CN115304963A - Initial-stage high-adhesion water-resistant environment-friendly metal coating - Google Patents

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

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CN115304963A
CN115304963A CN202211030571.0A CN202211030571A CN115304963A CN 115304963 A CN115304963 A CN 115304963A CN 202211030571 A CN202211030571 A CN 202211030571A CN 115304963 A CN115304963 A CN 115304963A
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emulsion
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CN115304963B (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
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    • 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
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    • 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
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    • 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
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    • C09D5/08—Anti-corrosive paints
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

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Abstract

The invention discloses an initial-stage 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 dioxide, 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 assistant, 0.05-0.15 part of defoaming agent, 0.2-0.4 part of buffering agent, 0.5-0.7 part of flash rust inhibitor, 0.1-0.3 part of flatting agent and 0.1-0.3 part of thickening agent. The invention has the advantages of low VOC, environmental protection and no toxicity, and meanwhile, the preparation process is simple and feasible, the cost is low, and the invention is suitable for common water-based metal paint and outdoor metal paint with variable weather. The initial water resistance and the adhesive force of the metal paint emulsion are superior to those of the common metal paint emulsion, the metal paint emulsion is suitable for construction in outdoor variable environments, the market competitiveness of the metal paint emulsion is greatly improved, and the construction requirements of customers are better met.

Description

Initial-stage high-adhesion water-resistant environment-friendly metal coating
Technical Field
The invention relates to the technical field of environment-friendly water-based metal paint emulsion, in particular to an initial-stage high-adhesion water-resistant environment-friendly metal paint.
Background
The traditional solvent type resin which is widely popularized and applied at present has higher content of Volatile Organic Compounds (VOC), so that irritant toxic gas exists in industrial production and resin application workshops, the health condition of workers can be influenced when the concentration is higher, and meanwhile, a large amount of volatile organic compounds are emitted into the atmosphere and also cause great pollution to the atmospheric environment.
Environment-friendly water-based metal paint emulsion is increasingly favored by people due to the characteristics of environmental friendliness, low VOC, easy cleaning, low odor, small damage to human bodies and the like. With the endless formation of various novel emulsifiers, monomers and functional monomers, various performances of the water-based metallic paint, such as glossiness, adhesive force, hardness, salt mist resistance, water resistance, weather resistance and the like, are greatly improved.
Along with the expansion of market demands and the fierce market competition, higher requirements are put forward on the application suitability and the application property of the water-based metallic paint. For example, in outdoor construction, the water-based metallic paint meets severe weather (rain, snow, etc.), and thus requires initial water resistance and adhesion, and the paint film is required to be dried into a film in a short time (especially, half an hour to one hour) and to have 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-stage high-adhesion water-resistant environment-friendly metal coating.
An initial-stage 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 (by weight),
water (W) 14-15 parts of (A), by weight,
wetting agent 0.1 to 0.3 portion of,
dispersing agent 0.3 to 0.5 portion of,
titanium white powder 8-12 parts of (by weight),
precipitated barium sulfate 4-6 parts of (A) a solvent,
zinc phosphate 4-6 parts of (A) a solvent,
color paste 0.4 to 0.6 portion of,
defoaming agent 0.05 to 0.15 portion of,
film forming aid 2-4 parts of (A), and (B),
defoaming agent 0.05 to 0.15 portion of,
buffering agent 0.2 to 0.4 portion of,
flash rust preventive 0.5 to 0.7 portion of,
leveling agent 0.1 to 0.3 portion of,
thickening agent 0.1-0.3 portion.
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) to (b),
water (I) 14.5 parts of (C), and (C),
wetting agent 0.2 part by weight of a reaction kettle,
dispersing agent 0.4 part by weight of a reaction kettle,
titanium white powder 10 parts of (a) to (b),
precipitated barium sulfate 5 parts of (a) a mixture of (b),
zinc phosphate 5 parts of (a) a mixture of (b),
color paste 0.5 part by weight of a reaction kettle,
defoaming agent 0.1 part by weight of a reaction kettle,
film forming aid 3 parts of (a) to (b),
defoaming agent 0.1 part by weight of a reaction kettle,
buffering agent 0.3 part by weight of a reaction kettle,
flash rust preventive 0.6 part by weight of a reaction kettle,
leveling agent 0.2 part of (by weight),
thickening agent 0.2 part.
Aiming at the defects of poor initial water resistance, poor initial adhesion, high cost and the like of the common water-based metal coating, the prepared metal coating with high gloss, high corrosion resistance, excellent weather resistance, good water resistance and excellent adhesion has good initial water resistance, high drying speed and excellent initial adhesion.
Preferably, the environment-friendly acrylic emulsion comprises the following raw materials in parts by weight:
styrene (meth) acrylic acid ester 10-20 parts of (by weight),
acrylic acid isooctyl ester 10-20 parts of (by weight),
methacrylic acid methyl ester 10-15 parts of (by weight),
acrylic acid 1-3 parts of (A) a solvent,
acrylic acid hydroxy ethyl ester 0.5 to 6 portions of the raw materials,
tert-dodecyl mercaptan 0.2 to 0.5 portion of,
propyltrimethoxysilane [ S1 ]] 0.5-1 part of (C),
sodium alkylphenol polyoxyethylene ether sulfate 0.5 to 2.5 portions of,
siloxane phosphates 0.5-2 parts of (A) to (B),
alkyl acrylic acid phosphoric acid ester 0.5-2 parts of (A) to (B),
ammonium persulfate 0.1-1 part of (A) to obtain,
[S2] 0.05 to 1 portion of the total weight of the components,
2,3,5,6-tetrahydroxy-2-hexene-4-lactone 0.05 to 1 portion of the total weight of the components,
[S3] 0.1 to 0.7 portion.
Preferably, the raw materials further comprise organic modified graphene powder, and the mass ratio of the organic modified graphene powder to styrene is 0-2.5:10-20 parts of; 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 hexamethylene diamine, mixing, reacting at 180-220 ℃ for 10-15h under high pressure, cooling, washing until the filtrate is neutral, drying, adding methyl acrylate, uniformly dispersing, adding methyl acrylate, stirring for 10-20h at 70-90 ℃ under the protection of nitrogen, adding ethylene diamine, continuously stirring for 5-10h, centrifuging, washing, and drying to obtain the organic modified graphene powder.
Preferably, the mass ratio of the activated graphene to the activated hexamethylenediamine to the activated methyl acrylate to the activated ethylenediamine is 4-8:0.01-0.1:0.1-1:0.1-1.
Preferably, the activated graphene is obtained by performing heat treatment on graphene powder by using concentrated acid.
According to the invention, the graphene is activated by adopting mixed acid, active carboxyl is formed on the surface of the graphene, hexamethylenediamine is used as a modifier to form active amino on the graphene in 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, then chlorohydrin is used for hydroxylation on the surface of the graphene, and a product can be combined with the monomers in the system to obtain a cross-linked whole in the system in a dendritic structure, so that the hydrophobic property 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: uniformly mixing concentrated nitric acid and concentrated sulfuric acid, cooling to room temperature, adding graphene powder, performing condensation reflux treatment at 60-80 ℃ for 2-6h, cooling to room temperature, standing for 10-20h, 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 acrylate phosphate as main polymerization monomers, takes acrylic acid as a crosslinking monomer, prepares the environment-friendly acrylic emulsion under the action of initiation of ammonium persulfate, can use water as a continuous phase in the polymerization process, and is assisted with alkylphenol polyoxyethylene ether sodium sulfate and siloxane phosphate for compounding, reduces the interfacial tension between two phases of water and oil, has higher polymerization reaction rate, high molecular weight and complex structure of the product, controllable viscosity, avoids the use of high-price solvent oil, and has small environmental pollution and low cost.
The sodium alkylphenol polyoxyethylene ether sulfate and the siloxane phosphate are compounded, so that on the basis of ensuring emulsifying power, small emulsion granularity and mechanical stability, the emulsion is endowed with good chemical stability, gel in the polymerization process is avoided, and meanwhile, the two molecules are alternately arranged, so that electrostatic repulsion between the surfaces of emulsion particles caused by independently using the sodium alkylphenol polyoxyethylene ether sulfate can be reduced, free radicals can enter the emulsion particles more easily to participate in reaction, and the polymerization rate is effectively improved; by adding the 3-propyl trimethoxy silane, the surface energy is low, the 3-propyl trimethoxy silane can be grafted in a main chain structure of latex particles, and silicon-containing groups tend to migrate to the surface of the latex film, so that a protective film can be formed on the surface of the latex film, and the water resistance and the aging resistance of the latex film 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 graphene powder is added into the system, the compatibility with the used polymeric monomer is excellent, meanwhile, the hydrophobic long-chain structure is fully dispersed into a latex film system, the hydrophobic property and the water resistance of latex can be further improved, and the initial water resistance and the adhesive force of the subsequent metal coating obtained within 0.5h can be obviously enhanced.
The preparation method of the environment-friendly acrylic emulsion comprises the following steps:
(1) Adding sodium alkylphenol polyoxyethylene ether sulfate into water, stirring, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and organic modified graphene powder under stirring, continuously stirring for 40-50min, and adding 3-propyl trimethoxy silane before stirring to obtain an emulsion;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, heating to 75-85 ℃, adding the emulsion, and stirring to obtain a premixed solution;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent; adding the ammonium persulfate diluent into the premixed solution, stirring for 10-20min at 80-90 ℃, dropwise adding the rest of emulsion and the rest of ammonium persulfate aqueous solution into the premixed solution under the stirring state for 2-4h, and preserving heat for 0.5-1.5h at 80-90 ℃ after dropwise adding is finished to obtain a prefabricated material;
(3) Cooling the prefabricated material to 70-72 ℃, dropwise adding hydrogen peroxide while stirring, continuing stirring after dropwise adding, dropwise adding 2,3,5,6-tetrahydroxy-2-hexene-4-lactone aqueous solution while stirring, 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 sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is 55-65:35-45.
Preferably, in the step (1), the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1-2:10-20.
Preferably, in the step (2), the mass ratio of the sodium alkylphenol polyoxyethylene ether 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 dosage to the second dosage of ammonium persulfate is 60-80:20-40.
Preferably, in the ammonium persulfate diluent 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, in the 2,3,5,6-tetrahydroxy-2-hexene-4-lactone aqueous solution of step (3), the mass ratio of water to 2,3,5,6-tetrahydroxy-2-hexene-4-lactone 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, firstly, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate and alkyl acrylic acid phosphate into a water dispersion of partial alkylphenol polyoxyethylene ether sodium sulfate to prepare an emulsion, then adding the rest alkylphenol polyoxyethylene ether sodium sulfate into water to form a backing material, adding part of the emulsion into the water to prepare a seed emulsion, wherein the system is stable, an ammonium persulfate initiator is not added in the stage, the siloxane phosphate and the alkylphenol polyoxyethylene ether sodium sulfate are compounded and adsorbed on the surface layer of acrylic acid beads, so that the acrylic acid can be suspended in a water continuous phase, then adding the ammonium persulfate initiator into the water continuous phase to decompose to start to generate emulsion particles, and then adding the rest of the emulsion and the ammonium persulfate into the emulsion, wherein the reaction process is complete, the solid content of the product is high and can reach 42-47%, the viscosity is controllable (less than 150cp, the particle size is uniform (90-140 nm), the pH is 7.5-8.5, and the Tg is 35-45 ℃.
The environment-friendly acrylic emulsion is added into the metal coating, even if the metal coating is exposed to severe rainy and snowy days in the outdoor construction process, the initial water resistance and adhesive force of the metal coating are excellent at 0.5h, and a paint film is not swelled after being soaked in water, can form a film within 30min by matching with the high hydrophobic and waterproof performance of the paint film, so as to cope with changeable days.
The invention has the advantages of low VOC, environmental protection and no toxicity, and meanwhile, the preparation process is simple and feasible, the cost is low, the invention is suitable for common water-based metal paint and outdoor metal paint with variable weather, and the paint has good water resistance, corrosion resistance, weather resistance, glossiness, adhesive force and hardness. The initial water resistance and the adhesive force of the metal paint emulsion are superior to those of the common metal paint emulsion, the metal paint emulsion is suitable for construction in outdoor variable environments, the market competitiveness of the metal paint emulsion is greatly improved, and the construction requirements of customers are better met.
Drawings
Fig. 1 is an infrared absorption spectrum of the organic modified graphene powder of example 4 and the graphene powder of comparative example 4.
FIG. 2 is a graph showing the contact angle test of the acrylic emulsion coating films obtained in example 4 and comparative example 4.
FIG. 3 is a water absorption test chart of acrylic emulsion coating films obtained in example 4 and comparative example 4.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 defoaming agent, 3 parts of film-forming assistant, 0.1 part of defoaming agent, 0.3 part of buffering agent, 0.6 part of flash rust inhibitor, 0.2 part of flatting agent and 0.2 part of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 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 tert-dodecyl mercaptan, 0.5 part of 3-propyltrimethoxysilane, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of siloxane phosphate, 0.5 part of alkyl acrylate 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 sodium alkylphenol polyoxyethylene sulfate for dissolving, stirring for 15min, sequentially adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate and alkyl acrylate phosphate, and stirring for 45min; 3-propyltrimethoxysilane is added to the emulsifier dropwise over the last half hour.
2. Preparing a reaction kettle: adding 35 parts of water into a reaction kettle, stirring, adding 1 part of alkylphenol polyoxyethylene sodium sulfate, heating to 80 ℃, adding 4% prepared emulsion, adding 0.15 part of ammonium persulfate diluted by 0.7 part of water after 2min, and reacting for 15min at the temperature of 82-85 ℃.
3. And simultaneously dropwise adding the rest of the emulsion and 0.1 part of ammonium persulfate diluted by 1.6 parts of water for 3 hours, and preserving the heat for 1 hour at 82-85 ℃ after the dropwise adding is finished.
4. Cooling to 70-72 deg.C, adding 0.05 part of diluted hydrogen peroxide solution of 0.7 part of water dropwise, adding dropwise for 5min, and stirring for 5min. Then, 0.05 part of 2,3,5,6-tetrahydroxy-2-hexene-4-lactone dissolved in 1 part of water is added dropwise for 10min. And keeping the temperature for 45min.
5. The temperature is reduced to 45 ℃, 0.7 part of ammonia water diluted by 1 part of water is added to adjust the pH value, and the mixture is stirred for 5min. Cooling to 40 ℃, filtering by a 120-mesh screen and discharging.
Comparative example 1
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 defoaming agent, 3 parts of film-forming assistant, 0.1 part of defoaming agent, 0.3 part of buffering agent, 0.6 part of flash rust inhibitor, 0.2 part of flatting agent and 0.2 part of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 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 tert-dodecyl mercaptan, 0.5 part of 3-propyltrimethoxysilane, 2.5 parts of alkylphenol polyoxyethylene ether sodium sulfate, 0.5 part of alkyl acrylate 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: adding 15 parts of water, stirring, adding 1.5 parts of sodium alkylphenol polyoxyethylene sulfate to dissolve, stirring for 15min, sequentially adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan and siloxane phosphate, and stirring for 45min. 3-propyltrimethoxysilane is added to the emulsifier dropwise over the last half hour.
2. Preparing a reaction kettle: adding 35 parts of water into a reaction kettle, stirring, adding 1 part of alkylphenol polyoxyethylene sodium sulfate, heating to 80 ℃, adding 4% prepared emulsion, adding 0.15 part of ammonium persulfate diluted by 0.7 part of water after 2min, and reacting for 15min at the temperature of 82-85 ℃.
3. And simultaneously dropwise adding the rest of the emulsion and 0.1 part of ammonium persulfate diluted by 1.6 parts of water for 3 hours, and preserving the heat for 1 hour at 82-85 ℃ after the dropwise adding is finished.
4. Cooling to 70-72 deg.C, adding 0.05 part of diluted hydrogen peroxide solution of 0.7 part of water dropwise, adding dropwise for 5min, and stirring for 5min. Then, 0.05 part of 2,3,5,6-tetrahydroxy-2-hexene-4-lactone dissolved in 1 part of water is added dropwise for 10min. And keeping the temperature for 45min.
5. The temperature is reduced to 45 ℃, 0.7 part of ammonia water diluted by 1 part of water is added to adjust the pH value, and the mixture is stirred for 5min. Cooling to 40 ℃, filtering by a 120-mesh screen and discharging.
Comparative example 2
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 defoaming agent, 3 parts of film-forming assistant, 0.1 part of defoaming agent, 0.3 part of buffering agent, 0.6 part of flash rust inhibitor, 0.2 part of flatting agent and 0.2 part of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 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 tert-dodecyl mercaptan, 0.5 part of 4-propyltrimethoxysilane, 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: adding 15 parts of water, stirring, adding 1.5 parts of sodium alkylphenol polyoxyethylene sulfate, dissolving, stirring for 15min, sequentially adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan and siloxane phosphate, and stirring for 45min. 3-propyltrimethoxysilane is added to the emulsifier dropwise over the last half hour.
2. Preparing a reaction kettle: adding 35 parts of water into a reaction kettle, stirring, adding 1 part of alkylphenol polyoxyethylene sodium sulfate, heating to 80 ℃, adding 4% prepared emulsion, adding 0.15 part of ammonium persulfate diluted by 0.7 part of water after 2min, and reacting for 15min at the temperature of 82-85 ℃.
3. And simultaneously dropwise adding the rest of the emulsion and 0.1 part of ammonium persulfate diluted by 1.6 parts of water for 3 hours, and preserving the heat for 1 hour at 82-85 ℃ after the dropwise adding is finished.
4. Cooling to 70-72 deg.C, adding 0.05 part of diluted hydrogen peroxide solution of 0.7 part of water dropwise, adding dropwise for 5min, and stirring for 5min. Then, 0.05 part of 2,3,5,6-tetrahydroxy-2-hexene-4-lactone dissolved in 1 part of water is added dropwise for 10min. And keeping the temperature for 45min.
5. The temperature is reduced to 45 ℃, 0.7 part of ammonia water diluted by 1 part of water is added to adjust the pH value, and the mixture is stirred for 5min. Cooling to 40 ℃, filtering by a 120-mesh screen and discharging.
Comparative example 3
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 defoaming agent, 3 parts of film-forming assistant, 0.1 part of defoaming agent, 0.3 part of buffering agent, 0.6 part of flash rust inhibitor, 0.2 part of flatting agent and 0.2 part of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 15 parts of styrene, 13 parts of isooctyl acrylate, 13 parts of methyl methacrylate, 1 part of acrylic acid, 0.3 part of tert-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: adding 15 parts of water, stirring, adding 1.5 parts of sodium alkylphenol polyoxyethylene sulfate to dissolve, stirring for 15min, sequentially adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, tert-dodecyl mercaptan and siloxane phosphate, and stirring for 45min.
2. Preparing a reaction kettle: adding 35 parts of water into a reaction kettle, stirring, adding 1 part of alkylphenol polyoxyethylene sodium sulfate, heating to 80 ℃, adding 4% prepared emulsion, adding 0.15 part of ammonium persulfate diluted by 0.7 part of water after 2min, and reacting for 15min at the temperature of 82-85 ℃.
3. And simultaneously dropwise adding the rest of the emulsion and 0.1 part of ammonium persulfate diluted by 1.6 parts of water for 3 hours, and preserving heat for 1 hour at 82-85 ℃ after the dropwise adding is finished.
4. Cooling to 70-72 deg.C, adding 0.05 part of diluted hydrogen peroxide solution of 0.7 part of water dropwise, adding dropwise for 5min, and stirring for 5min. Then, 0.05 part of 2,3,5,6-tetrahydroxy-2-hexene-4-lactone dissolved in 1 part of water is added dropwise for 10min. And keeping the temperature for 45min.
5. The temperature is reduced to 45 ℃, 0.7 part of ammonia water diluted by 1 part of water is added to adjust the pH value, and the mixture is stirred for 5min. Cooling to 40 ℃, filtering by a 120-mesh screen and discharging.
The solid content, viscosity, pH value and particle size of the acrylic emulsion obtained in the above example 1 and comparative examples 1 to 3 are within the index control range.
The performance test indexes (test with reference to HG/T4758-2014) of the water-based metallic paint coatings obtained in the above example 1 and the comparative examples 1-3 are as follows:
example 1 Comparative example 1 Comparative example 2 Comparative example 3
Gloss (60 degree gloss) 81 76.9 76 78
Initial water resistance, adhesion (0.5 h) Non-swelling bag for soaking water Non-swelling bag for soaking water Non-swelling bag for soaking water Slight bulge of water
Water resistance (24 h) 168h no abnormality 168h no abnormality 168h no abnormality 168h no abnormality
Hardness of pencil HB HB HB HB
Lattice test Level 0 Level 0 Grade 0 Grade 0
Salt fog resistance 120h non-bulge 120h slight bulge 120h slight bulge 120h slight bulge
Open time 8min 12min 10min 15min
Example 2
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 dioxide, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film-forming assistant, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of flash rust inhibitor, 0.2kg of flatting agent and 0.2kg of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 10kg of styrene, 20kg of isooctyl acrylate, 10kg of methyl methacrylate, 3kg of acrylic acid, 0.5kg of hydroxyethyl acrylate, 0.5kg of tert-dodecyl mercaptan, 0.5kg of 3-propyltrimethoxysilane, 0.5kg of organic modified graphene powder, 2.5kg of sodium alkylphenol polyoxyethylene ether sulfate, 0.5kg of siloxane phosphate, 2kg of alkyl acrylate phosphate, 0.1kg of ammonium persulfate, 1kg of hydrogen peroxide, 0.05kg 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, carrying out condensation reflux treatment at 80 ℃ for 2h, cooling to room temperature, standing for 20h, removing acid, washing with water to be neutral, and drying to obtain activated graphene;
adding 4kg of activated graphene into 30kg of ethylene glycol, uniformly stirring, adding into a high-pressure reaction kettle, adding 0.01kg of hexamethylenediamine, reacting at 220 ℃ for 10h, cooling, washing until the filtrate is neutral, drying, adding into 30kg of methanol, adding 0.1kg of methyl acrylate, stirring at 90 ℃ for 10h under the protection of nitrogen, adding 1kg of ethylenediamine, continuously stirring for 5h, 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 sodium alkylphenol polyoxyethylene ether sulfate into water, and stirring, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 2:10, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and organic modified graphene powder under stirring, continuously stirring for 50min, and adding 3-propyl trimethoxy silane to obtain an emulsion before stirring;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 0.8:40, heating to 75 ℃, adding the emulsion, and stirring to obtain a premixed solution, wherein the mass of the used 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 the ammonium persulfate diluent into the premixed liquid, stirring for 20min at 80 ℃, simultaneously dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.4;
the mass ratio of the first dosage to the second dosage of the ammonium persulfate is 80:20;
the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is 65:35;
(3) Cooling the prefabricated material to 72 ℃, dropwise adding hydrogen peroxide into the prefabricated material under a stirring state, continuously 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.
Example 3
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 dioxide, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film-forming assistant, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of flash rust inhibitor, 0.2kg of flatting agent and 0.2kg of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 20kg of styrene, 10kg of isooctyl acrylate, 15kg of methyl methacrylate, 1kg of acrylic acid, 6kg of hydroxyethyl acrylate, 0.2kg of tert-dodecyl mercaptan, 1kg of 3-propyltrimethoxy silane, 2.5kg of organically modified graphene powder, 0.5kg of sodium alkylphenol polyoxyethylene ether sulfate, 2kg of siloxane phosphate, 0.5kg of alkyl acrylate 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, carrying out condensation reflux treatment at 60 ℃ for 6h, cooling to room temperature, standing for 10h, removing acid, washing with water to be neutral, and drying to obtain activated graphene;
adding 8kg of activated graphene into 20kg of ethylene glycol, uniformly stirring, adding the activated graphene into a high-pressure reaction kettle, adding 0.1kg of hexamethylenediamine, reacting for 15h at the temperature of 180 ℃, cooling, washing until filtrate is neutral, drying, adding the filtrate into 20kg of methanol, adding 1kg of methyl acrylate, stirring for 20h at the temperature of 70 ℃ under the protection of nitrogen, adding 0.1kg of ethylenediamine, continuously stirring for 10h, 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 sodium alkylphenol polyoxyethylene ether sulfate into water, and stirring, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1:20, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and organic modified graphene powder under stirring, continuously stirring for 40min, and adding 3-propyl trimethoxy silane to obtain an emulsion before stirring;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1.2:30, heating to 85 ℃, adding the emulsion, and stirring to obtain a premixed solution, wherein the mass of the emulsified solution accounts for 3% of the total mass of the emulsified solution;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of the water to the ammonium persulfate is (9): 1; adding the ammonium persulfate diluent into the premixed liquid, stirring for 10min at 90 ℃, simultaneously dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.8;
the mass ratio of the first dosage to the second dosage of the ammonium persulfate is 60:40;
the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is 55:45, a first step of;
(3) Cooling the prefabricated material to 70 ℃, dropwise adding hydrogen peroxide into the prefabricated material under the stirring state, continuously 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.
Example 4
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 dioxide, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film-forming assistant, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of flash rust inhibitor, 0.2kg of flatting agent and 0.2kg of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 15kg of styrene, 15kg of isooctyl acrylate, 13kg of methyl methacrylate, 2kg of acrylic acid, 3kg of hydroxyethyl acrylate, 0.32kg of tert-dodecyl mercaptan, 0.8kg of 3-propyltrimethoxysilane, 1.5kg of organic modified graphene powder, 1.5kg of sodium alkylphenol polyoxyethylene ether sulfate, 1.32kg of siloxane phosphate, 1.26kg of alkyl acrylate 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, carrying out condensation reflux treatment at 70 ℃ for 4h, cooling to room temperature, standing for 15h, removing acid, washing with water to be neutral, and drying to obtain activated graphene;
adding 6kg of activated graphene into 25kg of ethylene glycol, uniformly stirring, adding the activated graphene into a high-pressure reaction kettle, adding 0.06kg of hexamethylenediamine, reacting for 13 hours at the temperature of 200 ℃, cooling, washing until filtrate is neutral, drying, adding the filtrate 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 sodium alkylphenol polyoxyethylene ether sulfate into water, and stirring, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1.5:15, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and organic modified graphene powder under stirring, continuing stirring for 45min, and adding 3-propyl trimethoxy silane to obtain an emulsion before stirring;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1:35, heating to 80 ℃, adding the emulsion, and stirring to obtain a premixed solution, wherein the mass of the emulsion accounts for 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 the ammonium persulfate diluent into the premixed liquid, stirring for 15min at 85 ℃, simultaneously dropwise adding the rest emulsion and the rest ammonium persulfate aqueous solution (the mass ratio of water to ammonium persulfate is 1.6;
the mass ratio of the first dosage to the second dosage of ammonium persulfate is 70:30, of a nitrogen-containing gas;
the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is 60:40;
(3) Cooling the prefabricated material to 71 ℃, dropwise adding hydrogen peroxide into the prefabricated material under a stirring state, continuously 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.
Comparative example 4
An initial-stage high-adhesion water-resistant environment-friendly metal coating 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 dioxide, 5kg of precipitated barium sulfate, 5kg of zinc phosphate, 0.5kg of color paste, 0.1kg of defoaming agent, 3kg of film-forming assistant, 0.1kg of defoaming agent, 0.3kg of buffering agent, 0.6kg of flash rust inhibitor, 0.2kg of flatting agent and 0.2kg of thickening agent.
The environment-friendly acrylic emulsion comprises the following raw materials: 15kg of styrene, 15kg of isooctyl acrylate, 13kg of methyl methacrylate, 2kg of acrylic acid, 3kg of hydroxyethyl acrylate, 0.32kg of tert-dodecyl mercaptan, 0.8kg of 3-propyltrimethoxysilane, 1.5kg of graphene powder, 1.5kg of sodium alkylphenol polyoxyethylene ether sulfate, 1.32kg of siloxane phosphate, 1.26kg of alkyl acrylate 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 sodium alkylphenol polyoxyethylene ether sulfate into water, and stirring, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1.5:15, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and graphene powder under stirring, continuously stirring for 45min, and adding 3-propyl trimethoxy silane to obtain an emulsion before stirring;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1:35, heating to 80 ℃, adding the emulsion, and stirring to obtain a premixed solution, wherein the mass of the emulsified solution accounts for 4% of the total mass of the emulsified solution;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent, wherein the mass ratio of water to ammonium persulfate is 7:1.5; adding the ammonium persulfate diluent into the premixed solution, stirring for 15min at 85 ℃, simultaneously dropwise adding the rest of the emulsified liquid and the rest of the aqueous solution of the ammonium persulfate (the mass ratio of water to the ammonium persulfate is 1.6: 0.1) into the premixed solution for 3h under the stirring state, and preserving heat for 1h at 85 ℃ after the dropwise adding is finished to obtain a prefabricated material;
the mass ratio of the first dosage to the second dosage of ammonium persulfate is 70:30, of a nitrogen-containing gas;
the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is 60:40;
(3) Cooling the prefabricated material to 71 ℃, dropwise adding hydrogen peroxide into the prefabricated material under a stirring state, continuously 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.
The organic modified graphene powder obtained in example 4 and the graphene powder obtained in comparative example 4 were subjected to an infrared absorption spectrum test using a fourier transform infrared spectrometer, as shown in fig. 1.
3430cm in spectrogram of graphene powder -1 The wide and strong peak is attributed to the hydroxyl contained in the graphene, and the intensity of the stretching vibration peak of the hydroxyl in the spectrogram of the organic modified graphene powder is obviously weakened because part of the hydroxyl participates in the reaction in the process of synthesizing the organic modified graphene powder.
1730cm in spectrogram of graphene powder -1 And 1620cm -1 The peak at (b) is due to stretching vibration of C = O and C = C, while the peak corresponding to C = O in the spectrum of the organically modified graphene powder disappears because graphene is reduced during the preparation process. But the spectrogram of the organic 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 appeared in (A) is attributed to the peak of stretching vibration of amide group C = O, 2920cm -1 And 2852cm -1 The peak appearing at corresponds to-CH 2 1184cm of symmetric and asymmetric stretching vibration peak -1 The characteristic peak at (a) is attributed to the stretching vibration peak of C-N.
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 micro-sampler was used to drop a drop of water on the film, the state of the drop of water on the film was photographed by a CCD, and the contact angle was characterized by a contact angle measuring instrument JC2000D, manufactured by digital technical equipment, inc., in Shanghai, china and morning, 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 environmental protection type acrylic acid emulsions obtained in example 4 and comparative example 4 were subjected to water absorption analysis. 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 at 90 +/-2 ℃ until the weight is constant; tearing off the adhesive film, and accurately weighing 0.5 +/-0.05 g; placing the adhesive film in a beaker filled with 50g of deionized water, sealing and standing for 72 hours to ensure that the adhesive film absorbs water to saturation, taking out the adhesive film, drying the surface water of the adhesive film by using filter paper and accurately weighing the mass of the adhesive film, wherein the water absorption of the emulsion film is calculated according to the following formula:
water absorption of latex film = (𝐺 0 −𝐺 1 ）/𝐺 0 × 100%
In the formula:𝐺 0 the mass of the latex film before water absorption is unit g;𝐺 0 the mass of the latex film after water absorption is unit g.
As shown in fig. 3, the latex film obtained in example 4 has a lower water absorption rate, which is the same as the above contact angle test result.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The initial-stage high-adhesion water-resistant environment-friendly metal coating is characterized by comprising the following raw materials in parts by weight:
environment-friendly acrylic emulsion 55-65 parts of (by weight), water (W) 14-15 parts of (A), by weight, wetting agent 0.1 to 0.3 portion of, dispersing agent 0.3 to 0.5 portion of, titanium white powder 8-12 parts of (by weight), precipitated barium sulfate 4-6 parts of (A) a solvent, zinc phosphate 4-6 parts of (A) a solvent, color paste 0.4 to 0.6 portion of, defoaming agent 0.05 to 0.15 portion of, film forming aid 2-4 parts of (by weight), defoaming agent 0.05 to 0.15 portion of, buffering agent 0.2 to 0.4 portion of, flash rust preventionAgent for treating cancer 0.5 to 0.7 portion of, leveling agent 0.1 to 0.3 portion of, thickening agent 0.1 to 0.3 portion
。
2. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight:
environment-friendly acrylic emulsion 60 parts of (a) to (b), water (W) 14.5 parts of (C), and (C), wetting agent 0.2 part by weight of a reaction kettle, dispersing agent 0.4 part by weight of a reaction kettle, titanium white powder 10 parts of (a) to (b), precipitated barium sulfate 5 parts of (a) a mixture of (b), zinc phosphate 5 parts of (a) a mixture of (b), color paste 0.5 part of (by weight), defoaming agent 0.1 part by weight of a reaction kettle, film forming aid 3 parts of (by weight) of (B), defoaming agent 0.1 part of (by weight), buffering agent 0.3 part by weight of a reaction kettle, flash rust preventive 0.6 part by weight of a reaction kettle, leveling agent 0.2 part by weight of a reaction kettle, thickening agent 0.2 part
。
3. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 1 or 2, wherein the environment-friendly acrylic emulsion comprises the following raw materials in parts by weight:
styrene (meth) acrylic acid ester 10-20 parts of (by weight), acrylic acid isooctyl ester 10-20 parts of (by weight), methacrylic acid methyl ester 10-15 parts of (by weight), acrylic acid 1-3 parts of (A) a solvent, acrylic acid hydroxy ethyl ester 0.5 to 6 portions of the raw materials, tert-dodecyl mercaptan 0.2 to 0.5 portion of, 3-propyltrimethoxysilane 0.5-1 part of (C), sodium alkylphenol polyoxyethylene ether sulfate 0.5 to 2.5 portions of, siloxane phosphates 0.5-2 parts of (A) to (B), alkyl acrylic acid phosphoric ester 0.5-2 parts of (a) to (b), ammonium persulfate 0.1-1 part of (by weight), hydrogen peroxide solution 0.05 to 1 portion of the total weight of the components, 2,3,5,6-tetrahydroxy-2-hexene-4-lactone 0.05 to 1 portion of the total weight of the mixture, aqueous ammonia 0.1 to 0.7 portion
。
4. The initial high-adhesion water-resistant environment-friendly metallic paint as claimed in claim 3, wherein the raw materials further comprise organic modified graphene powder, and the mass ratio of the organic modified graphene powder to styrene is 0-2.5:10-20 parts of; the organic modified graphene powder is obtained by grafting methyl acrylate and ethylenediamine serving as functional monomers on the surface of activated graphene.
5. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 4, wherein the organic modified graphene powder is prepared by the following steps: adding ethylene glycol into activated graphene, uniformly stirring, adding hexamethylene diamine, mixing, reacting at 180-220 ℃ for 10-15h under high pressure, cooling, washing until filtrate is neutral, drying, adding methanol for uniform dispersion, adding methyl acrylate, stirring at 70-90 ℃ for 10-20h under the protection of nitrogen, adding ethylene diamine, continuously stirring for 5-10h, centrifuging, washing, and drying to obtain the organic modified graphene powder.
6. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 5, wherein the mass ratio of activated graphene to hexamethylenediamine to methyl acrylate to ethylenediamine is 4-8:0.01-0.1:0.1-1:0.1-1.
7. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 3, wherein the activated graphene is obtained by heat treatment of graphene powder with concentrated acid.
8. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 3, wherein the activated graphene is prepared by the following specific steps: uniformly mixing concentrated nitric acid and concentrated sulfuric acid, cooling to room temperature, adding graphene powder, performing condensation reflux treatment at 60-80 ℃ for 2-6h, cooling to room temperature, standing for 10-20h, removing acid, washing with water until the washing liquid is neutral, and drying.
9. The initial high-adhesion water-resistant environment-friendly metal coating as claimed in claim 3, wherein in the preparation process of the environment-friendly acrylic emulsion:
(1) Adding sodium alkylphenol polyoxyethylene ether sulfate into water, stirring, adding styrene, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-dodecyl mercaptan, siloxane phosphate, alkyl acrylate phosphate and organic modified graphene powder under stirring, continuously stirring for 40-50min, and adding 3-propyl trimethoxy silane before stirring to obtain an emulsion;
(2) Adding the rest sodium alkylphenol polyoxyethylene ether sulfate into water, heating to 75-85 ℃, adding the emulsion, and stirring to obtain a premixed solution;
diluting ammonium persulfate into water to obtain ammonium persulfate diluent; adding the ammonium persulfate diluent into the premixed solution, stirring for 10-20min at 80-90 ℃, dropwise adding the rest of emulsion and the rest of ammonium persulfate aqueous solution into the premixed solution under the stirring state for 2-4h, and preserving heat for 0.5-1.5h at 80-90 ℃ after dropwise adding is finished to obtain a prefabricated material;
(3) Cooling the prefabricated material to 70-72 ℃, dropwise adding hydrogen peroxide while stirring, continuing stirring after dropwise adding, dropwise adding 2,3,5,6-tetrahydroxy-2-hexene-4-lactone aqueous solution while stirring, 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.
10. The initial high-adhesion water-resistant environment-friendly metal paint as claimed in claim 9, wherein the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate used in the step (1) to the sodium alkylphenol polyoxyethylene ether sulfate used in the step (2) is preferably 55-65:35-45 parts of;
preferably, in the step (1), the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 1-2:10-20 parts of;
preferably, in the step (2), the mass ratio of the sodium alkylphenol polyoxyethylene ether sulfate to the water is 0.8-1.2:30-40 parts of;
preferably, the mass of the emulsion used in the premix of the step (2) accounts for 3-5% of the total mass of the emulsion;
preferably, in the step (2), the mass ratio of the first dosage to the second dosage of ammonium persulfate is 60-80:20-40 parts of;
preferably, in the ammonium persulfate diluent 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, in the 2,3,5,6-tetrahydroxy-2-hexene-4-lactone aqueous solution of step (3), the mass ratio of water to 2,3,5,6-tetrahydroxy-2-hexene-4-lactone 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.
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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