CN115141546B - High-water-resistance water-based paint and preparation method thereof - Google Patents
High-water-resistance water-based paint and preparation method thereof Download PDFInfo
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- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
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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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention discloses a high-water-resistance water-based paint and a preparation method thereof, wherein the paint comprises the following raw materials in parts by weight: 80-100 parts of modified acrylic resin, 2-4 parts of talcum powder, 1-3 parts of mica powder, 0.05-0.1 part of defoamer, 1.5-3 parts of dispersant, 3-8 parts of film forming additive, 5-8 parts of reinforcing filler and 150-200 parts of water; the modified acrylic resin molecules are in a grid structure, a great amount of long-chain fluorocarbon is contained in the side chains, the good hydrophobic effect is achieved, and meanwhile, polyethylene wax is inserted between the molecules, so that after the prepared water-based paint is formed into a film, a fluorocarbon hydrophobic layer-polyethylene wax layer-fluorocarbon hydrophobic layer cross layer structure is formed, the water resistance of the water-based paint is greatly improved, meanwhile, the polyethylene wax molecules are inserted, and the back adhesion phenomenon of the prepared coating film can not occur.
Description
Technical Field
The invention relates to the field of paint preparation, in particular to a high-water-resistance water-based paint and a preparation method thereof.
Background
The 21 st century is a green and environment-friendly century. The resource and energy are saved, and no pollution is the main development direction of the world paint. The vast majority of the rust-proof paint anticorrosive paint used at home at present is solvent-type paint, and the biggest defects of the paint are environmental pollution, flammability and explosiveness, harm to human bodies and waste of a large amount of resources and energy sources. The organic volatile VOC content of the solvent type paint products in the current market is up to 50% -60%, the annual emission of the organic volatile VOC is approximately 20 ten thousand tons, the environment is polluted, the energy is wasted, and therefore, the development of the high-performance water-based paint is the focus of the domestic and foreign paint industry. The existing water-based paint widely applied in the market comprises water-based inorganic zinc-rich paint, water-based epoxy paint, water-based acrylic paint and the like, and the conventional acrylic resin has poor water resistance, low adhesive film hardness and poor anti-back adhesion, so that the paint has poor effect in the use process.
Disclosure of Invention
The invention aims to provide a high-water-resistance water-based paint and a preparation method thereof, and solves the problems of poor water resistance, low adhesive film hardness and poor anti-back adhesion of the water-based paint at the present stage.
The aim of the invention can be achieved by the following technical scheme:
the high-water-resistance water-based paint comprises the following raw materials in parts by weight: 80-100 parts of modified acrylic resin, 2-4 parts of talcum powder, 1-3 parts of mica powder, 0.05-0.1 part of defoamer, 1.5-3 parts of dispersant, 3-8 parts of film forming additive, 5-8 parts of reinforcing filler and 150-200 parts of water.
Further, the defoamer is one or more of defoamer GP330, defoamer GPE3000 and defoamer DF103, the dispersant is one or more of sodium oleate, sokalan CP5 dispersant and Ecodisp90 dispersant, and the film forming additive is one or more of propylene glycol methyl ether acetate, propylene glycol diethyl ether and propylene glycol methyl ether.
Further, the modified acrylic resin is prepared by the following steps:
step A1: uniformly mixing 4-nitrophthalic anhydride, sodium hydroxide and deionized water, stirring and adding cuprous chloride at the rotation speed of 300-500r/min and the temperature of 25-30 ℃, heating to 60-70 ℃, dropwise adding vinyl chloride, reacting for 3-5h, filtering to remove filter residues, washing the filtrate with water, and distilling to obtain an intermediate 1;
the reaction process is as follows:
step A2: uniformly mixing a hydroxyl phosphorus lime supported palladium carbon catalyst, an intermediate 1 and deionized water, stirring at the rotation speed of 500-600r/min and the temperature of 75-85 ℃, introducing hydrogen, reacting for 10-15h, adding reactants into carbon tetrachloride, stirring for 10-15min, filtering to remove filter residues, and distilling the filtrate at the temperature of 80-90 ℃ to obtain an intermediate 2;
the reaction process is as follows:
step A3: uniformly mixing the intermediate 2, the perfluorinated butyl acrylate, the methacrylic acid, the methyl methacrylate and the azodiisobutyronitrile to obtain a mixture, uniformly mixing the dimethylbenzene and the n-butanol, stirring at the rotating speed of 200-300r/min and the temperature of 90-100 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1-1.5h, dropwise adding a benzoyl peroxide solution, continuously reacting for 2-3h, and sieving with a 300-mesh sieve to obtain the pre-modified acrylic resin;
the reaction process is as follows:
step A4: uniformly mixing polyethylene wax and maleic anhydride, introducing nitrogen to remove air, melting and stirring for 20-30min at the rotation speed of 120-150r/min and the temperature of 110-130 ℃, heating to the temperature of 140-145 ℃, adding dibenzoyl peroxide, reacting for 2-3h to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding modified polyethylene wax at the rotation speed of 150-200r/min and the temperature of 5-10 ℃, reacting for 8-10h, heating to the temperature of 60-70 ℃, reacting for 30-40min, adding triethylamine, acetic anhydride and nickel acetate, continuously reacting for 3-5h, cooling to the temperature of 0 ℃, filtering to remove filtrate, and obtaining the modified acrylic resin.
Further, the dosage ratio of the 4-nitrophthalic anhydride, sodium hydroxide, deionized water, cuprous chloride and vinyl chloride in the step A1 is 0.5mol:1mol:120mL:3g:1.4mol.
Further, the dosage ratio of the hydroxyapatite supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol:0.06g:5mL.
Further, the dosage ratio of the intermediate 2, the perfluorobutyl acrylate, the methacrylic acid, the methyl methacrylate, the azodiisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g to 6g to 13g to 18g to 0.15g to 70g to 20g to 10mL, and the mass fraction of the benzoyl peroxide solution is 10%.
Further, the dosage mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15:100:0.1, and the dosage ratio of the pre-modified acrylic resin, the modified polyethylene wax, the triethylamine, the acetic anhydride and the nickel acetate is 6.8g:5.5g:5mL:12mL:3.5g.
Further, the reinforcing filler is prepared by the following steps:
uniformly mixing graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid, reacting for 5-7h at the rotation speed of 150-200r/min and the temperature of 80-85 ℃, cooling to room temperature, adding deionized water, standing for 10-15h, filtering to remove filtrate, adding filter cakes into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 3-5h at the temperature of 0-3 ℃, heating to the temperature of 30-35 ℃, reacting for 1-3h, adding deionized water, heating to the temperature of 80-90 ℃, reacting for 5-7h, adding hydrogen peroxide, reacting for 2-3h at the room temperature, adding reactants into hydrochloric acid solution, washing to the center with deionized water, ultrasonically stripping for 2-3h to obtain graphene oxide, uniformly mixing graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, ball milling for 30-40min at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, and drying the substrate to obtain the reinforcing filler.
Further, the dosage ratio of graphite to potassium persulfate to phosphorus pentoxide to concentrated sulfuric acid is 3g to 2.5g to 12mL, the dosage ratio of filter cake to concentrated sulfuric acid to sodium nitrate to potassium permanganate to deionized water to hydrogen peroxide is 3g to 50mL to 2.5g to 15g to 500mL to 20mL, the mass fraction of concentrated sulfuric acid is 98%, and the dosage of polymethylhydrosiloxane is 6-8% of the mass of graphene oxide.
The preparation method of the high-water-resistance water-based paint specifically comprises the following steps:
and weighing the raw materials of modified acrylic resin, talcum powder, mica powder, defoamer, dispersant, film forming auxiliary agent, reinforcing filler and water, and uniformly blending to prepare the water-based paint.
The invention has the beneficial effects that: in the process of preparing the high water-resistant water-based paint, modified acrylic resin and reinforcing filler are prepared, 4-nitrophthalic anhydride is taken as a raw material for hydrolysis under alkaline condition, cuprous chloride is taken as a catalyst for reaction with vinyl chloride to prepare an intermediate 1, the intermediate 1 is subjected to reduction treatment under the action of a hydroxyapatite-supported palladium carbon catalyst, so that nitro groups on the intermediate 1 are converted into amino groups to prepare an intermediate 2, the perfluorobutyl acrylate, methacrylic acid and methyl methacrylate are copolymerized to prepare a pre-modified acrylic resin, the polyethylene wax is subjected to melt grafting by using maleic anhydride to prepare modified polyethylene wax, the modified polyethylene wax is subjected to reaction with the pre-modified acrylic resin, so that an anhydride structure on the modified polyethylene wax is reacted with amino groups on side chains of the pre-modified acrylic resin, the modified polyethylene wax is grafted on the pre-modified acrylic resin molecules, the modified acrylic resin molecules are in a grid structure, the side chains have a large amount of long chain, the graphene is intercalated into a hydrophobic layer, the graphene oxide layer is formed, the water-resistant coating is further prepared, the water-resistant paint is prepared, the water-resistant layer is formed by the graphene oxide layer is formed, and the water-resistant coating is further prepared, and the water-resistant layer is formed by the graphene oxide-oriented water-resistant coating is further prepared, the coating film hardness is effectively improved by adding the coating film and talcum powder and mica powder in a compounding way, and the coating film is not easy to damage under the action of external force after being solidified.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high-water-resistance water-based paint comprises the following raw materials in parts by weight: 80 parts of modified acrylic resin, 2 parts of talcum powder, 1 part of mica powder, 3300.05 parts of defoamer GP, 1.5 parts of sodium oleate, 3 parts of propylene glycol methyl ether acetate, 5-8 parts of reinforcing filler and 150 parts of water;
the water-based paint is prepared by the following steps:
weighing the raw materials, and uniformly blending the raw materials to prepare the water-based paint.
The modified acrylic resin is prepared by the following steps:
step A1: uniformly mixing 4-nitrophthalic anhydride, sodium hydroxide and deionized water, stirring and adding cuprous chloride under the conditions of the rotating speed of 300r/min and the temperature of 25 ℃, heating to the temperature of 60 ℃, dropwise adding vinyl chloride, reacting for 3 hours, filtering to remove filter residues, washing filtrate with water, and distilling to obtain an intermediate 1;
step A2: uniformly mixing a hydroxyl phosphorus lime supported palladium-carbon catalyst, an intermediate 1 and deionized water, stirring at a rotating speed of 500r/min and a temperature of 75 ℃, introducing hydrogen, reacting for 10 hours, adding reactants into carbon tetrachloride, stirring for 10 minutes, filtering to remove filter residues, and distilling the filtrate at a temperature of 80 ℃ to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, the perfluorinated butyl acrylate, the methacrylic acid, the methyl methacrylate and the azodiisobutyronitrile to obtain a mixture, uniformly mixing the dimethylbenzene and the n-butanol, stirring at the rotating speed of 200r/min and the temperature of 90 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1h, dropwise adding a benzoyl peroxide solution, continuously reacting for 2h, and sieving with a 300-mesh sieve to obtain the pre-modified acrylic resin;
step A4: uniformly mixing polyethylene wax and maleic anhydride, introducing nitrogen to remove air, melting and stirring for 20min at the rotation speed of 120r/min and the temperature of 110 ℃, heating to the temperature of 140 ℃, adding dibenzoyl peroxide, reacting for 2h to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding modified polyethylene wax at the rotation speed of 150r/min and the temperature of 5 ℃, reacting for 8h, heating to the temperature of 60 ℃, reacting for 30min, adding triethylamine, acetic anhydride and nickel acetate, continuously reacting for 3h, cooling to the temperature of 0 ℃, filtering to remove filtrate, and obtaining modified acrylic resin.
The dosage ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the chloroethylene in the step A1 is 0.5mol:1mol:120mL:3g:1.4mol.
The dosage ratio of the hydroxyl phosphorus lime supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol:0.06g:5mL.
The dosage ratio of the intermediate 2, the perfluorobutyl acrylate, the methacrylic acid, the methyl methacrylate, the azodiisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g to 6g to 13g to 18g to 0.15g to 70g to 20g to 10mL, and the mass fraction of the benzoyl peroxide solution is 10%.
The dosage mass ratio of the polyethylene wax to the maleic anhydride to the dibenzoyl peroxide in the step A4 is 15:100:0.1, and the dosage ratio of the pre-modified acrylic resin to the modified polyethylene wax to the triethylamine to the acetic anhydride to the nickel acetate is 6.8g:5.5g:5mL:12mL:3.5g.
The reinforcing filler is prepared by the following steps:
uniformly mixing graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid, reacting for 5 hours at the rotating speed of 150r/min and the temperature of 80 ℃, cooling to room temperature, adding deionized water, standing for 10 hours, filtering to remove filtrate, adding filter cakes into concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 3 hours at the temperature of 0 ℃, heating to the temperature of 30 ℃, reacting for 1 hour, adding deionized water, heating to the temperature of 80 ℃, reacting for 5 hours, adding hydrogen peroxide, reacting for 2 hours at room temperature, adding reactants into hydrochloric acid solution, washing with deionized water to the center, ultrasonically stripping for 2 hours, preparing graphene oxide, adding graphene oxide and polymethyl hydrosiloxane into a ball milling tank, ball milling for 30 minutes at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, and drying a substrate to obtain the reinforcing filler.
The dosage ratio of graphite to potassium persulfate to phosphorus pentoxide to concentrated sulfuric acid is 3g to 2.5g to 12mL, the dosage ratio of filter cake to concentrated sulfuric acid to sodium nitrate to potassium permanganate to deionized water to hydrogen peroxide is 3g to 50mL to 2.5g to 15g to 500mL to 20mL, the mass fraction of concentrated sulfuric acid is 98%, and the dosage of polymethylhydrosiloxane is 6% of the mass of graphene oxide.
Example 2
The high-water-resistance water-based paint comprises the following raw materials in parts by weight: 90 parts of modified acrylic resin, 3 parts of talcum powder, 2 parts of mica powder, 30000.08 parts of defoamer GPE, 2 parts of Sokalan CP5 dispersing agent, 5 parts of propylene glycol ethyl ether, 6 parts of reinforcing filler and 180 parts of water;
the water-based paint is prepared by the following steps:
weighing the raw materials, and uniformly blending the raw materials to prepare the water-based paint.
The modified acrylic resin is prepared by the following steps:
step A1: uniformly mixing 4-nitrophthalic anhydride, sodium hydroxide and deionized water, stirring and adding cuprous chloride under the conditions of the rotating speed of 300r/min and the temperature of 28 ℃, heating to 65 ℃, dropwise adding vinyl chloride, reacting for 4 hours, filtering to remove filter residues, washing filtrate with water, and distilling to obtain an intermediate 1;
step A2: uniformly mixing a hydroxyl phosphorus lime supported palladium-carbon catalyst, an intermediate 1 and deionized water, stirring at a rotating speed of 500r/min and a temperature of 80 ℃, introducing hydrogen, reacting for 13h, adding reactants into carbon tetrachloride, stirring for 13min, filtering to remove filter residues, and distilling the filtrate at a temperature of 85 ℃ to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, the perfluorinated butyl acrylate, the methacrylic acid, the methyl methacrylate and the azodiisobutyronitrile to obtain a mixture, uniformly mixing the dimethylbenzene and the n-butanol, stirring at the rotating speed of 200r/min and the temperature of 95 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1.3h, dropwise adding a benzoyl peroxide solution, continuously reacting for 2.5h, and sieving with a 300-mesh sieve to obtain the pre-modified acrylic resin;
step A4: uniformly mixing polyethylene wax and maleic anhydride, introducing nitrogen to remove air, melting and stirring for 25min at the rotation speed of 120r/min and the temperature of 120 ℃, heating to the temperature of 143 ℃, adding dibenzoyl peroxide, reacting for 2.5h to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding modified polyethylene wax at the rotation speed of 180r/min and the temperature of 7 ℃, reacting for 9h, heating to the temperature of 65 ℃, reacting for 35min, adding triethylamine, acetic anhydride and nickel acetate, continuing to react for 4h, cooling to the temperature of 0 ℃, filtering to remove filtrate, and obtaining modified acrylic resin.
The dosage ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the chloroethylene in the step A1 is 0.5mol:1mol:120mL:3g:1.4mol.
The dosage ratio of the hydroxyl phosphorus lime supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol:0.06g:5mL.
The dosage ratio of the intermediate 2, the perfluorobutyl acrylate, the methacrylic acid, the methyl methacrylate, the azodiisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g to 6g to 13g to 18g to 0.15g to 70g to 20g to 10mL, and the mass fraction of the benzoyl peroxide solution is 10%.
The dosage mass ratio of the polyethylene wax to the maleic anhydride to the dibenzoyl peroxide in the step A4 is 15:100:0.1, and the dosage ratio of the pre-modified acrylic resin to the modified polyethylene wax to the triethylamine to the acetic anhydride to the nickel acetate is 6.8g:5.5g:5mL:12mL:3.5g.
The reinforcing filler is prepared by the following steps:
uniformly mixing graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid, reacting for 6 hours at the condition of the rotating speed of 180r/min and the temperature of 83 ℃, cooling to room temperature, adding deionized water, standing for 13 hours, filtering to remove filtrate, adding filter cakes into concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 4 hours at the temperature of 2 ℃, heating to the temperature of 33 ℃, reacting for 2 hours, adding deionized water, heating to the temperature of 85 ℃, reacting for 6 hours, adding hydrogen peroxide, reacting for 2.5 hours at room temperature, adding reactants into hydrochloric acid solution, washing to the center by using deionized water, ultrasonically stripping for 2.5 hours, preparing graphene oxide, uniformly mixing graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, ball milling for 35 minutes at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, and drying a substrate to prepare the reinforcing filler.
The dosage ratio of graphite to potassium persulfate to phosphorus pentoxide to concentrated sulfuric acid is 3g to 2.5g to 12mL, the dosage ratio of filter cake to concentrated sulfuric acid to sodium nitrate to potassium permanganate to deionized water to hydrogen peroxide is 3g to 50mL to 2.5g to 15g to 500mL to 20mL, the mass fraction of concentrated sulfuric acid is 98%, and the dosage of polymethylhydrosiloxane is 7% of the mass of graphene oxide.
Example 3
The high-water-resistance water-based paint comprises the following raw materials in parts by weight: 100 parts of modified acrylic resin, 4 parts of talcum powder, 3 parts of mica powder, 1030.1 parts of defoamer DF, 8 parts of Ecodisp903 parts of propylene glycol methyl ether, 8 parts of reinforcing filler and 200 parts of water;
the water-based paint is prepared by the following steps:
weighing the raw materials, and uniformly blending the raw materials to prepare the water-based paint.
The modified acrylic resin is prepared by the following steps:
step A1: uniformly mixing 4-nitrophthalic anhydride, sodium hydroxide and deionized water, stirring and adding cuprous chloride under the conditions of the rotating speed of 500r/min and the temperature of 30 ℃, heating to the temperature of 70 ℃, dropwise adding vinyl chloride, reacting for 5 hours, filtering to remove filter residues, washing filtrate with water, and distilling to obtain an intermediate 1;
step A2: uniformly mixing a hydroxyl phosphorus lime supported palladium-carbon catalyst, an intermediate 1 and deionized water, stirring at the rotation speed of 600r/min and the temperature of 85 ℃, introducing hydrogen, reacting for 10-15h, adding reactants into carbon tetrachloride, stirring for 15min, filtering to remove filter residues, and distilling the filtrate at the temperature of 90 ℃ to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, the perfluorinated butyl acrylate, the methacrylic acid, the methyl methacrylate and the azodiisobutyronitrile to obtain a mixture, uniformly mixing the dimethylbenzene and the n-butanol, stirring at the rotating speed of 300r/min and the temperature of 100 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1.5h, dropwise adding a benzoyl peroxide solution, continuously reacting for 3h, and sieving with a 300-mesh sieve to obtain the pre-modified acrylic resin;
step A4: uniformly mixing polyethylene wax and maleic anhydride, introducing nitrogen to remove air, melting and stirring for 30min at the rotation speed of 150r/min and the temperature of 130 ℃, heating to the temperature of 145 ℃, adding dibenzoyl peroxide, reacting for 3h to obtain modified polyethylene wax, dispersing the pre-modified acrylic resin in toluene, adding the modified polyethylene wax at the rotation speed of 200r/min and the temperature of 10 ℃, reacting for 10h, heating to the temperature of 70 ℃, reacting for 40min, adding triethylamine, acetic anhydride and nickel acetate, continuously reacting for 5h, cooling to the temperature of 0 ℃, filtering to remove filtrate, and obtaining the modified acrylic resin.
The dosage ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the chloroethylene in the step A1 is 0.5mol:1mol:120mL:3g:1.4mol.
The dosage ratio of the hydroxyl phosphorus lime supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol:0.06g:5mL.
The dosage ratio of the intermediate 2, the perfluorobutyl acrylate, the methacrylic acid, the methyl methacrylate, the azodiisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g to 6g to 13g to 18g to 0.15g to 70g to 20g to 10mL, and the mass fraction of the benzoyl peroxide solution is 10%.
The dosage mass ratio of the polyethylene wax to the maleic anhydride to the dibenzoyl peroxide in the step A4 is 15:100:0.1, and the dosage ratio of the pre-modified acrylic resin to the modified polyethylene wax to the triethylamine to the acetic anhydride to the nickel acetate is 6.8g:5.5g:5mL:12mL:3.5g.
The reinforcing filler is prepared by the following steps:
uniformly mixing graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid, reacting for 7 hours at the rotation speed of 200r/min and the temperature of 85 ℃, cooling to room temperature, adding deionized water, standing for 15 hours, filtering to remove filtrate, adding filter cakes into concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 5 hours at the temperature of 3 ℃, heating to the temperature of 35 ℃, reacting for 3 hours, adding deionized water, heating to the temperature of 90 ℃, reacting for 7 hours, adding hydrogen peroxide, reacting for 3 hours at room temperature, adding reactants into hydrochloric acid solution, washing with deionized water to the center, ultrasonically stripping for 3 hours, preparing graphene oxide, adding graphene oxide and polymethyl hydrosiloxane into a ball milling tank, ball milling for 40 minutes at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, and drying a substrate to obtain the reinforcing filler.
The dosage ratio of graphite to potassium persulfate to phosphorus pentoxide to concentrated sulfuric acid is 3g to 2.5g to 12mL, the dosage ratio of filter cake to concentrated sulfuric acid to sodium nitrate to potassium permanganate to deionized water to hydrogen peroxide is 3g to 50mL to 2.5g to 15g to 500mL to 20mL, the mass fraction of concentrated sulfuric acid is 98%, and the dosage of polymethylhydrosiloxane is 8% of the mass of graphene oxide.
Comparative example 1
This comparative example uses acrylic resin instead of modified acrylic resin as compared with example 1, and the rest of the procedure is the same.
Comparative example 2
This comparative example was compared to example 1 without the addition of reinforcing filler, the remainder of the procedure being identical.
Comparative example 3
The comparative example is an acrylic water paint disclosed in chinese patent CN111073420 a.
The water-based paint prepared in examples 1-3 and comparative examples 1-3 were tested for water resistance according to GB/T1733-1993, scratch resistance according to GB/T9279-1988, and anti-sticking according to GB/T1762-1980, and the results are shown in the following table;
as can be seen from the above table, the water-based paint prepared in examples 1-3 has no obvious change on the surface of a paint film after being soaked in water for 72 hours, no scratch appears on the surface of the paint film after 500g of load treatment, and the filter paper is attached to the surface of the paint film for treatment, so that the filter paper cannot be adhered to the paint film, and the water-based paint has good water resistance, scratch resistance and anti-back adhesion effects.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. A high water-resistant water-based paint is characterized in that: comprises the following raw materials in parts by weight: 80-100 parts of modified acrylic resin, 2-4 parts of talcum powder, 1-3 parts of mica powder, 0.05-0.1 part of defoamer, 1.5-3 parts of dispersant, 3-8 parts of film forming additive, 5-8 parts of reinforcing filler and 150-200 parts of water;
the modified acrylic resin is prepared by the following steps:
step A1: mixing 4-nitrophthalic anhydride, sodium hydroxide and deionized water, stirring, adding cuprous chloride, heating, dropwise adding vinyl chloride, filtering to remove filter residues after the reaction is finished, washing filtrate with water, and distilling to obtain an intermediate 1;
step A2: mixing and stirring a hydroxyl phosphorus lime supported palladium-carbon catalyst, an intermediate 1 and deionized water, introducing hydrogen, reacting, adding reactants into carbon tetrachloride, stirring, filtering to remove filter residues, and distilling the filtrate to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, the perfluorinated butyl acrylate, the methacrylic acid, the methyl methacrylate and the azodiisobutyronitrile to prepare a mixture, mixing and stirring dimethylbenzene and n-butanol, introducing nitrogen for protection, slowly adding the mixture, dropwise adding a benzoyl peroxide solution after the reaction, and continuously reacting to prepare the pre-modified acrylic resin;
step A4: mixing polyethylene wax and maleic anhydride, carrying out melt stirring, heating, adding dibenzoyl peroxide, carrying out reaction to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding modified polyethylene wax, carrying out reaction, heating for continuous reaction, adding triethylamine, acetic anhydride and nickel acetate, continuously reacting, cooling and filtering to obtain modified acrylic resin;
the reinforcing filler is prepared by the following steps:
uniformly mixing graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid, reacting for 5-7h at the rotation speed of 150-200r/min and the temperature of 80-85 ℃, cooling to room temperature, adding deionized water, standing for 10-15h, filtering to remove filtrate, adding filter cakes into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 3-5h at the temperature of 0-3 ℃, heating to the temperature of 30-35 ℃, reacting for 1-3h, adding deionized water, heating to the temperature of 80-90 ℃, reacting for 5-7h, adding hydrogen peroxide, reacting for 2-3h at the room temperature, adding reactants into hydrochloric acid solution, washing with deionized water to neutrality, ultrasonically stripping for 2-3h to obtain graphene oxide, uniformly mixing graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, ball milling for 30-40min at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, and drying the substrate to obtain the reinforcing filler.
2. The high water resistant aqueous coating of claim 1, wherein: the defoaming agent is one or more of a defoaming agent GP330, a defoaming agent GPE3000 and a defoaming agent DF103, the dispersing agent is one or more of sodium oleate, a Sokalan CP5 dispersing agent and an Ecodisp90 dispersing agent, and the film forming additive is one or more of propylene glycol methyl ether acetate, propylene glycol diethyl ether and propylene glycol methyl ether.
3. The high water resistant aqueous coating of claim 1, wherein: the dosage ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the chloroethylene in the step A1 is 0.5mol:1mol:120mL:3g:1.4mol.
4. The high water resistant aqueous coating of claim 1, wherein: the dosage ratio of the hydroxyl phosphorus lime supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol:0.06g:5mL.
5. The high water resistant aqueous coating of claim 1, wherein: the dosage ratio of the intermediate 2, the perfluorobutyl acrylate, the methacrylic acid, the methyl methacrylate, the azodiisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g to 6g to 13g to 18g to 0.15g to 70g to 20g to 10mL, and the mass fraction of the benzoyl peroxide solution is 10%.
6. The high water resistant aqueous coating of claim 1, wherein: the dosage mass ratio of the polyethylene wax to the maleic anhydride to the dibenzoyl peroxide in the step A4 is 15:100:0.1, and the dosage ratio of the pre-modified acrylic resin to the modified polyethylene wax to the triethylamine to the acetic anhydride to the nickel acetate is 6.8g:5.5g:5mL:12mL:3.5g.
7. The method for preparing the high-water-resistance water-based paint according to claim 1, which is characterized in that: the method specifically comprises the following steps:
and weighing the raw materials of modified acrylic resin, talcum powder, mica powder, defoamer, dispersant, film forming auxiliary agent, reinforcing filler and water, and uniformly blending to prepare the water-based paint.
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| US4086153A (en) * | 1975-10-09 | 1978-04-25 | Toyo Kohan Co., Ltd. | Method of producing a composite coated steel sheet |
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| CN108070294A (en) * | 2017-12-30 | 2018-05-25 | 上海墨传新材料科技有限公司 | High abrasion aqueous ink used for plastic and preparation method thereof |
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| US4174335A (en) * | 1975-07-22 | 1979-11-13 | Mitsui Petrochemical Industries, Ltd. | Aqueous dispersions of olefinic resin compositions and process for preparation thereof |
| US4086153A (en) * | 1975-10-09 | 1978-04-25 | Toyo Kohan Co., Ltd. | Method of producing a composite coated steel sheet |
| WO2009024398A1 (en) * | 2007-08-20 | 2009-02-26 | Robert Bosch Gmbh | Molding compound and method for producing a molding compound |
| CN101619543A (en) * | 2009-07-27 | 2010-01-06 | 成都德美精英化工有限公司 | Thickening agent synthesized by acrylic ester and preparation method thereof |
| CN108070294A (en) * | 2017-12-30 | 2018-05-25 | 上海墨传新材料科技有限公司 | High abrasion aqueous ink used for plastic and preparation method thereof |
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