CN112812647B - Low-VOC (volatile organic compound) and high-solid-content water-based paint based on acrylic resin and preparation process thereof - Google Patents
Low-VOC (volatile organic compound) and high-solid-content water-based paint based on acrylic resin and preparation process thereof Download PDFInfo
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- 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
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- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a low-VOC high-solid-content water-based paint based on acrylic resin and a preparation method thereof.
Description
Technical Field
The invention belongs to the field of chemical coatings, and particularly relates to a low-VOC high-solid-content water-based paint based on acrylic resin and a preparation process thereof.
Background
The acrylate coating is a synthetic ester coating with excellent performance, has a series of outstanding advantages such as excellent gloss retention, color retention, weather resistance, environmental protection, convenient construction, various curing modes and the like, and is widely applied to the fields of automobiles, household appliances, decoration and the like. The solid content of the acrylic resin which is widely used at present is generally not high, which can cause poor construction performance of the coating and unsatisfactory fullness of a coating, and the use of a large amount of organic solvent in the resin can cause harm to the environment, and the problems are urgently needed to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the low-VOC high-solid-content water-based paint based on the acrylic resin and the preparation process thereof, the VOC content is low and the solid content is high in the spraying process, the physical property of the paint is not reduced after the spraying and baking, and the paint still keeps excellent performances in the aspects of adhesive force, acid and alkali resistance and the like on the premise of reducing the viscosity, improving the solid content and relatively low VOC.
The specific technical scheme of the invention is as follows:
the low-VOC high-solid-content water-based paint based on the acrylic resin is prepared from the following raw materials, by weight, 42-50 parts of modified acrylic resin emulsion, 1-9 parts of film-forming auxiliary agent and 20-50 parts of pigment and filler;
the modified acrylic resin emulsion is prepared from the following raw materials, by weight, 40-100 parts of hyperbranched polyurethane acrylate copolymer, 0.2-0.3 part of functionalized silicon carbide and 10-80 parts of deionized water;
the hyperbranched polyurethane acrylate copolymer is prepared from the following raw materials, by weight, 10-30 parts of acrylic acid functional monomer, 40-100 parts of acrylic acid non-functional monomer and 0.2-1 part of initiator;
the acrylic functional monomer is prepared from the following raw materials in parts by weight, 10-15 parts of acetoacetoxyethyl methacrylate and 10-20 parts of hyperbranched polyurethane acrylate; the non-functional monomer is one or more selected from 10-50 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 20-40 parts of hydroxyethyl methacrylate and 20-50 parts of hydroxyethyl acrylate; the initiator is potassium persulfate or ammonium persulfate;
the functionalized silicon carbide is prepared from the following raw materials, by weight, 80-150 parts of distilled water, 5-30 parts of ethanol, 10 parts of silicon carbide and 0.5-5 parts of aminosilane coupling agent. The amino silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane or N-theta (aminoethyl) -gamma-aminopropyl trimethoxysilane, preferably gamma-aminopropyl triethoxysilane;
the hyperbranched polyurethane acrylate is prepared from the following raw materials, by weight, 20-100 parts of diisocyanate, 10-50 parts of oligomer polyol, 20-50 parts of hydroxypropyl acrylate, 0.1-1 part of catalyst, 1-20 parts of hyperbranched polyester, 0.1-1 part of polymerization inhibitor, 5-20 parts of anhydride and 1-5 parts of neutralizer;
the diisocyanate is at least one of toluene diisocyanate or isophorone diisocyanate, preferably isophorone diisocyanate;
the oligomer polyol is hydroxyl polypropylene glycol;
the catalyst is dibutyltin dilaurate;
the hyperbranched polyester, such as Boltorn type hyperbranched polyatomic alcohol which takes acrylic ester as a core and is produced by Perstorp company, has the hydroxyl functionality of 6-64 and the number average molecular weight of 2100-5100;
the polymerization inhibitor is one of 4-hydroxypiperidinol oxygen free radical, hydroquinone, p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol, and is preferably hydroquinone;
the acid anhydride is one of phthalic anhydride, mellitic acid anhydride and perfluoropropionic anhydride, and is preferably perfluoropropionic anhydride;
the neutralizing agent is at least one of dimethylethanolamine, triethylamine, triethanolamine, diethanolamine and monoethanolamine, and triethylamine is preferred;
the invention also provides a preparation method of the acrylic resin-based low-VOC high-solid-content water-based paint, which comprises the following steps:
and (3) taking the modified acrylic resin emulsion, the film-forming assistant and the pigment filler according to the formula ratio, stirring at a high speed, and grinding for 2-4h to obtain the water-based paint.
The film-forming assistant consists of a leveling agent, a wetting agent, an anti-settling agent, a defoaming agent and a thickening agent, wherein the leveling agent is at least one of a BYK-333 leveling agent, a BYK-375 leveling agent and a TEGO Glide 450 leveling agent, and preferably is a BYK-375 leveling agent; the wetting agent is at least one of TEGO 245 wetting dispersant, TEGO 250 wetting dispersant, TEGO 260 wetting dispersant and BYK-194 wetting dispersant, and is preferably TEGO 250 wetting dispersant; the anti-settling agent is an anti-settling agent BYK 410; the defoaming agent is a defoaming agent BYK 028; the thickener is a TEGO Visco plus 3030 thickener; the film-forming additive comprises 0.5-0.8 part of BYK-375 flatting agent, 0.5-0.8 part of TEGO 250 wetting dispersant, 0.3-0.8 part of BYK410 anti-settling agent, 0.5-0.8 part of BYK028 defoaming agent and 0.2-0.4 part of TEGO ViscoPlus 3030 thickening agent in parts by mass; the pigment and filler comprises, by weight, 10-20 parts of superfine aluminum silicate quartz powder, 10-15 parts of titanium dioxide, 10-15 parts of calcium sulfate and 5-10 parts of talcum powder.
The preparation method of the modified acrylic resin emulsion comprises the following steps:
adding the hyperbranched polyurethane acrylate copolymer, the functionalized silicon carbide aqueous dispersion and deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH to 9.0-10.0 by using ammonia water, and filtering to obtain the modified acrylic resin emulsion.
The preparation method of the hyperbranched polyurethane acrylate copolymer comprises the following steps:
adding acrylic acid functional monomers and non-functional monomer mixtures into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, adding an initiator aqueous solution into a reactor, stirring and polymerizing, then heating to 90-95 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of a system to 8.0-9.0, cooling and filtering to obtain the hyperbranched polyurethane acrylate copolymer.
The preparation method of the hyperbranched polyurethane acrylate in the functional monomer comprises the following steps:
(1) adding diisocyanate, hydroxypropyl acrylate, a catalyst and a polymerization inhibitor into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 2-5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches a theoretical endpoint;
(2) adding oligomer polyol into the intermediate product, stirring and reacting for 1-3h at 70 ℃, cooling to 50 ℃, adding an acetone solution of hyperbranched polyester, reacting for 2-4h at 50 ℃, adding anhydride as a solvent, heating to 100 ℃ for reacting for 2-5h, decompressing to remove the solvent, cooling to 40 ℃, adding a neutralizing agent for neutralizing to form salt, and obtaining the hyperbranched polyurethane acrylate.
The preparation method of the functionalized silicon carbide comprises the following steps:
adding distilled water, ethanol and silicon carbide in formula amount into a four-neck flask provided with a condenser tube, a thermometer and a stirrer, stirring at high speed, diluting an aminosilane coupling agent by using ethanol, slowly adding into the flask, adjusting the pH of the system to 3-4 by using dilute hydrochloric acid, and stirring for reacting for 2-4 h. Distilling by using a thin film evaporation device, recovering ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1h to obtain the amino functionalized silicon carbide aqueous dispersion.
The low-VOC and high-solid-content water-based paint based on the acrylic resin, which is prepared by the invention, has low VOC content and high solid content in the spraying process, does not reduce the physical properties of the paint after spraying and baking, and still maintains excellent performances in the aspects of adhesive force, acid and alkali resistance and the like on the premise of reducing viscosity, improving solid content and relatively low VOC.
Detailed Description
The raw materials used in the invention belong to the products sold on the market except for special instructions.
Example 1
(1) Adding 50 parts of isophorone diisocyanate, 40 parts of hydroxypropyl acrylate, 0.2 part of hydroquinone and 0.1 part of dibutyltin dilaurate into a four-neck flask provided with a condenser tube, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches the theoretical endpoint;
(2) adding 20 parts of hydroxy polypropylene glycol into the intermediate product, stirring and reacting at 70 ℃ for 3h, cooling to 50 ℃, adding an acetone solution containing 10 parts of hyperbranched polyester, reacting at 50 ℃ for 4h, adding 15 parts of perfluoropropionic anhydride into dioxane serving as a solvent, heating to 100 ℃ for reacting for 5h, decompressing and removing the solvent, cooling to 40 ℃, adding 3 parts of triethylamine for neutralizing to form salt, and obtaining hyperbranched polyurethane acrylate;
(3) adding 10 parts of acetoacetoxyethyl methacrylate, 15 parts of hyperbranched polyurethane acrylate, 20 parts of methyl methacrylate, 10 parts of butyl acrylate, 20 parts of hydroxyethyl methacrylate and 30 parts of hydroxyethyl acrylate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer; adding 0.2 part of ammonium persulfate aqueous solution into a reactor, stirring and polymerizing, heating to 90 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of the system to 8.0-9.0, cooling and filtering to obtain a hyperbranched polyurethane acrylate copolymer;
(4) adding 100 parts of distilled water, 10 parts of ethanol and 10 parts of silicon carbide into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring at a high speed, diluting 2 parts of aminosilane coupling agent gamma-aminopropyltriethoxysilane by using 10 parts of ethanol, slowly adding the diluted aminosilane coupling agent gamma-aminopropyltriethoxysilane into the flask, adjusting the pH value of a system to 3-4 by using diluted hydrochloric acid, stirring for reacting for 4 hours, distilling by using a thin film evaporation device, recovering ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1 hour to obtain an amino-functionalized silicon carbide aqueous dispersion;
(5) adding 40 parts of hyperbranched polyurethane acrylate copolymer, 0.2 part of functionalized silicon carbide aqueous dispersion and 10 parts of deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH value to 9.0-10.0 by using ammonia water, and filtering to obtain a modified acrylic resin emulsion;
(6) 45 parts of modified acrylic resin emulsion, 0.5 part of BYK-375 flatting agent, 0.6 part of TEGO 250 wetting dispersant, 0.3 part of BYK410 anti-settling agent, 0.5 part of BYK028 defoaming agent, 0.4 part of TEGO ViscoPlus 3030 thickener, 10 parts of superfine aluminum silicate quartz powder, 15 parts of titanium dioxide, 10 parts of calcium sulfate and 5 parts of talcum powder are stirred at high speed and ground for 4 hours to obtain the water-based paint.
Example 2
(1) Adding 20 parts of toluene diisocyanate, 20 parts of hydroxypropyl acrylate, 0.1 part of 4-hydroxypiperidinol oxyradical and 1 part of dibutyltin dilaurate into a four-neck flask provided with a condenser tube, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches the theoretical endpoint;
(2) adding 10 parts of hydroxyl polypropylene glycol into the intermediate product, stirring and reacting at 70 ℃ for 3h, cooling to 50 ℃, adding an acetone solution containing 1 part of hyperbranched polyester, reacting at 50 ℃ for 4h, adding 5 parts of phthalic anhydride as a solvent, heating to 100 ℃ for reacting for 5h, decompressing, removing the solvent, cooling to 40 ℃, adding 1 part of dimethylethanolamine, and neutralizing to form salt to obtain hyperbranched polyurethane acrylate;
(3) adding 12 parts of acetoacetoxyethyl methacrylate, 10 parts of hyperbranched polyurethane acrylate, 10 parts of methyl methacrylate, 15 parts of butyl acrylate, 30 parts of hydroxyethyl methacrylate and 20 parts of hydroxyethyl acrylate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer; adding 0.5 part of potassium persulfate aqueous solution into a reactor, stirring and polymerizing, heating to 90 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of a system to 8.0-9.0, cooling and filtering to obtain a hyperbranched polyurethane acrylate copolymer;
(4) adding 80 parts of distilled water, 5 parts of ethanol and 10 parts of silicon carbide into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring at a high speed, diluting 0.5 part of aminosilane coupling agent gamma-aminopropyltrimethoxysilane by using 5 parts of ethanol, slowly adding the diluted aminosilane coupling agent gamma-aminopropyltrimethoxysilane into the flask, adjusting the pH value of a system to 3-4 by using diluted hydrochloric acid, stirring for reacting for 4 hours, distilling by using a thin film evaporation device, recovering the ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1 hour to obtain an amino functionalized silicon carbide aqueous dispersion;
(5) adding 60 parts of hyperbranched polyurethane acrylate copolymer, 0.3 part of functionalized silicon carbide aqueous dispersion and 50 parts of deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH value to 9.0-10.0 by using ammonia water, and filtering to obtain modified acrylic resin emulsion;
(6) 42 parts of modified acrylic resin emulsion, 0.5 part of BYK-333 leveling agent, 0.6 part of TEGO 245 wetting dispersant, 0.3 part of BYK410 anti-settling agent, 0.5 part of BYK028 defoaming agent, 0.4 part of TEGO ViscoPlus 3030 thickener, 10 parts of superfine aluminum silicate quartz powder, 15 parts of titanium dioxide, 10 parts of calcium sulfate and 5 parts of talcum powder are stirred at high speed and ground for 4 hours to obtain the water-based paint.
Example 3
(1) Adding 100 parts of isophorone diisocyanate, 50 parts of hydroxypropyl acrylate, 1 part of p-hydroxyanisole and 1 part of dibutyltin dilaurate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches the theoretical endpoint;
(2) adding 50 parts of hydroxyl polypropylene glycol into the intermediate product, stirring and reacting at 70 ℃ for 3h, cooling to 50 ℃, adding an acetone solution containing 20 parts of hyperbranched polyester, reacting at 50 ℃ for 4h, adding 20 parts of mellitic anhydride into dioxane serving as a solvent, heating to 100 ℃, reacting for 5h, decompressing, removing the solvent, cooling to 40 ℃, adding 5 parts of triethanolamine, and neutralizing to form salt to obtain hyperbranched polyurethane acrylate;
(3) adding 15 parts of acetoacetoxyethyl methacrylate, 20 parts of hyperbranched polyurethane acrylate, 50 parts of methyl methacrylate, 20 parts of butyl acrylate, 40 parts of hydroxyethyl methacrylate and 50 parts of hydroxyethyl acrylate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer; adding 1 part of ammonium persulfate aqueous solution into a reactor, stirring and polymerizing, heating to 90 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of the system to 8.0-9.0, cooling and filtering to obtain a hyperbranched polyurethane acrylate copolymer;
(4) adding 150 parts of distilled water, 15 parts of ethanol and 10 parts of silicon carbide into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring at a high speed, diluting 5 parts of aminosilane coupling agent N-theta (aminoethyl) -gamma-aminopropyltrimethoxysilane) by using 15 parts of ethanol, slowly adding the diluted aminosilane coupling agent N-theta (aminoethyl) -gamma-aminopropyltrimethoxysilane) into the flask, adjusting the pH value of a system to 3-4 by using dilute hydrochloric acid, stirring for reacting for 4 hours, distilling by using a thin film evaporation device, recovering the ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1 hour to obtain an amino functionalized silicon carbide water dispersion;
(5) adding 100 parts of hyperbranched polyurethane acrylate copolymer, 0.2 part of functionalized silicon carbide aqueous dispersion and 80 parts of deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH value to 9.0-10.0 by using ammonia water, and filtering to obtain modified acrylic resin emulsion;
(6) taking 50 parts of modified acrylic resin emulsion, 0.8 part of TEGO Glide 450 flatting agent, 0.6 part of TEGO 260 wetting dispersant, 0.8 part of BYK410 anti-settling agent, 0.8 part of BYK028 defoaming agent, 0.2 part of TEGO Visco plus 3030 thickener, 20 parts of superfine aluminum silicate quartz powder, 15 parts of titanium dioxide, 10 parts of calcium sulfate and 5 parts of talcum powder, stirring at high speed, and grinding for 4 hours to obtain the water-based paint.
Example 4
(1) Adding 40 parts of toluene diisocyanate, 30 parts of hydroxypropyl acrylate, 0.6 part of 2, 6-di-tert-butyl-p-cresol and 0.6 part of dibutyltin dilaurate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches the theoretical endpoint;
(2) adding 30 parts of hydroxyl polypropylene glycol into the intermediate product, stirring and reacting at 70 ℃ for 3h, cooling to 50 ℃, adding an acetone solution containing 12 parts of hyperbranched polyester, reacting at 50 ℃ for 4h, adding 10 parts of phthalic anhydride as a solvent, heating to 100 ℃ for reacting for 5h, decompressing, removing the solvent, cooling to 40 ℃, adding 4 parts of diethanolamine, and neutralizing to form salt to obtain hyperbranched polyurethane acrylate;
(3) adding 13 parts of acetoacetoxyethyl methacrylate, 12 parts of hyperbranched polyurethane acrylate, 30 parts of methyl methacrylate, 12 parts of butyl acrylate, 25 parts of hydroxyethyl methacrylate and 40 parts of hydroxyethyl acrylate into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer; adding 0.8 part of potassium persulfate aqueous solution into a reactor, stirring and polymerizing, heating to 90 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of a system to 8.0-9.0, cooling and filtering to obtain a hyperbranched polyurethane acrylate copolymer;
(4) adding 120 parts of distilled water, 5 parts of ethanol and 10 parts of silicon carbide into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring at a high speed, diluting 4 parts of aminosilane coupling agent gamma-aminopropyltrimethoxysilane by using 5 parts of ethanol, slowly adding the aminosilane coupling agent gamma-aminopropyltrimethoxysilane into the flask, adjusting the pH value of a system to 3-4 by using dilute hydrochloric acid, stirring for reacting for 4 hours, distilling by using a thin film evaporation device, recovering ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1 hour to obtain an amino-functionalized silicon carbide aqueous dispersion;
(5) adding 80 parts of hyperbranched polyurethane acrylate copolymer, 0.2 part of functionalized silicon carbide aqueous dispersion and 60 parts of deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH value to 9.0-10.0 by using ammonia water, and filtering to obtain modified acrylic resin emulsion;
(6) and (2) taking 48 parts of modified acrylic resin emulsion, 0.5 part of BYK-375 flatting agent, 0.6 part of TEGO 250 wetting dispersant, 0.3 part of BYK410 anti-settling agent, 0.5 part of BYK028 defoaming agent, 0.4 part of TEGO ViscoPlus 3030 thickener, 10 parts of superfine aluminum silicate quartz powder, 15 parts of titanium dioxide, 10 parts of calcium sulfate and 5 parts of talcum powder, stirring at a high speed, and grinding for 4 hours to obtain the water-based paint.
Test examples
The performance of the aqueous paints obtained in examples 1 to 4 was tested, and the specific performance parameters are shown in table 1, and it can be seen from table 1 that the aqueous paints obtained in examples 1 and 4 maintain excellent performance in adhesion, acid and alkali resistance, etc. under the premise of relatively low VOC and high solid content.
TABLE 1 results of measuring the properties of the aqueous paints obtained in examples 1 to 4
Claims (6)
1. A low VOC, high solid content water paint based on acrylic resin is characterized in that: the paint is prepared from the following raw materials, by weight, 42-50 parts of modified acrylic resin emulsion, 1-9 parts of film-forming aid and 20-50 parts of pigment and filler;
the modified acrylic resin emulsion is prepared from the following raw materials, by weight, 40-100 parts of hyperbranched polyurethane acrylate copolymer, 0.2-0.3 part of functionalized silicon carbide and 10-80 parts of deionized water;
the hyperbranched polyurethane acrylate copolymer is prepared from the following raw materials, by weight, 10-30 parts of acrylic acid functional monomer, 40-100 parts of acrylic acid non-functional monomer and 0.2-1 part of initiator;
the acrylic functional monomer is prepared from the following raw materials in parts by weight, 10-15 parts of acetoacetoxyethyl methacrylate and 10-20 parts of hyperbranched polyurethane acrylate;
the non-functional monomer is one or more selected from 10-50 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 20-40 parts of hydroxyethyl methacrylate and 20-50 parts of hydroxyethyl acrylate;
the initiator is potassium persulfate or ammonium persulfate;
the hyperbranched polyurethane acrylate is prepared from the following raw materials, by weight, 20-100 parts of diisocyanate, 10-50 parts of oligomer polyol, 20-50 parts of hydroxypropyl acrylate, 0.1-1 part of catalyst, 1-20 parts of hyperbranched polyester, 0.1-1 part of polymerization inhibitor, 5-20 parts of anhydride and 1-5 parts of neutralizer;
the diisocyanate is isophorone diisocyanate;
the oligomer polyol is hydroxyl polypropylene glycol;
the catalyst is dibutyltin dilaurate;
the hyperbranched polyester is Boltorn type hyperbranched polyatomic alcohol which takes acrylic ester as a core and is produced by Perstorp company, the hydroxyl functionality is 6-64, and the number average molecular weight is 2100-5100;
the polymerization inhibitor is hydroquinone;
the acid anhydride is perfluoropropionic anhydride;
the neutralizing agent is triethylamine;
the preparation method of the hyperbranched polyurethane acrylate comprises the following steps:
(1) adding diisocyanate, hydroxypropyl acrylate, a catalyst and a polymerization inhibitor into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring for 2 hours at 25 ℃, heating to 50 ℃, continuing to react for 2-5 hours, titrating the content of isocyanate groups by a di-n-butylamine method, and obtaining an intermediate product when the content of-NCO groups reaches a theoretical endpoint;
(2) adding oligomer polyol into the intermediate product, stirring and reacting for 1-3h at 70 ℃, cooling to 50 ℃, adding an acetone solution of hyperbranched polyester, reacting for 2-4h at 50 ℃, adding anhydride as a solvent, heating to 100 ℃ and reacting for 2-5h, decompressing and removing the solvent, cooling to 40 ℃, adding a neutralizing agent, and neutralizing to form salt to obtain hyperbranched polyurethane acrylate;
the functionalized silicon carbide is prepared from the following raw materials, by weight, 80-150 parts of distilled water, 5-30 parts of ethanol, 10 parts of silicon carbide and 0.5-5 parts of aminosilane coupling agent.
2. The aqueous paint according to claim 1, characterized in that: the amino silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane.
3. A method of preparing the aqueous paint of claim 1, characterized in that: and (3) taking the modified acrylic resin emulsion, the film-forming assistant and the pigment filler according to the formula ratio, stirring at a high speed, and grinding for 2-4h to obtain the water-based paint.
4. The method for producing an aqueous paint according to claim 3, characterized in that: the preparation method of the modified acrylic resin emulsion comprises the following steps:
adding the hyperbranched polyurethane acrylate copolymer, the functionalized silicon carbide aqueous dispersion and deionized water into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, uniformly stirring, adjusting the pH to 9.0-10.0 by using ammonia water, and filtering to obtain the modified acrylic resin emulsion.
5. The method for producing an aqueous paint according to claim 4, characterized in that: the preparation method of the hyperbranched polyurethane acrylate copolymer comprises the following steps:
adding an acrylic acid functional monomer and a non-functional monomer mixture into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, adding an initiator aqueous solution into a reactor, stirring and polymerizing, then heating to 90-95 ℃, keeping the temperature, cooling, adding ammonia water to adjust the pH value of a system to 8.0-9.0, cooling and filtering to obtain a hyperbranched polyurethane acrylate copolymer;
the acrylic functional monomer is prepared from the following raw materials in parts by weight, 10-15 parts of acetoacetoxyethyl methacrylate and 10-20 parts of hyperbranched polyurethane acrylate.
6. The method for producing an aqueous paint according to claim 4, characterized in that: the preparation method of the functionalized silicon carbide aqueous dispersion comprises the following steps:
adding distilled water, ethanol and silicon carbide in a formula amount into a four-neck flask provided with a condenser pipe, a thermometer and a stirrer, stirring at a high speed, diluting an aminosilane coupling agent by using ethanol, slowly adding the aminosilane coupling agent into the flask, adjusting the pH value of the system to 3-4 by using dilute hydrochloric acid, stirring for reacting for 2-4h, distilling by using a thin film evaporation device, recovering the ethanol, adding ammonia water to adjust the pH value of the system to 9.0-10.0, and continuously stirring for 1h to obtain the amino-functionalized silicon carbide aqueous dispersion.
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