CN115141546A - 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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 defoaming agent, 1.5-3 parts of dispersing agent, 3-8 parts of film-forming additive, 5-8 parts of reinforcing filler and 150-200 parts of water; modified acrylic resin molecule is latticed structure, and the side chain contains a large amount of long chain halothane and has fine hydrophobic effect, has inserted polyethylene wax simultaneously between the molecule for behind the aqueous coating film forming of preparation, form halothane hydrophobic layer-polyethylene wax layer-halothane hydrophobic layer cross layer structure, promoted aqueous coating's water resistance greatly, the insertion of polyethylene wax molecule simultaneously makes preparation film can not appear sticking back the phenomenon.
Description
Technical Field
The invention relates to the field of paint preparation, and particularly relates to a high-water-resistance water-based paint and a preparation method thereof.
Background
The 21 st century is the green and environmental protection century. Resource conservation, energy conservation and no pollution are the main development directions of the world coatings. The most of the antirust paint anticorrosive coatings used in China at present are solvent-based coatings, and the most serious defects of the coatings are environmental pollution, flammability and explosiveness, harm to human bodies and waste of a large amount of resources and energy. The content of Volatile Organic Compounds (VOC) of solvent type coating products in the current market reaches 50-60%, and the annual emission of Volatile Organic Compounds (VOC) is nearly 20 ten thousand tons, so that the environment is polluted and energy is wasted, and therefore, the development of high-performance water-based coatings is the focus of coating industries at home and abroad. The existing market widely uses water-based paint such as water-based inorganic zinc-rich, water-based epoxy paint, water-based acrylic paint and the like, and the conventional acrylate resin has poor water resistance, low film hardness and poor anti-tack property, so that the effect of the paint in the using process is poor.
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 film hardness and poor anti-tack property of the water-based paint at the present stage.
The purpose of the invention can be realized by the following technical scheme:
a 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 defoaming agent, 1.5-3 parts of dispersing agent, 3-8 parts of film-forming additive, 5-8 parts of reinforcing filler and 150-200 parts of water.
Further, the defoaming agent is one or more of a defoaming agent GP330, a defoaming agent GPE3000 and a defoaming agent DF103 which are mixed in any proportion, the dispersing agent is one or more of sodium oleate, a SokalanCP5 dispersing agent and an Ecodisp90 dispersing agent which are mixed in any proportion, and the film forming additive is one or more of propylene glycol methyl ether acetate, propylene glycol ethyl ether and propylene glycol methyl ether which are mixed in any proportion.
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 under the conditions that the rotating speed is 300-500r/min and the temperature is 25-30 ℃, heating to 60-70 ℃, dropwise adding chloroethylene, 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 hydroxyl apatite ash loaded palladium carbon catalyst, the 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 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, butyl perfluoroacrylate, methacrylic acid, methyl methacrylate and azodiisobutyronitrile to obtain a mixture, uniformly mixing xylene and n-butyl alcohol, stirring at the rotation speed of 200-300r/min and at the temperature of 90-100 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1-1.5h, dropwise adding a benzoyl peroxide solution, continuing to react for 2-3h, and sieving with a 300-mesh sieve to obtain 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 at the temperature of 110-130 ℃, heating to the temperature of 140-145 ℃, adding dibenzoyl peroxide to react for 2-3h to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding the modified polyethylene wax to react for 8-10h at the rotation speed of 150-200r/min and at the temperature of 5-10 ℃, heating to the temperature of 60-70 ℃, reacting for 30-40min, adding triethylamine, acetic anhydride and nickel acetate to continue reacting for 3-5h, cooling to the temperature of 0 ℃, and filtering to remove filtrate to obtain the modified acrylic resin.
Furthermore, the dosage ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the vinyl chloride in the step A1 is 0.5mol.
Further, the usage ratio of the palladium-carbon catalyst supported by hydroxyapatite in step A2, the intermediate 1 and deionized water is 0.01mol.
Further, the dosage ratio of the intermediate 2, the butyl perfluoroacrylate, the methacrylic acid, the methyl methacrylate, the azobisisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g.
Furthermore, the mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15.
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 a filter cake into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 3-5h at the temperature of 0-3 ℃, heating to 30-35 ℃, reacting for 1-3h, adding deionized water, heating to 80-90 ℃, reacting for 5-7h, adding hydrogen peroxide, reacting for 2-3h at room temperature, adding reactants into a hydrochloric acid solution for washing, cleaning to the center with deionized water, ultrasonically stripping for 2-3h to prepare graphene oxide, uniformly mixing the graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, ball milling for 30-40min under the condition that the frequency of a main disc is 50Hz, washing with petroleum ether, centrifuging a substrate, and preparing the reinforcing filler.
Further, the use ratio of graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid is 3g, and is as follows, 1.5g.
A preparation method of a high-water-resistance water-based paint specifically comprises the following steps:
weighing raw materials of modified acrylic resin, talcum powder, mica powder, a defoaming agent, a dispersing agent, a film-forming assistant, a reinforcing filler and water, and uniformly blending to prepare the water-based paint.
The invention has the beneficial effects that: the invention prepares modified acrylic resin and reinforced filler in the process of preparing a high water-resistant water-based paint, the modified acrylic resin takes 4-nitrophthalic anhydride as raw material to hydrolyze under alkaline condition, then cuprous chloride is taken as catalyst to react with chloroethylene to prepare an intermediate 1, the intermediate 1 is reduced under the action of hydroxyl apatite ash loaded palladium carbon catalyst to convert nitro on the intermediate 1 into amino to prepare an intermediate 2, the intermediate 2, butyl perfluoroacrylate, methacrylic acid and methyl methacrylate are copolymerized to prepare pre-modified acrylic resin, polyethylene wax is melt grafted by maleic anhydride to prepare modified polyethylene wax, the modified polyethylene wax reacts with pre-modified acrylic resin to react an anhydride structure on a side chain of the pre-modified acrylic resin to prepare the modified acrylic resin, the modified polyethylene wax is grafted on a pre-modified acrylic resin molecule, the modified acrylic resin molecule is a grid structure, a large amount of long-chain fluorocarbon has good hydrophobic effect, polyethylene wax is inserted between molecules, after the prepared water-based paint forms a film, a hydrophobic layer-hydrophobic layer cross layer structure is formed, the water-resistant graphene side chain fluorocarbon coating is prepared, the graphene oxide coating film of the modified acrylic resin is greatly, the graphene oxide coating film is prepared, the graphene oxide coating is further, the graphene oxide coating film is prepared, the graphene oxide coating film is not subjected to obtain the graphene oxide, the graphene film coating, the graphene oxide coating film coating, the graphene oxide coating effect is improved, the graphene oxide coating effect is improved graphene coating, the graphene coating effect, the talcum powder and the mica powder are compounded and added, so that the hardness of the coating is effectively improved, and the coating is not easy to damage under the action of external force after being cured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A 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, 5363 parts of defoaming agent GP3300.05, 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 obtain 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 that the rotating speed is 300r/min and the temperature is 25 ℃, heating to 60 ℃, dropwise adding chloroethylene, reacting for 3 hours, filtering to remove filter residues, washing the filtrate with water, and distilling to obtain an intermediate 1;
step A2: uniformly mixing hydroxyl apatite ash-loaded palladium-carbon catalyst, the intermediate 1 and deionized water, stirring at the rotation speed of 500r/min and the 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 the temperature of 80 ℃ to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, butyl perfluoroacrylate, methacrylic acid, methyl methacrylate and azobisisobutyronitrile to obtain a mixture, uniformly mixing xylene and n-butyl alcohol, stirring at the rotation 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 passing through a 300-mesh screen to obtain 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 the 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, continuing to react for 3h, cooling to the temperature of 0 ℃, and filtering to remove filtrate to obtain the modified acrylic resin.
The use 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.
The use amount ratio of the hydroxyl phosphorus lime supported palladium carbon catalyst, the intermediate 1 and the deionized water in the step A2 is 0.01mol.
The dosage ratio of the intermediate 2, the butyl perfluoroacrylate, the methacrylic acid, the methyl methacrylate, the azobisisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g.
The mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15.
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 rotation 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 a filter cake into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 3 hours at the temperature of 0 ℃, heating to 30 ℃, reacting for 1 hour, adding deionized water, heating to 80 ℃, reacting for 5 hours, adding hydrogen peroxide, reacting at room temperature for 2 hours, adding reactants into a hydrochloric acid solution, washing, cleaning to the center with deionized water, ultrasonically stripping for 2 hours to prepare graphene oxide, uniformly mixing the graphene oxide and polymethylhydrosiloxane, adding into a pot, performing ball milling for 30 minutes at the main disc frequency of 50Hz, washing with petroleum ether, centrifuging, drying a substrate, and preparing the reinforcing filler.
The preparation method comprises the following steps that the using ratio of the graphite, the potassium persulfate, the phosphorus pentoxide and the concentrated sulfuric acid is 3g, namely 12mL, the using ratio of the filter cake, the concentrated sulfuric acid, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide is 3g, 505 g.
Example 2
A 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, 5363 parts of defoamer GPE30000.08, 2 parts of Sokalan CP5 dispersant, 5 parts of propylene glycol 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 obtain 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 that the rotating speed is 300r/min and the temperature is 28 ℃, heating to 65 ℃, dropwise adding chloroethylene, reacting for 4 hours, filtering to remove filter residues, washing the filtrate with water, and distilling to obtain an intermediate 1;
step A2: uniformly mixing hydroxyl apatite ash-loaded palladium-carbon catalyst, the intermediate 1 and deionized water, stirring at the rotation speed of 500r/min and the temperature of 80 ℃, introducing hydrogen, reacting for 13 hours, adding reactants into carbon tetrachloride, stirring for 13 minutes, filtering to remove filter residues, and distilling filtrate at the temperature of 85 ℃ to obtain an intermediate 2;
step A3: uniformly mixing the intermediate 2, butyl perfluoroacrylate, methacrylic acid, methyl methacrylate and azodiisobutyronitrile to obtain a mixture, uniformly mixing xylene and n-butyl alcohol, stirring at the rotation speed of 200r/min and at 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 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 the 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, continuously reacting for 4h, cooling to the temperature of 0 ℃, filtering to remove filtrate, and thus obtaining the modified acrylic resin.
The use 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.
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.
The use ratio of the intermediate 2, the butyl perfluoroacrylate, the methacrylic acid, the methyl methacrylate, the azobisisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g, 6g, 13g, 7070705 g.
The mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15.
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 rotation 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 a filter cake into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 4 hours at the temperature of 2 ℃, heating to 33 ℃, reacting for 2 hours, adding deionized water, heating to 85 ℃, reacting for 6 hours, adding hydrogen peroxide, reacting for 2.5 hours at room temperature, adding reactants into a hydrochloric acid solution, washing, cleaning to the center with deionized water, ultrasonically stripping for 2.5 hours to prepare graphene oxide, uniformly mixing the graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, carrying out ball milling for 35 minutes under the condition that the main disc frequency is 50Hz, washing with petroleum ether, centrifuging, and drying a substrate to prepare the reinforcing filler.
The preparation method comprises the following steps that the using ratio of the graphite, the potassium persulfate, the phosphorus pentoxide and the concentrated sulfuric acid is 3g, namely 12mL, the using ratio of the filter cake, the concentrated sulfuric acid, the sodium nitrate, the potassium permanganate, the deionized water and the hydrogen peroxide is 3g, 505 g.
Example 3
A 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, 5363 parts of defoamer DF1030.1, 903 parts of EcodisP, 8 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 obtain 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 that the rotating speed is 500r/min and the temperature is 30 ℃, heating to 70 ℃, dropwise adding chloroethylene, 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 apatite ash-loaded palladium-carbon catalyst, the 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, butyl perfluoroacrylate, methacrylic acid, methyl methacrylate and azodiisobutyronitrile to obtain a mixture, uniformly mixing xylene and n-butyl alcohol, stirring at the rotation speed of 300r/min and at the temperature of 100 ℃, introducing nitrogen for protection, slowly adding the mixture, reacting for 1.5 hours, dropwise adding a benzoyl peroxide solution, continuously reacting for 3 hours, and sieving with a 300-mesh sieve to obtain 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 145 ℃, adding dibenzoyl peroxide, reacting for 3h to obtain modified polyethylene wax, dispersing pre-modified acrylic resin in toluene, adding modified polyethylene wax at the rotation speed of 200r/min and the temperature of 10 ℃, reacting for 10h, heating to 70 ℃, reacting for 40min, adding triethylamine, acetic anhydride and nickel acetate, continuously reacting for 5h, cooling to 0 ℃, and filtering to remove filtrate to obtain the modified acrylic resin.
The use ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the vinyl chloride in the step A1 is 0.5mol.
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.
The dosage ratio of the intermediate 2, the butyl perfluoroacrylate, the methacrylic acid, the methyl methacrylate, the azobisisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g.
The mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15.
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 a filter cake into the concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, reacting for 5 hours at the temperature of 3 ℃, heating to 35 ℃, reacting for 3 hours, adding deionized water, heating to 90 ℃, reacting for 7 hours, adding hydrogen peroxide, reacting for 3 hours at room temperature, adding reactants into a hydrochloric acid solution, washing, cleaning to the center with deionized water, ultrasonically stripping for 3 hours to obtain graphene oxide, uniformly mixing the graphene oxide and polymethylhydrosiloxane, adding into a ball milling tank, performing ball milling for 40 minutes under the condition that the main disc frequency is 50Hz, washing with petroleum ether, centrifuging, drying a substrate, and preparing the reinforcing filler.
The mass fraction of the graphite, the potassium persulfate, the phosphorus pentoxide and the concentrated sulfuric acid is 98%, and the mass fraction of the polymethylhydrosiloxane is 8% of the mass of the graphene oxide.
Comparative example 1
This comparative example compared with example 1, the acrylic resin was used in place of the modified acrylic resin, and the same procedure was followed.
Comparative example 2
This comparative example compares to example 1 without the addition of reinforcing filler and the rest of the procedure is the same.
Comparative example 3
The comparative example is an acrylic acid water-based paint disclosed in Chinese patent CN 111073420A.
The water-based paint prepared in the examples 1-3 and the comparative examples 1-3 is subjected to water resistance detection according to the GB/T1733-1993, scratch resistance detection according to the GB/T9279-1988 and anti-after-tack detection according to the GB/T1762-1980, and the results are shown in the table;
from the above table, it can be seen that the surface of the paint film of the water-based paint prepared in examples 1-3 does not change significantly after being soaked in water for 72 hours, no scratch is formed 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 does not stick to the paint film, which indicates that the water-based paint has good water resistance, scratch resistance and anti-sticking effects.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A high-water-resistance water-based paint is characterized in that: the feed 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 defoaming agent, 1.5-3 parts of dispersing agent, 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 and stirring 4-nitrophthalic anhydride, sodium hydroxide and deionized water, adding cuprous chloride, heating, dropwise adding chloroethylene, filtering to remove filter residue after reaction is finished, washing the filtrate with water, and distilling to obtain an intermediate 1;
step A2: mixing and stirring hydroxyl apatite supported palladium-carbon catalyst, the intermediate 1 and deionized water, introducing hydrogen for reaction, 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, butyl perfluoroacrylate, methacrylic acid, methyl methacrylate and azobisisobutyronitrile to obtain a mixture, mixing and stirring xylene and n-butyl alcohol, introducing nitrogen for protection, slowly adding the mixture, reacting, dropwise adding a benzoyl peroxide solution, and continuing to react to obtain pre-modified acrylic resin;
step A4: mixing polyethylene wax and maleic anhydride, carrying out melting 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, carrying out continuous reaction, cooling and filtering to obtain the modified acrylic resin.
2. The water-based paint with high water resistance as claimed in claim 1, wherein: the defoamer is one or more of defoamer GP330, defoamer GPE3000 and defoamer DF103 which are mixed in any proportion, the dispersant is one or more of sodium oleate, sokalan CP5 dispersant and Ecodis P90 dispersant which are mixed in any proportion, and the film forming aid is one or more of propylene glycol methyl ether acetate, propylene glycol ethyl ether and propylene glycol methyl ether which are mixed in any proportion.
3. The high-water-resistance water-based paint according to claim 1, characterized in that: the use ratio of the 4-nitrophthalic anhydride, the sodium hydroxide, the deionized water, the cuprous chloride and the vinyl chloride in the step A1 is 0.5mol.
4. The water-based paint with high water resistance as claimed in 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.
5. The water-based paint with high water resistance as claimed in claim 1, wherein: the dosage ratio of the intermediate 2, the butyl perfluoroacrylate, the methacrylic acid, the methyl methacrylate, the azobisisobutyronitrile, the xylene, the n-butanol and the benzoyl peroxide solution in the step A3 is 15g.
6. The high-water-resistance water-based paint according to claim 1, characterized in that: the mass ratio of the polyethylene wax, the maleic anhydride and the dibenzoyl peroxide in the step A4 is 15.
7. The preparation method of the high-water-resistance water-based paint according to claim 1, characterized in that: the method specifically comprises the following steps:
weighing raw materials of modified acrylic resin, talcum powder, mica powder, a defoaming agent, a dispersing agent, a film-forming auxiliary agent, a reinforcing filler and water, and uniformly blending to obtain 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 |
| US4174335A (en) * | 1975-07-22 | 1979-11-13 | Mitsui Petrochemical Industries, Ltd. | Aqueous dispersions of olefinic resin compositions and process for preparation thereof |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Effective date of registration: 20230817 Address after: No. 21, Xinlong Road, Zhonglou District, Changzhou City, Jiangsu Province, 213000 Applicant after: JIANGSU HAOYUE PAINT Co.,Ltd. Address before: Room 2103, Block B, Wanda Office Building, Bengshan District, Bengbu City, Anhui Province, 233000 Applicant before: Bengbu Pengbang Construction Labor Service Co.,Ltd. |
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