CN113025177A - Water-based acrylic polyurethane coating and preparation method thereof - Google Patents
Water-based acrylic polyurethane coating 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention relates to the technical field of coatings, in particular to a water-based acrylic polyurethane coating, which consists of a component A and a component B, wherein: the component A comprises: the paint comprises low hydroxyl value water-based acrylic resin, a dispersing agent, a defoaming agent, a leveling agent, nano titanium dioxide, a pigment, a filler, hyperbranched resin, a film-forming assistant, a catalyst, an anti-settling agent, a thickening agent and deionized water; the component B comprises: isocyanate curing agent and cosolvent. Also discloses a preparation method of the water-based acrylic polyurethane coating. The water-based acrylic polyurethane coating obtained by the invention has the advantages of low hydroxyl value, low cost, good water resistance and chemical resistance, plumpy and bright paint film, high salt spray resistance, lasting weather resistance, strong decoration, convenient construction and the like.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based acrylic polyurethane coating and a preparation method thereof.
Background
With the progress of social civilization, people also gradually recognize the adverse consequences of environmental pollution to society and daily life of people, and national and local governments at all levels also successively establish environmental laws and regulations related to paint production and coating. The water-based acrylic polyurethane coating takes water as a dispersion medium, has low VOC (volatile organic compounds) emission content during construction, and meets the requirement of environmental protection.
At present, the water-based acrylic polyurethane coating on the market mainly has the defects of poor water resistance, low fullness and poor bending resistance of a coating film, weather resistance, chemical resistance, corrosion resistance and paint film leveling property which are greatly weaker than those of a solvent-based acrylic polyurethane coating, the coating performance is improved to obtain a compact paint film, the requirement of the hydroxyl content of a part of water-based acrylic emulsion is higher and is generally more than 3.5%, the use amount of an isocyanate curing agent is increased, the cost of the water-based acrylic polyurethane coating is far higher than that of the solvent-based coating, and the popularization and the application are not facilitated. In addition, conventional oil-soluble isocyanate curing agents are not stably dispersed in aqueous systems to affect diffusion and crosslinking during film formation and ultimately affect the properties of the coating film.
In patent CN 110669419a "water-based acrylic polyurethane coating and preparation method thereof", a high hydroxyl value and low hydroxyl value mass ratio of 1: 0.5-0.8 of waterborne acrylic resin is used as a main film forming substance, and a waterborne acrylic polyurethane coating prepared by using a hydrophilic isocyanate curing agent has excellent mechanical property, water resistance and chemical resistance, but the weather resistance is only 500h and is far lower than that of a solvent-type acrylic polyurethane coating. In patent CN 110746870a, "a high performance water-based acrylic polyurethane bi-component coating", the water resistance, weather resistance, wear resistance and hardness of the coating film are improved by reinforcing in polymer emulsion, organic silicon dispersion, and additives, but the salt spray resistance is not evaluated, and the acid and alkali resistance is not outstanding.
In order to overcome the above disadvantages of the simple aqueous acrylic urethane coating, modification of an aqueous acrylic resin with a functional monomer or resin has been the subject of intense research.
The polyester resin has wide raw material sources, excellent flexibility, colorability, fullness and good weather resistance, but has the defects of easy hydrolysis, no high temperature resistance and high film-forming shrinkage. The polyester modified waterborne acrylic resin has the advantages of both. For example, in patent CN201611071377.1 "a polyester modified waterborne acrylic resin and its preparation and use in varnish", a coating prepared by copolymerizing an unsaturated polyester and an acrylate monomer by radical polymerization has excellent impact resistance and better toughness. However, the outdoor durability is limited by the alkyd condensed ester group as the backbone.
The fluorine modified acrylic resin is superior to pure acrylic resin in weather resistance, stain resistance and chemical resistance, and additionally endows the coating with good high and low temperature resistance and low friction performance. In the film forming process, the water-based fluorine modified acrylic resin with low surface tension can effectively improve the wettability and leveling property of a paint film to a base material, and after the film is formed, a fluorine-containing protective film with low surface tension is formed on the surface of the base material, so that the water resistance of the paint film is effectively improved. For example, in patent CN201110068559.4 "a polyester modified fluoroacrylic acid resin, its preparation method and its coating", a fluoromonomer such as trifluorobutyl methacrylate and hexafluorobutyl acrylate is used to modify an acrylic resin with a polyester resin, and the coating made from the resin is obviously used to make fluoroacrylic acid resin for helicopter skin coating in the aspects of distinctness of image, hardness, acid and alkali resistance, etc. However, when the resin is polymerized by free radicals, the reactivity ratio of the fluorine-containing acrylate and various acrylates needs to be strictly considered to control the uniformity of the molecular weight of the resin. In addition, the fluorine-containing polymer has low surface tension, poor wetting property to pigments and fillers and certain limitation on compatibility with film forming additives, thickeners and dispersants.
Disclosure of Invention
The invention provides a water-based acrylic polyurethane coating and a preparation method thereof, aiming at solving the technical defects, and the water-based acrylic polyurethane coating has the advantages of low hydroxyl value, water resistance, corrosion resistance and the like.
The invention discloses a water-based acrylic polyurethane coating, which consists of a component A and a component B, wherein the component A comprises the following components in parts by weight:
the component A comprises: 55-65 parts of low-hydroxyl-value water-based acrylic resin, 0.2-0.8 part of dispersing agent, 0.2-0.5 part of defoaming agent, 0.1-0.3 part of flatting agent, 10-30 parts of nano titanium dioxide, 0-10 parts of pigment, 3-10 parts of filler, 1-5 parts of hyperbranched resin, 3-5 parts of film-forming assistant, 0.05-0.15 part of catalyst, 0.5-2 parts of anti-settling agent, 0.2-0.8 part of thickening agent and 5-10 parts of deionized water;
the component B comprises: 60-70 parts of isocyanate curing agent and 30-40 parts of cosolvent according to the mass parts.
The mass ratio of the component A to the component B is 7: 1-1.2.
The low hydroxyl value water-based acrylic resin is prepared by the following steps:
step 1, preparation of acrylic prepolymer: mixing 5-36 parts of methyl methacrylate, 1-14 parts of butyl acrylate, 1-14 parts of isooctyl ester, 1-20 parts of methacrylic acid, 15-40 parts of hydroxyethyl acrylate, 1-5 parts of vinyl versatate, 0.1-2.0 parts of radical initiator and 0.05-0.5 part of mercaptoethanol to obtain a monomer mixture, adding 20-40 parts of ether cosolvent into a reaction kettle, stirring and heating to 100 ℃ and 130 ℃, dropwise adding the monomer mixture, dropwise adding within the time range of 1-3 hours, and preserving heat for 1-2 hours to obtain an acrylic prepolymer; the parts are all parts by mass;
step two, preparing the low hydroxyl value water-based acrylic resin: adding 5-15 parts of 1, 4-cyclohexanedicarboxylic acid, 1-10 parts of hexahydrophthalic anhydride, 5-10 parts of fluorinated alcohol, 0.01-0.02 part of organic tin catalyst and 25-45 parts of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing the methanol under reduced pressure, continuously adding 35-45 parts of the acrylic prepolymer in the step I, 1-7 parts of monoacid, 7-20 parts of neopentyl glycol, 1-8 parts of methyl propylene glycol, 2-10 parts of dimethylolpropionic acid and 0.02 part of organic tin catalyst into the reaction kettle, heating to 145-155 ℃, keeping the temperature for 1 hour, heating to 175-185 ℃, keeping the temperature for 1 hour, heating to 195-205 ℃, keeping the temperature for reaction to be clear, cooling to below 180 ℃, adding xylene, heating to 210-220 ℃, carrying out reflux mgesterification, and reducing the acid value to 15 KOH/g, removing xylene under reduced pressure, cooling to 100 ℃, adding 15-20 parts of ether cosolvent, uniformly stirring, cooling to below 80 ℃, adding amine for neutralization, adjusting the pH value to 8-9, adding deionized water, and adjusting the solid content to 40-55% to obtain the low-hydroxyl-value water-based acrylic resin; the above parts are all parts by mass.
Wherein the ether cosolvent is one or more of diethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether glycolate and diethylene glycol monobutyl ether.
Wherein the fluorinated alcohol is one or more of 2,2, 2-trifluoroethanol, 2,2,3,3, 3-pentafluoro-1-propanol, 1, 1, 1,3,3, 3-hexafluoro-2-propanol and tetrafluoroethanol.
Wherein the free radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide tert-butyl peroxide, tert-butyl peroxypivalate, cumene hydroperoxide and diisopropyl peroxydicarbonate.
Wherein the organotin catalyst is selected from one or more of TMG250 and TMG 256.
Preferably, the method comprises the following steps: the dispersant in the component A is modified polyurethane dispersant, such as Borchi 1750 or Borchi 0851;
the defoaming agent is polyether siloxane defoaming agent containing hydrophobic group, such as Tego 810 or Tego 901W;
the flatting agent is polyether modified polysiloxane flatting agent, such as BYK 346;
the nano titanium dioxide is rutile type nano titanium dioxide;
the pigment is one or more of organic or inorganic pigments, including but not limited to phthalocyanine green, high-pigment carbon black, BGS phthalocyanine blue;
the filler is one or more of precipitated barium sulfate and aluminum polyphosphate;
the hyperbranched resin is one of hyperbranched polyester resins, such as YG-HBP 075;
the film forming auxiliary agent is one or more of alcohol ether and alcohol ester, such as diethylene glycol butyl ether, dipropylene glycol methyl ether and propylene glycol diacetate;
the catalyst is a high activity metal carboxylate catalyst such as Borchi kat 24;
the anti-settling agent is one or more of organic bentonite powder, polyamide wax, fumed silica and associated polyurethane thickener;
the thickener is associative polyurethane thickener.
Preferably, the method comprises the following steps: the isocyanate curing agent in the component B is aliphatic isocyanate curing agent, such as Wanhua HT-100, Wanhua HT-600, and Asahi chemical reaction into TPA-100;
the cosolvent is one or more of propylene glycol diacetate and ethylene glycol butyl ether acetate.
In the technical scheme of the invention, 1, 4-cyclohexane dicarboxylic acid without conjugated double bonds and hexahydrophthalic anhydride are adopted for preparing the low-hydroxyl-value water-based acrylic resin, so that the weather resistance of a paint film can be improved, and the resin can obtain self-emulsifying property by dimethylolpropionic acid and can improve the stability. Compared with the traditional low-hydroxyl acrylic acid and fluorine-containing acrylic resin in the market, the invention has the difference that firstly, the fluorine-containing monomer is introduced for fluorination, the water resistance, high temperature resistance, low friction and solvent resistance of the resin are improved by utilizing the low surface tension characteristic of the fluorine-containing group, and secondly, the reactivity ratio among the monomers is required to be considered when different fluorine-containing acrylate monomers are synthesized, and the invention utilizes the fluorine-containing alcohol monomer for polycondensation, so that the molecular weight of the synthesized resin is more uniform, and the comprehensive performance is more excellent. The hyperbranched resin is prepared, the characteristics of high branching of the structure and numerous terminal functional groups are utilized, so that the coating has strong reaction crosslinking property, the crosslinking density of the paint film is increased, the hardness and the chemical corrosion resistance of the paint film are improved, the problem of the back adhesion of the paint film at high temperature is solved, and the fluidity and the workability of a system can be improved due to the good solubility and the low viscosity of the hyperbranched resin. The selected nano titanium dioxide has the defects of high refractivity and high optical activity, not only can absorb ultraviolet rays, but also can reflect and scatter the ultraviolet rays, improve the aging resistance of the coating, delay pulverization and discoloration and the like. The high-activity metal carboxylate catalyst improves the reaction activity of hydroxyl and isocyanate groups and accelerates the drying of a paint film. The anti-settling agent and the thickening agent are used in a matching way, so that the storage stability and the construction performance of the coating are improved, and the one-time spraying thickness of the coating is increased.
The technical scheme of the invention has the following beneficial effects:
firstly, the traditional polyester resin contains benzene rings and has limited weather resistance. The acrylic resin is modified by using non-conjugated 1, 4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride combined with neopentyl glycol, methyl propylene glycol and dimethylolpropionic acid, so that the impact resistance and the weather resistance of the acrylic resin are improved. Meanwhile, the self-emulsifying property of the dimethylolpropionic acid improves the dispersibility of the resin in water;
secondly, in order to obtain a modified resin with uniform molecular weight. In the process of synthesizing the polyester resin, a fluorinated alcohol monomer is added for polycondensation, and then the polyester resin is modified with acrylic resin. Compared with the fluorine-containing acrylate modified acrylate monomer, the prepared water-based acrylic resin has better molecular weight uniformity and low viscosity, and the solid content is more than or equal to 45 percent;
the hydroxyl content of the hydroxyl acrylic resin prepared by the invention is 2.0-2.5%, the dosage of an isocyanate curing agent is reduced, the cost is greatly reduced, and the reaction activity and the crosslinking density of the hydroxyl and the isocyanate curing agent are effectively improved by matching with the high activity of a terminal functional group in the hyperbranched resin and the action of a metal carboxylate catalyst;
fourthly, the prepared water-based acrylic polyurethane coating is bright and full, has good mechanical property and leveling property and is convenient to construct. The VOC content is less than or equal to 250g/L, the water resistance is no abnormity for 300h, the acid resistance (50g/LH2SO4) is no abnormity for 240h, the alkali resistance (50g/LNaOH) is no abnormity for 240h, the neutral salt spray resistance is more than 1200h, the rust, the bubble and the shedding are avoided, the artificial weathering resistance is 1500h, the rust, the bubble and the shedding are avoided, the chalking, the color change is grade 1, and the light loss is grade 2.
The water-based acrylic polyurethane coating obtained by the invention has the advantages of low hydroxyl value, low cost, good water resistance and chemical resistance, plumpy and bright paint film, high salt spray resistance, lasting weather resistance, strong decoration, convenient construction and the like.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the intended purpose, the following preferred embodiments are described in detail according to the specific implementation modes, structures, characteristics and effects of the present invention.
Example 1:
the embodiment discloses a preparation method of a water-based acrylic polyurethane coating, which comprises the following steps:
firstly, preparation: a low hydroxyl value water-based acrylic resin,
the method comprises the following steps: preparation of acrylic prepolymer: 15g of methyl methacrylate, 7g of butyl acrylate, 4g of isooctyl ester, 10g of methacrylic acid, 25g of hydroxyethyl acrylate, 3g of vinyl versatate, 1.5g of radical initiator and 0.3g of mercaptoethanol are mixed to obtain a monomer mixture, 25g of ether cosolvent is put into a reaction kettle, the temperature is increased to 100 ℃ and 130 ℃ by stirring, the monomer mixture is dropwise added, the dropwise addition is completed within 1-3 hours, and the acrylic prepolymer is obtained after heat preservation for 1-2 hours.
Step two: preparing a water-based acrylic resin: adding 1,4 cyclohexane dicarboxylic acid 5g, hexahydrophthalic anhydride 6g, alcohol fluoride 5g, organic tin catalyst 0.02g and appropriate amount of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing methanol under reduced pressure, adding acrylic prepolymer 45g, monoacid 1g, neopentyl glycol 9g, methyl propylene glycol 5g, dimethylolpropionic acid 5g and organic tin catalyst 0.02g into the reaction kettle, heating to 150 ℃, keeping the temperature for 1 hour, heating to 180 ℃, keeping the temperature for 1 hour, heating to 200 ℃, keeping the temperature, cooling to below 180 ℃, adding xylene, heating to 210 and 220 ℃ for reflux esterification, reducing the acid value to 15mgKOH/g, removing xylene under reduced pressure, cooling to 100 ℃, adding ether cosolvent 18.9g, stirring uniformly, cooling to below 80 ℃, adding appropriate amount of amine for neutralization, adjusting the pH value to 8-9, adding ionized water under the shearing action, and adjusting the solid content to 45% to obtain the low-hydroxyl-value water-based acrylic resin.
Preparing water-based acrylic polyurethane paint, adding 50g of deionized water, 2g of dispersing agent and 3g of defoaming agent into a dispersion kettle, stirring at a high speed for dispersion, then adding 300g of nano titanium dioxide, 30g of phthalocyanine green, 20g of precipitated barium sulfate, 10g of aluminum polyphosphate and 5g of anti-settling agent, stirring at a high speed uniformly, sanding until the fineness is less than or equal to 30 mu m, adding 600g of the low-hydroxyl-value water-based acrylic resin in example 1 into the sanded slurry, then sequentially adding 2g of leveling agent, 20g of hyperbranched resin, 30g of film-forming assistant, 0.5g of catalyst and 2g of thickening agent, and adjusting the viscosity to obtain the component A.
650g of isocyanate curing agent and 350g of cosolvent are uniformly dispersed to prepare the component B.
Example 2:
the embodiment discloses a preparation method of a water-based acrylic polyurethane coating, which comprises the following steps:
firstly, preparation: a low hydroxyl value water-based acrylic resin,
the method comprises the following steps: preparation of acrylic prepolymer: 15g of methyl methacrylate, 7g of butyl acrylate, 4g of isooctyl ester, 10g of methacrylic acid, 25g of hydroxyethyl acrylate, 3g of vinyl versatate, 1.5g of radical initiator and 0.3g of mercaptoethanol are mixed to obtain a monomer mixture, 25g of ether cosolvent is put into a reaction kettle, the temperature is increased to 100 ℃ and 130 ℃ by stirring, the monomer mixture is dropwise added, the dropwise addition is completed within 1-3 hours, and the acrylic prepolymer is obtained after heat preservation for 1-2 hours.
Step two: low hydroxyl value aqueous acrylic resin: adding 1,4 cyclohexane dicarboxylic acid, 6g hexahydrophthalic anhydride, 5g alcohol fluoride, 0.02g organic tin catalyst and a proper amount of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing methanol under reduced pressure, continuously adding 35g of acrylic prepolymer in the step one, 1g monoacid, 9g neopentyl glycol, 5g methyl propylene glycol, 10g dimethylolpropionic acid and 0.02g organic tin catalyst into the reaction kettle, heating to 150 ℃, keeping the temperature for 1 hour, heating to 180 ℃, keeping the temperature for 1 hour, heating to 200 ℃, keeping the temperature for reaction to be clear, cooling to below 180 ℃, adding xylene, heating to 210-220 ℃ for reflux esterification, reducing the acid value to 15mgKOH/g, removing xylene under reduced pressure, cooling to 100 ℃, adding 18.9g ether cosolvent, uniformly stirring, cooling to below 80 ℃, adding a proper amount of amine for neutralization, adjusting the pH value to 8-9, adding ionized water under the shearing action, and adjusting the solid content to 45% to obtain the low-hydroxyl-value water-based acrylic resin.
Preparing water-based acrylic polyurethane paint, adding 50g of deionized water, 2g of dispersing agent and 3g of defoaming agent into a dispersion kettle, stirring at a high speed for dispersion, then adding 300g of nano titanium dioxide, 30g of phthalocyanine green, 20g of precipitated barium sulfate, 10g of aluminum polyphosphate and 5g of anti-settling agent, stirring at a high speed uniformly, sanding until the fineness is less than or equal to 30 mu m, adding 600g of low-hydroxyl-value water-based acrylic resin in example 2 into the sanded slurry, then sequentially adding 2g of leveling agent, 20g of hyperbranched resin, 30g of film-forming assistant, 0.5g of catalyst and 2g of thickening agent, and adjusting the viscosity to obtain the component A.
650g of isocyanate curing agent and 350g of cosolvent are uniformly dispersed to prepare the component B.
Example 3:
the embodiment discloses a preparation method of a water-based acrylic polyurethane coating, which comprises the following steps:
preparing the low hydroxyl value water-based acrylic resin,
the method comprises the following steps: preparation of acrylic prepolymer: 15g of methyl methacrylate, 7g of butyl acrylate, 4g of isooctyl ester, 10g of methacrylic acid, 25g of hydroxyethyl acrylate, 3g of vinyl versatate, 1.5g of radical initiator and 0.3g of mercaptoethanol are mixed to obtain a monomer mixture, 25g of ether cosolvent is put into a reaction kettle, the temperature is increased to 100 ℃ and 130 ℃ by stirring, the monomer mixture is dropwise added, the dropwise addition is completed within 1-3 hours, and the acrylic prepolymer is obtained after heat preservation for 1-2 hours.
Step two: low hydroxyl value aqueous acrylic resin: adding 1,4 cyclohexane dicarboxylic acid 5g, hexahydrophthalic anhydride 6g, alcohol fluoride 10g, organic tin catalyst 0.02g and appropriate amount of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing methanol under reduced pressure, adding acrylic prepolymer 45g, monoacid 1g, neopentyl glycol 4g, methyl propylene glycol 5g, dimethylolpropionic acid 5g and organic tin catalyst 0.02g into the reaction kettle, heating to 150 ℃, keeping the temperature for 1 hour, heating to 180 ℃, keeping the temperature for 1 hour, heating to 200 ℃, keeping the temperature, cooling to below 180 ℃, adding xylene, heating to 210 and 220 ℃ for reflux esterification, reducing the acid value to 15mgKOH/g, removing xylene under reduced pressure, reducing the temperature to 100 ℃, adding ether cosolvent 15g, stirring uniformly, reducing the temperature to below 80 ℃, adding appropriate amount of amine for neutralization, adjusting the pH value to 8-9, adding ionized water under the shearing action, and adjusting the solid content to 45% to obtain the low-hydroxyl-value water-based acrylic resin.
100g of deionized water, 8g of dispersing agent and 3g of defoaming agent are added into a dispersion kettle, high-speed stirring and dispersion are carried out, then 200g of nano titanium dioxide, 30g of high-color carbon black, 30g of precipitated barium sulfate, 20g of aluminum polyphosphate and 18g of anti-settling agent are added, high-speed stirring is carried out, then sanding is carried out until the fineness is less than or equal to 30 mu m, 700g of low-hydroxyl-value water-based acrylic resin in example 3 is added into the sanded slurry, then 2g of flatting agent, 50g of hyperbranched resin, 40g of film-forming assistant, 0.8g of catalyst and 6g of thickening agent are sequentially added, and the viscosity is adjusted, thus obtaining the component A.
And (3) uniformly dispersing 700g of isocyanate curing agent and 300g of cosolvent to obtain the component B.
Example 4:
the embodiment discloses a preparation method of a water-based acrylic polyurethane coating, which comprises the following steps:
preparing the low hydroxyl value water-based acrylic resin,
the method comprises the following steps: preparation of acrylic prepolymer: 15g of methyl methacrylate, 7g of butyl acrylate, 4g of isooctyl ester, 10g of methacrylic acid, 25g of hydroxyethyl acrylate, 3g of vinyl versatate, 1.5g of radical initiator and 0.3g of mercaptoethanol are mixed to obtain a monomer mixture, 25g of ether cosolvent is put into a reaction kettle, the temperature is increased to 100 ℃ and 130 ℃ by stirring, the monomer mixture is dropwise added, the dropwise addition is completed within 1-3 hours, and the acrylic prepolymer is obtained after heat preservation for 1-2 hours.
Step two: low hydroxyl value aqueous acrylic resin: adding 1,4 cyclohexane dicarboxylic acid, 6g hexahydrophthalic anhydride, 10g fluorinated alcohol, 0.02g organic tin catalyst and a proper amount of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing methanol under reduced pressure, continuously adding 35g of acrylic acid prepolymer in the step one, 1g monoacid, 4g neopentyl glycol, 5g methyl propylene glycol, 10g dimethylolpropionic acid and 0.02g organic tin catalyst into the reaction kettle, heating to 150 ℃, keeping the temperature for 1 hour, heating to 180 ℃, keeping the temperature for 1 hour, heating to 200 ℃, keeping the temperature to be clear, cooling to below 180 ℃, adding xylene, heating to 210 and 220 ℃ for reflux esterification, reducing the acid value to 15mgKOH/g, removing xylene under reduced pressure, reducing the temperature to 100 ℃, adding 15g ether cosolvent, uniformly stirring, reducing the temperature to below 80 ℃, adding a proper amount of amine for neutralization, adjusting the pH value to 8-9, under the shearing action, adding ionized water to adjust the solid content to 45 percent to obtain the low hydroxyl value water-based acrylic resin.
100g of deionized water, 8g of dispersing agent and 3g of defoaming agent are added into a dispersion kettle, high-speed stirring and dispersion are carried out, then 200g of nano titanium dioxide, 30g of high-color carbon black, 30g of precipitated barium sulfate, 20g of aluminum polyphosphate and 18g of anti-settling agent are added, high-speed stirring is carried out, then sanding is carried out until the fineness is less than or equal to 30 mu m, 700g of low-hydroxyl-value water-based acrylic resin in example 4 is added into the sanded slurry, then 2g of flatting agent, 50g of hyperbranched resin, 40g of film-forming assistant, 0.8g of catalyst and 6g of thickening agent are sequentially added, and the viscosity is adjusted, thus obtaining the component A.
And (3) uniformly dispersing 700g of isocyanate curing agent and 300g of cosolvent to obtain the component B.
The aqueous acrylic urethane coatings obtained in examples 1 to 4 were subjected to performance tests, and the results are as follows.
Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but may be embodied or carried out in various forms without departing from the spirit and scope of the invention.
Claims (10)
1. A water-based acrylic polyurethane coating is characterized in that: consists of a component A and a component B, wherein:
the component A comprises: 55-65 parts of low-hydroxyl-value water-based acrylic resin, 0.2-0.8 part of dispersing agent, 0.2-0.5 part of defoaming agent, 0.1-0.3 part of flatting agent, 10-30 parts of nano titanium dioxide, 0-10 parts of pigment, 3-10 parts of filler, 1-5 parts of hyperbranched resin, 3-5 parts of film-forming assistant, 0.05-0.15 part of catalyst, 0.5-2 parts of anti-settling agent, 0.2-0.8 part of thickening agent and 5-10 parts of deionized water;
the component B comprises: 60-70 parts of isocyanate curing agent and 30-40 parts of cosolvent according to the mass parts.
2. The water-based acrylic polyurethane coating according to claim 1, wherein: the mass ratio of the component A to the component B is 7: 1-1.2.
3. The aqueous acrylic polyurethane coating according to claim 1 or 2, wherein: the low hydroxyl value water-based acrylic resin is prepared by the following steps:
step 1, preparation of acrylic prepolymer: mixing 5-36 parts of methyl methacrylate, 1-14 parts of butyl acrylate, 1-14 parts of isooctyl ester, 1-20 parts of methacrylic acid, 15-40 parts of hydroxyethyl acrylate, 1-5 parts of vinyl versatate, 0.1-2.0 parts of radical initiator and 0.05-0.5 part of mercaptoethanol to obtain a monomer mixture, adding 20-40 parts of ether cosolvent into a reaction kettle, stirring and heating to 100 ℃ and 130 ℃, dropwise adding the monomer mixture, dropwise adding within the time range of 1-3 hours, and preserving heat for 1-2 hours to obtain an acrylic prepolymer; the parts are all parts by mass;
step two, preparing the low hydroxyl value water-based acrylic resin: adding 5-15 parts of 1, 4-cyclohexanedicarboxylic acid, 1-10 parts of hexahydrophthalic anhydride, 5-10 parts of fluorinated alcohol, 0.01-0.02 part of organic tin catalyst and 25-45 parts of methanol solvent into a reaction kettle, reacting at 80-85 ℃ for 15 hours, removing the methanol under reduced pressure, continuously adding 35-45 parts of the acrylic prepolymer in the step I, 1-7 parts of monoacid, 7-20 parts of neopentyl glycol, 1-8 parts of methyl propylene glycol, 2-10 parts of dimethylolpropionic acid and 0.02 part of organic tin catalyst into the reaction kettle, heating to 145-155 ℃, keeping the temperature for 1 hour, heating to 175-185 ℃, keeping the temperature for 1 hour, heating to 195-205 ℃, keeping the temperature to clear, cooling to below 180 ℃, adding xylene, heating to 210-220 ℃, carrying out reflux esterification, and lowering the acid value to 15mgKOH/g, removing xylene under reduced pressure, cooling to 100 ℃, adding 15-20 parts of ether cosolvent, uniformly stirring, cooling to below 80 ℃, adding amine for neutralization, adjusting the pH value to 8-9, adding deionized water, and adjusting the solid content to 40-55% to obtain the low-hydroxyl-value water-based acrylic resin; the above parts are all parts by mass.
4. The water-based acrylic polyurethane coating according to claim 3, wherein: wherein the ether cosolvent is one or more of diethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether glycolate and diethylene glycol monobutyl ether.
5. The water-based acrylic polyurethane coating according to claim 3, wherein: wherein the fluorinated alcohol is one or more of 2,2, 2-trifluoroethanol, 2,2,3,3, 3-pentafluoro-1-propanol, 1, 1, 1,3,3, 3-hexafluoro-2-propanol and tetrafluoroethanol.
6. The water-based acrylic polyurethane coating according to claim 3, wherein: wherein the free radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide tert-butyl peroxide, tert-butyl peroxypivalate, cumene hydroperoxide and diisopropyl peroxydicarbonate.
7. The water-based acrylic polyurethane coating according to claim 3, wherein: wherein the organotin catalyst is selected from one or more of TMG250 and TMG 256.
8. The water-based acrylic polyurethane coating according to claim 1, wherein: the dispersant in the component A is a modified polyurethane dispersant; the defoaming agent is a polyether siloxane defoaming agent containing hydrophobic groups; the flatting agent is polyether modified polysiloxane flatting agent; the nano titanium dioxide is rutile type nano titanium dioxide; the pigment is one or more of organic or inorganic pigments; the filler is one or more of precipitated barium sulfate and aluminum polyphosphate; the hyperbranched resin is one of hyperbranched polyester resins; the film forming auxiliary agent is one or more of alcohol ether and alcohol ester; the catalyst is a high-activity metal carboxylate catalyst; the anti-settling agent is one or more of organic bentonite powder, polyamide wax, fumed silica and associated polyurethane thickener; the thickener is associative polyurethane thickener.
9. The water-based acrylic polyurethane coating according to claim 1, wherein: the isocyanate curing agent in the component B is aliphatic isocyanate curing agent; the cosolvent is one or more of propylene glycol diacetate and ethylene glycol butyl ether acetate.
10. A method for preparing the aqueous acrylic polyurethane coating according to claim 1, which comprises: 5-10 parts of deionized water, 0.2-0.8 part of dispersant and 0.2-0.5 part of defoamer are added into a dispersion kettle, the mixture is stirred and dispersed, then 10-30 parts of nano titanium dioxide, 3-30 parts of pigment, 3-10 parts of filler and 0.5-2 parts of anti-settling agent are added, the mixture is stirred uniformly and then is sanded until the fineness is less than or equal to 30 mu m, 55-65 parts of low-hydroxyl-value water-based acrylic resin is added into the sanded slurry, then 0.1-0.3 part of flatting agent, 1-5 parts of hyperbranched resin, 3-5 parts of film-forming assistant and 0.05-0.15 part of catalyst are sequentially added, and then 0.2-0.8 part of thickener is used for adjusting the viscosity to 60-70s, thus obtaining the component A;
and (3) uniformly dispersing 60-70 parts of isocyanate curing agent and 30-40 parts of cosolvent to obtain the component B.
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