and 1.6 parts of ammonium persulfate diluted by water are added dropwise for 3 hours, and the temperature is kept for 1 hour at 82-85 ℃ after the addition is finished.
4. Cooling to 70-72 ℃, dropwise adding 0.7 part of hydrogen peroxide diluted by water, dropwise adding for 5min, and stirring for 5min. Then, 1 part of water-soluble 0.05 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was added dropwise for 10 minutes. Preserving the heat for 45min.
5. Cooling to 45 ℃, adding 0.7 part of ammonia water diluted by 1 part of water to adjust Ph value, and stirring for 5min. Cooling to 40 ℃, and filtering and discharging by a 120-mesh screen.
The acrylic emulsions obtained in example 1 and comparative examples 1 to 3 were all in the index control range in terms of solids content, viscosity, pH and particle size.
The performance test indexes (refer to HG/T4758-2014 test) of the aqueous metallic paint coatings obtained in the above example 1 and comparative examples 1-3 are as follows:
example 1 Comparative example 1 Comparative example 2 Comparative example 3
Gloss (60 degree light) 81 76.9 76 78
Initial water resistance and adhesion (0.5 h) No bulge when soaking in water No bulge when soaking in water No bulge when soaking in water Slightly bulge in the soaking water
Water resistance (24 h) 168h without abnormality 168h without abnormality 168h without abnormality 168h without abnormality
Hardness of pencil HB HB HB HB
Cross-hatch test Level 0 Level 0 Level 0 Level 0
Salt spray resistance 120h without bulge 120h slight bulge 120h slight bulge 120h slight bulge
Time of surface drying 8min 12min 10min 15min
Example 2
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60kg of the environment-friendly acrylic emulsion, 14.5kg of water, 0.2kg of wetting agent, 0.4kg of dispersing agent, 10kg of titanium pigment, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film forming auxiliary agent, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of anti-flash rust agent, 0.2kg of leveling agent and 0.2kg of thickening agent.
The raw materials of the environment-friendly acrylic emulsion comprise: 10kg of styrene, 20kg of isooctyl acrylate, 10kg of methyl methacrylate, 3kg of acrylic acid, 0.5kg of hydroxyethyl acrylate, 0.5kg of tertiary dodecyl mercaptan, 0.5kg of 3-propyl trimethoxysilane, 0.5kg of organically modified graphene powder, 2.5kg of alkylphenol polyoxyethylene ether sodium sulfate, 0.5kg of siloxane phosphate, 2kg of alkyl acrylic phosphate, 0.1kg of ammonium persulfate, 0.05kg of hydrogen peroxide, 1kg of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone and 0.7kg of ammonia water.
The organic modified graphene powder is prepared by the following specific steps: uniformly mixing 10kg of concentrated nitric acid and 15kg of concentrated sulfuric acid, cooling to room temperature, adding 1kg of graphene powder into the mixture, performing condensation reflux treatment at 80 ℃ for 2 hours, cooling to room temperature, standing for 20 hours, washing with water to be neutral after acid removal, and drying to obtain activated graphene;
adding 30kg of ethylene glycol into 4kg of activated graphene, uniformly stirring, adding into a high-pressure reaction kettle, adding 0.01kg of hexamethylenediamine, reacting for 10 hours at 220 ℃, cooling, washing until filtrate is neutral, drying, adding into 30kg of methanol, adding 0.1kg of methyl acrylate, stirring for 10 hours at 90 ℃ under the protection of nitrogen, adding 1kg of ethylenediamine, continuously stirring for 5 hours, centrifuging, washing, and drying to obtain the organic modified graphene powder.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene sodium sulfate into water, and stirring, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 2:10, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic acid phosphate and organically modified graphene powder into the mixture under stirring, continuously stirring for 50min, and adding 3-propyl trimethoxy silane to obtain emulsion before stirring is finished;
(2) Adding the rest alkylphenol polyoxyethylene sodium sulfate into water, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 0.8:40, heating to 75 ℃, adding the emulsion, and stirring to obtain a premix, wherein the mass of the emulsion accounts for 5% of the total mass of the emulsion;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of water to ammonium persulfate is 5:2; adding ammonium persulfate diluent into the premix, stirring at 80 ℃ for 20min, simultaneously dropwise adding the residual emulsion and the residual ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.4:0.12) into the premix in a stirring state, wherein the dropwise adding time is 2h, and preserving heat at 90 ℃ for 0.5h after the dropwise adding is finished to obtain a prefabricated material;
the mass ratio of the first usage amount to the second usage amount of ammonium persulfate is 80:20, a step of;
the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate used in the step (1) to the alkylphenol polyoxyethylene ether sodium sulfate used in the step (2) is 65:35;
(3) Cooling the prefabricated material to 72 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution (the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is 1:0.03) into the prefabricated material in a stirring state, preserving heat for 50min after dropwise adding, cooling to 45 ℃, adding diluted ammonia water (the mass ratio of water to ammonia water is 1:0.8), regulating the pH value of the system, stirring, cooling to 30 ℃, and sieving by a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
Example 3
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60kg of the environment-friendly acrylic emulsion, 14.5kg of water, 0.2kg of wetting agent, 0.4kg of dispersing agent, 10kg of titanium pigment, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film forming auxiliary agent, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of anti-flash rust agent, 0.2kg of leveling agent and 0.2kg of thickening agent.
The raw materials of the environment-friendly acrylic emulsion comprise: 20kg of styrene, 10kg of isooctyl acrylate, 15kg of methyl methacrylate, 1kg of acrylic acid, 6kg of hydroxyethyl acrylate, 0.2kg of tertiary dodecyl mercaptan, 1kg of 3-propyltrimethoxysilane, 2.5kg of organically modified graphene powder, 0.5kg of alkylphenol polyoxyethylene ether sodium sulfate, 2kg of siloxane phosphate, 0.5kg of alkyl acrylic phosphate, 1kg of ammonium persulfate, 0.05kg of hydrogen peroxide, 1kg of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone and 0.1kg of ammonia water.
The organic modified graphene powder is prepared by the following specific steps: uniformly mixing 20kg of concentrated nitric acid and 5kg of concentrated sulfuric acid, cooling to room temperature, adding 5kg of graphene powder into the mixture, performing condensation reflux treatment at 60 ℃ for 6 hours, cooling to room temperature, standing for 10 hours, washing with water to be neutral after acid removal, and drying to obtain activated graphene;
adding 20kg of ethylene glycol into 8kg of activated graphene, uniformly stirring, adding into a high-pressure reaction kettle, adding 0.1kg of hexamethylenediamine, reacting for 15 hours at 180 ℃, cooling, washing until filtrate is neutral, drying, adding into 20kg of methanol, adding 1kg of methyl acrylate, stirring for 20 hours at 70 ℃ under the protection of nitrogen, adding 0.1kg of ethylenediamine, continuously stirring for 10 hours, centrifuging, washing, and drying to obtain the organic modified graphene powder.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene sodium sulfate into water, and stirring, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1:20, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic acid phosphate and organically modified graphene powder into the mixture under stirring, continuously stirring for 40min, and adding 3-propyl trimethoxy silane to obtain emulsion before stirring is finished;
(2) Adding the rest alkylphenol polyoxyethylene sodium sulfate into water, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1.2:30, heating to 85 ℃, adding the emulsion, and stirring to obtain a premix, wherein the mass of the emulsion accounts for 3% of the total mass of the emulsion;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of water to ammonium persulfate is 9:1, a step of; adding ammonium persulfate diluent into the premix, stirring for 10min at 90 ℃, dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.8:0.08) into the premix at the same time under the stirring state, wherein the dropwise adding time is 4h, and preserving heat for 1.5h at 80 ℃ after the dropwise adding is finished to obtain a prefabricated material;
the mass ratio of the first usage amount to the second usage amount of the ammonium persulfate is 60:40, a step of performing a;
the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate used in the step (1) to the alkylphenol polyoxyethylene ether sodium sulfate used in the step (2) is 55:45;
(3) Cooling the prefabricated material to 70 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution (the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is 1:0.07) into the prefabricated material in a stirring state, preserving heat for 40min after dropwise adding, cooling to 55 ℃, adding diluted ammonia water (the mass ratio of water to ammonia water is 1:0.6), regulating the pH value of the system, stirring, cooling to 40 ℃, and sieving by a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
Example 4
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60kg of the environment-friendly acrylic emulsion, 14.5kg of water, 0.2kg of wetting agent, 0.4kg of dispersing agent, 10kg of titanium pigment, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film forming auxiliary agent, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of anti-flash rust agent, 0.2kg of leveling agent and 0.2kg of thickening agent.
The raw materials of the environment-friendly acrylic emulsion comprise: 15kg of styrene, 15kg of isooctyl acrylate, 13kg of methyl methacrylate, 2kg of acrylic acid, 3kg of hydroxyethyl acrylate, 0.32kg of tertiary dodecyl mercaptan, 0.8kg of 3-propyl trimethoxy silane, 1.5kg of organically modified graphene powder, 1.5kg of alkylphenol polyoxyethylene ether sodium sulfate, 1.32kg of siloxane phosphate, 1.26kg of alkyl acrylic phosphate, 0.55kg of ammonium persulfate, 0.57kg of hydrogen peroxide, 0.38kg of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone and 0.4kg of ammonia water.
The organic modified graphene powder is prepared by the following specific steps: uniformly mixing 15kg of concentrated nitric acid and 10kg of concentrated sulfuric acid, cooling to room temperature, adding 3kg of graphene powder into the mixture, performing condensation reflux treatment at 70 ℃ for 4 hours, cooling to room temperature, standing for 15 hours, washing with water to be neutral after acid removal, and drying to obtain activated graphene;
adding 25kg of ethylene glycol into 6kg of activated graphene, uniformly stirring, adding into a high-pressure reaction kettle, adding 0.06kg of hexamethylenediamine, reacting for 13 hours at the temperature of 200 ℃, cooling, washing until the filtrate is neutral, drying, adding into 25kg of methanol, adding 0.7kg of methyl acrylate, stirring for 15 hours at the temperature of 80 ℃ under the protection of nitrogen, adding 0.4kg of ethylenediamine, continuously stirring for 7.5 hours, centrifuging, washing, and drying to obtain the organic modified graphene powder.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene sodium sulfate into water, and stirring, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1.5:15, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic acid phosphate and organically modified graphene powder into the mixture under stirring, continuously stirring for 45min, and adding 3-propyl trimethoxy silane to obtain emulsion before stirring is finished;
(2) Adding the rest alkylphenol polyoxyethylene sodium sulfate into water, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1:35, heating to 80 ℃, adding the emulsion, and stirring to obtain a premix, wherein the mass of the emulsion is 4% of the total mass of the emulsion;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of water to ammonium persulfate is 7:1.5; adding ammonium persulfate diluent into the premix, stirring for 15min at 85 ℃, dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.6:0.1) into the premix at the same time under the stirring state, wherein the dropwise adding time is 3h, and preserving heat for 1h at 85 ℃ after the dropwise adding is finished to obtain a prefabricated material;
the mass ratio of the first usage amount to the second usage amount of the ammonium persulfate is 70:30;
the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate used in the step (1) to the alkylphenol polyoxyethylene ether sodium sulfate used in the step (2) is 60:40, a step of performing a;
(3) Cooling the prefabricated material to 71 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution (the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is 1:0.05) into the prefabricated material in a stirring state, preserving heat for 45min after dropwise adding, cooling to 50 ℃, adding diluted ammonia water (the mass ratio of water to ammonia water is 1:0.7), regulating the pH value of the system, stirring, cooling to 35 ℃, and sieving with a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
Comparative example 4
An initial high-adhesion water-resistant environment-friendly metal coating, which comprises the following raw materials: 60kg of the environment-friendly acrylic emulsion, 14.5kg of water, 0.2kg of wetting agent, 0.4kg of dispersing agent, 10kg of titanium pigment, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film forming auxiliary agent, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of anti-flash rust agent, 0.2kg of leveling agent and 0.2kg of thickening agent.
The raw materials of the environment-friendly acrylic emulsion comprise: 15kg of styrene, 15kg of isooctyl acrylate, 13kg of methyl methacrylate, 2kg of acrylic acid, 3kg of hydroxyethyl acrylate, 0.32kg of tertiary dodecyl mercaptan, 0.8kg of 3-propyl trimethoxysilane, 1.5kg of graphene powder, 1.5kg of alkylphenol polyoxyethylene ether sodium sulfate, 1.32kg of siloxane phosphate, 1.26kg of alkyl acrylic phosphate, 0.55kg of ammonium persulfate, 0.57kg of hydrogen peroxide, 0.38kg of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone and 0.4kg of ammonia water.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene sodium sulfate into water, and stirring, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1.5:15, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic phosphate and graphene powder in a stirring state, continuously stirring for 45min, and adding 3-propyl trimethoxy silane before stirring is finished to obtain an emulsion;
(2) Adding the rest alkylphenol polyoxyethylene sodium sulfate into water, wherein the mass ratio of the alkylphenol polyoxyethylene sodium sulfate to the water is 1:35, heating to 80 ℃, adding the emulsion, and stirring to obtain a premix, wherein the mass of the emulsion is 4% of the total mass of the emulsion;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of water to ammonium persulfate is 7:1.5; adding ammonium persulfate diluent into the premix, stirring for 15min at 85 ℃, dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.6:0.1) into the premix at the same time under the stirring state, wherein the dropwise adding time is 3h, and preserving heat for 1h at 85 ℃ after the dropwise adding is finished to obtain a prefabricated material;
the mass ratio of the first usage amount to the second usage amount of the ammonium persulfate is 70:30;
the mass ratio of the alkylphenol polyoxyethylene ether sodium sulfate used in the step (1) to the alkylphenol polyoxyethylene ether sodium sulfate used in the step (2) is 60:40, a step of performing a;
(3) Cooling the prefabricated material to 71 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution (the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is 1:0.05) into the prefabricated material in a stirring state, preserving heat for 45min after dropwise adding, cooling to 50 ℃, adding diluted ammonia water (the mass ratio of water to ammonia water is 1:0.7), regulating the pH value of the system, stirring, cooling to 35 ℃, and sieving with a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
Infrared absorption spectrum test was performed on the organically modified graphene powder obtained in example 4 and the graphene powder obtained in comparative example 4 using a fourier transform infrared spectrometer, as shown in fig. 1.
3430cm in spectrogram of graphene powder -1 Where occursThe broad and strong peak is attributed to the hydroxyl groups contained in graphene, and the intensity of the stretching vibration peak of the hydroxyl groups in the spectrogram of the organically modified graphene powder is obviously weakened because part of the hydroxyl groups participate in the reaction in the process of synthesizing the organically modified graphene powder.
1730cm in spectrogram of graphene powder -1 And 1620cm -1 The peaks at c=o and c=c are attributed to stretching vibration, while the peak corresponding to c=o in the spectrogram of the organically modified graphene powder disappears because the graphene is reduced during the preparation process. But the spectrogram of the organically modified graphene powder is 1564cm -1 A new characteristic peak appears due to the stretching vibration peak of the amine groups contained in the sample.
1730cm in spectrogram of organic modified graphene powder -1 The new peak appearing at this point is due to the telescopic vibration peak of the amidyl group c=o, 2920cm -1 And 2852cm -1 The peak appearing at this point corresponds to-CH 2 Symmetrical and asymmetrical stretching vibration peaks of 1184cm -1 The characteristic peak at this point is attributed to the C-N stretching vibration peak.
The environment-friendly acrylic emulsion obtained in example 4 and comparative example 4 was coated on an iron plate and formed into a film at room temperature, a drop of water was dropped on the film by a microsyringe, the state of the drop of water on the film was photographed by a CCD, the contact angle was characterized by a contact angle measuring instrument JC2000D of Shanghai middle morning digital equipment, and the contact angle was recorded.
As shown in fig. 2, the environmental-friendly acrylic emulsion coating film obtained in example 4 has a larger contact angle and exhibits hydrophobic properties.
The water absorption analysis was performed on the environment-friendly acrylic emulsions obtained in example 4 and comparative example 4. Weighing 4.0+/-0.5 g of each group of samples in a clean glass dish, and placing the samples in a constant-temperature blast drying oven to be dried to constant weight at 90+/-2 ℃; tearing off the adhesive film, and accurately weighing 0.5+/-0.05 g; placing the adhesive film in a beaker containing 50g of deionized water, sealing and standing for 72h to enable the adhesive film to absorb moisture to be saturated, taking out the adhesive film, sucking the moisture on the surface layer of the adhesive film by using filter paper, accurately weighing the adhesive film, and calculating the water absorption of the emulsion film according to the following formula:
latex film water absorption rate = (𝐺 0 −𝐺 1 ）/𝐺 0 × 100%
Wherein:𝐺 0 the mass of the emulsion film before water absorption is in g;𝐺 0 the mass of the latex film after water absorption is in g.
As shown in fig. 3, the latex film obtained in example 4 had a lower water absorption, which was the same as the contact angle test result described above.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (13)

1. The initial high-adhesion water-resistant environment-friendly metal coating is characterized by comprising the following raw materials in parts by weight:
55-65 parts of environment-friendly acrylic emulsion,
14-15 parts of water, and the water is mixed with the water,
0.1-0.3 part of wetting agent,
0.3 to 0.5 part of dispersing agent,
8-12 parts of titanium dioxide,
4-6 parts of precipitated barium sulfate,
4-6 parts of zinc phosphate,
0.4 to 0.6 part of color paste,
0.05 to 0.15 portion of defoaming agent,
2-4 parts of film forming auxiliary agent,
0.05 to 0.15 portion of defoaming agent,
0.2 to 0.4 part of buffer,
0.5 to 0.7 part of flash rust inhibitor,
0.1 to 0.3 part of flatting agent,
0.1-0.3 part of thickener;
the environment-friendly acrylic emulsion comprises the following raw materials in parts by weight:
10-20 parts of styrene, and the like,
10-20 parts of isooctyl acrylate,
10-15 parts of methyl methacrylate,
1-3 parts of acrylic acid,
0.5-6 parts of hydroxyethyl acrylate,
0.2 to 0.5 part of tertiary dodecyl mercaptan,
0.5-1 part of 3-propyl trimethoxy silane,
0.5 to 2.5 portions of alkylphenol polyoxyethylene ether sodium sulfate,
0.5-2 parts of siloxane phosphate,
0.5-2 parts of alkyl acrylic acid phosphate,
0.1-1 part of ammonium persulfate,
0.05 to 1 part of hydrogen peroxide,
0.05 to 1 part of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone,
0.1-0.7 part of ammonia water;
the raw materials of the environment-friendly acrylic emulsion also comprise organic modified graphene powder, and the mass ratio of the organic modified graphene powder to the styrene is 0-2.5:10-20 parts of a base;
the organic modified graphene powder is prepared by the following specific steps: adding ethylene glycol into activated graphene, uniformly stirring, adding hexamethylenediamine, mixing, reacting at 180-220 ℃ for 10-15 hours under high pressure, cooling, washing until filtrate is neutral, drying, adding methanol, uniformly dispersing, adding methyl acrylate, stirring at 70-90 ℃ for 10-20 hours under nitrogen protection, adding ethylenediamine, continuously stirring for 5-10 hours, centrifuging, washing, and drying to obtain organic modified graphene powder;
the activated graphene is obtained by heat treatment of graphene powder by adopting concentrated acid;
the preparation process of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding alkylphenol polyoxyethylene ether sodium sulfate into water, stirring, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tertiary dodecyl mercaptan, siloxane phosphate, alkyl acrylic phosphate and organically modified graphene powder in a stirring state, continuing stirring for 40-50min, and adding 3-propyl trimethoxy silane before stirring is finished to obtain an emulsion;
(2) Adding the residual alkylphenol polyoxyethylene ether sodium sulfate into water, heating to 75-85 ℃, adding the emulsion and stirring to obtain a premix;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent; adding ammonium persulfate diluent into the premix, stirring at 80-90 ℃ for 10-20min, simultaneously dropwise adding the residual emulsion and the residual ammonium persulfate aqueous solution into the premix in a stirring state for 2-4h, and preserving heat at 80-90 ℃ for 0.5-1.5h after the dropwise adding is finished to obtain a prefabricated material;
(3) Cooling the prefabricated material to 70-72 ℃, dropwise adding hydrogen peroxide into the prefabricated material in a stirring state, continuing stirring after dropwise adding, dropwise adding 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution into the prefabricated material in a stirring state, preserving heat for 40-50min after dropwise adding, cooling to 45-55 ℃, adding diluted ammonia water to adjust the pH value of the system, stirring, cooling to 30-40 ℃, and sieving with a 120-mesh sieve to obtain the environment-friendly acrylic emulsion.
2. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 1, wherein the initial high-adhesion water-resistant environment-friendly metal coating comprises the following raw materials in parts by weight:
60 parts of environment-friendly acrylic emulsion,
14.5 parts of water, and the water is mixed with the water,
0.2 part of wetting agent, and the like,
0.4 part of a dispersing agent, and the mixture is prepared from the following components,
10 parts of titanium dioxide,
5 parts of precipitated barium sulfate,
5 parts of zinc phosphate, namely a zinc phosphate solution,
0.5 part of color paste,
0.1 part of an antifoaming agent, and the like,
3 parts of a film forming auxiliary agent,
0.1 part of an antifoaming agent, and the like,
0.3 part of a buffering agent, and the like,
0.6 part of flash rust inhibitor,
0.2 part of leveling agent, and the balance of the water-soluble polymer,
0.2 parts of thickener.
3. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that the mass ratio of graphene to hexamethylenediamine to methyl acrylate to ethylenediamine after activation is 4-8:0.01-0.1:0.1-1:0.1-1.
4. The initial high-adhesion water-resistant environment-friendly metal coating is prepared from activated graphene by the following specific steps: mixing concentrated nitric acid and concentrated sulfuric acid, cooling to room temperature, adding graphene powder, condensing and refluxing at 60-80deg.C for 2-6 hr, cooling to room temperature, standing for 10-20 hr, removing acid, washing with water until the washing liquid is neutral, and drying.
5. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that the mass ratio of alkylphenol polyoxyethylene ether sodium sulfate used in the step (1) to alkylphenol polyoxyethylene ether sodium sulfate used in the step (2) is 55-65:35-45.
6. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the step (1), the mass ratio of alkylphenol polyoxyethylene sodium sulfate to water is 1-2:10-20.
7. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the step (2), the mass ratio of alkylphenol polyoxyethylene sodium sulfate to water is 0.8-1.2:30-40.
8. The initial high-adhesion water-resistant environment-friendly metal coating according to claim 1, wherein the mass of the emulsion used in the premix liquid in the step (2) is 3-5% of the total mass of the emulsion.
9. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the step (2), the mass ratio of the first usage amount to the second usage amount of ammonium persulfate is 60-80:20-40.
10. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the ammonium persulfate diluent in the step (2), the mass ratio of water to ammonium persulfate is 5-9:1-2.
11. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the aqueous solution of ammonium persulfate in the step (2), the mass ratio of water to ammonium persulfate is 1.4-1.8:0.08-0.12.
12. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that in the 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone aqueous solution in the step (3), the mass ratio of water to 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is 1:0.03-0.07.
13. The initial high-adhesion water-resistant environment-friendly metal coating is characterized in that the mass ratio of water to ammonia in the diluted ammonia water in the step (3) is 1:0.6-0.8.
CN202211030571.0A 2022-08-26 2022-08-26 Initial high-adhesion water-resistant environment-friendly metal coating Active CN115304963B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433098A (en) * 2016-09-28 2017-02-22 安徽大学 Preparation method of graphene/polyacrylic ester-silicon-containing hyperbranched waterborne polyurethane multi-element composite emulsion
CN108285505A (en) * 2018-01-12 2018-07-17 成都巴德富科技有限公司 One kind zero adds ordor removing interior wall lotion and preparation method thereof
CN110028857A (en) * 2019-04-09 2019-07-19 河北晨阳工贸集团有限公司 A kind of one-component high adhesion force environmental protection sealing wax and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433098A (en) * 2016-09-28 2017-02-22 安徽大学 Preparation method of graphene/polyacrylic ester-silicon-containing hyperbranched waterborne polyurethane multi-element composite emulsion
CN108285505A (en) * 2018-01-12 2018-07-17 成都巴德富科技有限公司 One kind zero adds ordor removing interior wall lotion and preparation method thereof
CN110028857A (en) * 2019-04-09 2019-07-19 河北晨阳工贸集团有限公司 A kind of one-component high adhesion force environmental protection sealing wax and preparation method thereof

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