CN109554055B - Aqueous thick-coating type aqueous acrylic acid hybrid epoxy floor paint and preparation method thereof - Google Patents
Aqueous thick-coating type aqueous acrylic acid hybrid epoxy floor paint and preparation method thereof Download PDFInfo
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- CN109554055B CN109554055B CN201810953121.6A CN201810953121A CN109554055B CN 109554055 B CN109554055 B CN 109554055B CN 201810953121 A CN201810953121 A CN 201810953121A CN 109554055 B CN109554055 B CN 109554055B
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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
- C09D151/00—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
- 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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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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 relates to a water-based thick-coating water-based acrylic acid hybrid epoxy floor paint which consists of a component A and a component B; wherein the component A comprises the following components in percentage by weight: 60-72% of water-based acrylic acid hybridized epoxy resin emulsion, 3-5% of pigment, 2-8% of titanium dioxide, 2-15% of precipitated barium sulfate, 1-2% of hardening and wear-resisting agent, 0.3-0.5% of water-based dispersant, 0.1-0.2% of water-based defoamer, 0.2-0.3% of water-based flatting agent, 0.2-0.4% of surfactant, 0.5-1% of water-based polyamide wax slurry, 7-10% of deionized water, 2-3% of film-forming assistant, 3-5% of cosolvent, 0.3-0.6% of paint neutralizer and 1-2% of water-based graphene slurry; wherein the component B is an epoxy curing agent. The floor paint provided by the invention has the advantages that: fast drying, no foaming of thick coating, good leveling property, good abrasive property, good water resistance, good chemical resistance, high gloss, good weather resistance, low VOCs and the like.
Description
Technical Field
The invention relates to a water-based thick-coating water-based acrylic acid hybrid epoxy floor paint and a preparation method thereof, belonging to the technical field of paints.
Background
Along with the national vigorous improvement on the environment, governments and industries in China also have a relevant oil ban policy, China terrace Association also stipulates that the national parts of province and city respond to local government calls, forbid the use of solvent-based epoxy terrace paint and solvent-based acrylic polyurethane terrace paint, but through market verification of a period of time, a lot of construction problems appear in water-based epoxy terrace paint, such as: 1. the humidity is too high, the drying is too slow, the film forming effect of the floor paint is very poor, and a series of problems of low hardness, low luster, poor water resistance, poor wear resistance, poor adhesion, floating color, floating and the like of a paint film are caused; 2. the usable time of the water-based epoxy floor paint is too short, generally only about 1 hour, and the requirements of field construction cannot be met; 3. compared with a solvent type epoxy floor, the water-based epoxy floor has low gloss, short service time and poor appearance effect compared with a solvent ring-pull floor, so that the market acceptance degree is poor; 4. in the construction process, constructors must blow all around by adopting fans, convection of an underground garage is enhanced, water-based volatilization is accelerated, the garage with a small area has no problem, and the operation cannot be carried out at all when the area of the garage exceeds 5 ten thousand square meters.
The one-time thick coating of the water-based epoxy floor paint at least reaches 120 microns, which means that the one-time thickness of a wet film is about 240 microns, and when the water-based epoxy floor paint is constructed in an underground garage, the moisture in the paint film cannot be volatilized for a long time due to the closed environment, no air circulation and high humidity.
Disclosure of Invention
The technology adopts a novel reaction mechanism, utilizes an acrylic acid hybrid epoxy emulsion as a base material, acrylic ester is hybridized to an epoxy group, the drying speed of the epoxy emulsion is greatly improved, the epoxy group is reacted with polyamide to form epoxy performance by matching with a modified alicyclic amine waterborne epoxy curing agent, and an acrylic acid hybrid group is formed into a film by utilizing a self-crosslinking reaction, so that the excellent drying speed, appearance effect, gloss and water resistance are brought to a paint film, more importantly, the drying speed of the paint film is not influenced by a humid low-temperature environment. Meanwhile, crosslinking and hybridization reactions in the curing process of the paint film do not generate gas, so that the paint film can be thickly coated at one time without foaming. Through a series of tests and demonstration tests, the paint film is verified to have the following properties: fast drying, no foaming of thick coating, good leveling property, good abrasive property, good water resistance, good chemical resistance, high gloss, good weather resistance and the like. The method is suitable for the fields of outdoor floors, workshop floors, garage floors, court floors, airport floors, station floors, market floors and the like.
In a first aspect of the present invention, there is provided:
a water-based thick-coating water-based acrylic acid hybrid epoxy floor paint is composed of a component A and a component B;
wherein the component A comprises the following components in percentage by weight: 60-72% of water-based acrylic acid hybridized epoxy resin emulsion, 3-5% of pigment, 2-8% of titanium dioxide, 2-15% of precipitated barium sulfate, 1-2% of hardening and wear-resisting agent, 0.3-0.5% of water-based dispersant, 0.1-0.2% of water-based defoamer, 0.2-0.3% of water-based flatting agent, 0.2-0.4% of surfactant, 0.5-1% of water-based polyamide wax slurry, 7-10% of deionized water, 2-3% of film-forming assistant, 3-5% of cosolvent, 0.3-0.6% of paint neutralizer and 1-2% of water-based graphene slurry;
wherein the component B is an epoxy curing agent.
The weight ratio of the component A to the component B is 100: 5 to 15.
The pigment is one or a mixture of more of phthalocyanine green G, titanium nickel yellow, titanium chromium brown, cobalt green, cobalt blue, iron chromium black, iron zinc chromium brown, copper chromium black or bismuth yellow.
The hardening and wear-resisting agent is alumina-based wear-resisting particles.
The cosolvent is selected from glycol ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol ether, propylene glycol monomethyl ether acetate, ethanol, n-butanol or isopropanol and the like.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1-1.2: 0.2-0.3, uniformly mixing 40-55 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator accounting for 0.3-0.5 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 75-85 ℃ in a nitrogen atmosphere, dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 3-5: 2-4: 0.4-0.8, wherein the adding amount of the mixed monomer is 10-12% of the weight of the mixed reaction solution, and after the reaction is finished, the product is subjected to centrifugal separation and washing to obtain the anionic polymer microspheres;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.2-1.5: 5-7: mixing 25-30 anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent and 60-70 vol.% of ethanol aqueous solution, heating to 90-95 ℃, reacting for 2-4 h, adjusting the pH to 3-4 with dilute nitric acid, aging for 30-40 h at 20-30 ℃ to obtain sol, concentrating the sol under reduced pressure, and performing centrifugal separation to obtain microspheres coated with aluminum sol; and then roasting the microspheres to remove the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
The initiator is potassium persulfate; the anionic monomer is sodium p-vinylbenzene sulfonate, and the reaction time in the step 1 is 6-10 h.
The pore-foaming agent is methyl cellulose; the roasting is carried out at 1050-1100 ℃ for 1-3 h.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3-3.5: 4-4.5: 0.8-1.0, preparing polyol, isocyanate and a chain extender, mixing the polyol and the isocyanate, reacting for 0.5-2 h at 84-90 ℃ in the presence of an organic tin catalyst, adding the chain extender, and continuing to react for 1-1.5 h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 1-3 h at 82-88 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end capping for 1-1.5 h, adding a neutralizing agent for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, E44 epoxy resin, ethyl methacrylate, tung oil, vinyl-terminated polymethylphenyl siloxane to deionized water is 1.5-2: 8-10: 1.2-1.5: 0.5-0.7: 0.4-0.8: 20-24;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 1-5 wt% of polyvinyl alcohol and 0.5-1 wt% of an emulsifier, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 3-5, heating to 80-85 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate according to a volume ratio of 1: 2-4, wherein the volume ratio of the monomer mixed liquid to the modified epoxy resin emulsion is 1: and 5-8, after the dropwise addition is finished, continuously reacting for 1-1.5 h, and then adding a neutralizing agent for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The polyalcohol is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butyl diethylene glycol, glycerol or polyethylene glycol; the isocyanate is toluene diisocyanate.
The emulsifier is polyoxyethylene octyl phenol ether-10.
The organotin catalyst is dibutyltin dilaurate.
The chain extender is one or a mixture of more of l, 4-butanediol, neopentyl glycol, ethylene glycol, diethylene glycol, glycerol, maleic anhydride, trimethylolpropane, ethylenediamine, diethylenetriamine, triethylene tetramine or dimethylolpropionic acid.
The neutralizer is sodium bicarbonate, triethylamine, methylamine or triethanolamine.
In a second aspect of the present invention, there is provided:
the preparation method of the water-based thick-coating water-based acrylic acid hybrid epoxy floor paint comprises the following steps:
s1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: grinding the fineness to 30 microns by a sand mill;
s5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
Advantageous effects
The floor paint provided by the invention has the advantages that: fast drying, no foaming of thick coating, good leveling property, good abrasive property, good water resistance, good chemical resistance, high gloss, good weather resistance, low VOCs and the like.
According to the floor paint, the polyurethane modified epoxy resin is used as the base resin of the aqueous acrylic hybrid epoxy resin emulsion, and after vinyl end capping treatment is carried out on the base resin, in the subsequent acrylate polymerization process, acrylate can be crosslinked with an epoxy group on one hand, and on the other hand, acrylate can be directly polymerized with vinyl to form a three-dimensional network, so that the wear resistance and weather resistance of the floor paint can be effectively improved by using the epoxy resin subjected to the vinyl end capping treatment.
Meanwhile, the hardening wear-resisting agent adopted in the invention is hollow alumina microspheres, and after the hollow alumina microspheres are premixed with the waterborne acrylic acid hybrid epoxy resin emulsion, the emulsion can be wrapped in the microsphere core, and the cured epoxy resin and the filler can be effectively integrally fixed through the curing action of the epoxy curing agent, so that the crosslinking firmness of the filler in a paint film is improved, and the wear resistance of the floor paint is obviously improved.
Because the anionic monomer is adopted during the preparation of the polymer microsphere, and the alumina particles in the alumina sol are positively charged, when the polymer microsphere is applied to the preparation process of the alumina sol, the alumina sol can be coated on the surface of the microsphere more, and the wear resistance of the microsphere obtained after sintering can be improved.
Detailed Description
Example 1
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Example 2
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | AEH-20 Dow chemical | 69 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.8 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.4 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.3 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 4 |
| Titanium white powder | R996 | 6 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 6 |
| Hardening wear-resistant auxiliary | MT801 Chongqing Mai Diagram | 1 |
| Film forming aid | PDGA Dow | 2.5 |
| Cosolvent | Ethylene glycol monobutyl ether | 4 |
| Amine neutralizing agents | Ethylene diamine | 0.6 |
| Deionized water | Self-made | 3.9 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Example 3
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | AEH-20 Dow chemical | 72 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.5 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.3 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.4 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 5 |
| Titanium white powder | R996 | 2 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 5 |
| Hardening wear-resistant auxiliary | MT801 Chongqing Mai Diagram | 2 |
| Film forming aid | PDGA Dow | 3 |
| Cosolvent | Ethylene glycol monobutyl ether | 5 |
| Amine neutralizing agents | Ethylene diamine | 0.4 |
| Deionized water | Self-made | 2.9 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Example 4
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | AEH-20 Dow chemical | 60 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 1 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.5 |
| Aqueous leveling agent | 4100 digao | 0.2 |
| Surface active agent | OF Chengdu chemical engineering | 0.2 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.1 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 3 |
| Titanium white powder | R996 | 8 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 12 |
| Hardening wear-resistant auxiliary | MT801 Chongqing Mai Diagram | 1 |
| Film forming aid | PDGA Dow | 2 |
| Cosolvent | Ethylene glycol monobutyl ether | 3 |
| Amine neutralizing agents | Ethylene diamine | 0.3 |
| Deionized water | Self-made | 6.7 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 2 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Example 5
The raw materials are adopted according to the mixture ratio shown in the following table:
the preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Example 6
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | Self-made | 72 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.5 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.3 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.4 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 5 |
| Titanium white powder | R996 | 4 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 2 |
| Hardening wear-resistant auxiliary | Self-made | 2 |
| Film forming aid | PDGA Dow | 3 |
| Cosolvent | Ethylene glycol monobutyl ether | 5 |
| Amine neutralizing agents | Ethylene diamine | 0.4 |
| Deionized water | Self-made | 3.9 |
| Graphene paste 10％ | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
S1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3.2: 4.2: 0.9 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 1h at 86 ℃ in the presence of dibutyltin dilaurate, adding neopentyl glycol, and continuing to react for 1.2h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 2 hours at 85 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end-capping reaction for 1.2 hours, adding sodium bicarbonate for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, E44 epoxy resin, ethyl methacrylate, tung oil, vinyl-terminated polymethylphenyl siloxane to deionized water is 1.8: 9: 1.3: 0.6: 0.5: 22;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 2 wt% of polyvinyl alcohol and 0.6 wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 4, heating to 84 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 3, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 6, after the dropwise addition is finished, continuously reacting for 1.2h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1.1: 0.25, uniformly mixing 45 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator potassium persulfate accounting for 0.4 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 80 ℃ in a nitrogen atmosphere, and dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer sodium p-vinylbenzene sulfonate, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 4: 3: 0.6, the adding amount of the mixed monomer is 11 percent of the weight of the mixed reaction liquid, after 8 hours of reaction, the product is centrifugally separated and washed, and the anionic polymer microspheres are obtained;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.3: 6: 28, mixing the anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent methylcellulose and 65 vol.% of ethanol aqueous solution, heating to 92 ℃ for reaction for 3 hours, adjusting the pH to 3-4 by using dilute nitric acid, aging at 25 ℃ for 35 hours to obtain sol, and performing reduced pressure concentration and centrifugal separation on the sol to obtain microspheres coated with aluminum sol; and then roasting the microspheres for 2 hours at 1080 ℃, and removing the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
Example 7
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | Self-made | 72 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.5 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.3 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.4 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 5 |
| Titanium white powder | R996 | 4 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 2 |
| Hardening wear-resistant auxiliary | Self-made | 2 |
| Film forming aid | PDGA Dow | 3 |
| Cosolvent | Ethylene glycol monobutyl ether | 5 |
| Amine neutralizing agents | Ethylene diamine | 0.4 |
| Deionized water | Self-made | 3.9 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
S1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3: 4: 0.8 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 0.5h at 84 ℃ in the presence of dibutyltin dilaurate, adding neopentyl glycol, and continuously reacting for 1h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 1h at 82 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end-capping reaction for 1h, adding sodium bicarbonate for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, the E44 epoxy resin, the ethyl methacrylate, the tung oil, the vinyl-terminated polymethylphenyl siloxane to the deionized water is 1.5: 8: 1.2: 0.5: 0.4: 20;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 5wt% of polyvinyl alcohol and 1wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 5, mixing, heating to 85 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 4, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 5, after the dropwise addition is finished, continuously reacting for 1h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1: 0.2, uniformly mixing 40 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator potassium persulfate accounting for 0.3 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 75 ℃ in a nitrogen atmosphere, and dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer sodium p-vinylbenzene sulfonate, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 3: 2: 0.4, the adding amount of the mixed monomer is 10 percent of the weight of the mixed reaction liquid, after 6 hours of reaction, the product is centrifugally separated and washed, and the anionic polymer microspheres are obtained;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.2: 5: 25 mixing the anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent methylcellulose and 60 vol.% of ethanol aqueous solution, heating to 90 ℃ for reaction for 2 hours, adjusting the pH to 3-4 by using dilute nitric acid, aging at 20 ℃ for 30 hours to obtain sol, and performing reduced pressure concentration and centrifugal separation on the sol to obtain microspheres coated with aluminum sol; and then roasting the microspheres for 1h at 1050 ℃, and removing the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
Example 8
The raw materials are adopted according to the mixture ratio shown in the following table:
s1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3.5: 4.5: 1.0 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 2 hours at 90 ℃ in the presence of dibutyltin dilaurate, and adding neopentyl glycol to continue reacting for 1.5 hours to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 3 hours at 88 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end-capping reaction for 1.5 hours, adding sodium bicarbonate for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, the E44 epoxy resin, the ethyl methacrylate, the tung oil, the vinyl-terminated polymethylphenyl siloxane to the deionized water is 2: 10: 1.5: 0.7: 0.8: 24;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 5wt% of polyvinyl alcohol and 1wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 5, mixing, heating to 85 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 4, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 8, after the dropwise addition is finished, continuously reacting for 1.5h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1.2: 0.3, uniformly mixing 55wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator potassium persulfate accounting for 0.5wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 85 ℃ in a nitrogen atmosphere, and dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer sodium p-vinylbenzene sulfonate, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 5: 4: 0.8, the adding amount of the mixed monomer is 12 percent of the weight of the mixed reaction liquid, after 10 hours of reaction, the product is centrifugally separated and washed to obtain the anionic polymer microspheres;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.5: 7: 30, mixing anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent methylcellulose and 70vol.% of ethanol aqueous solution, heating to 95 ℃ for reaction for 4 hours, adjusting the pH to 3-4 by using dilute nitric acid, aging at 30 ℃ for 40 hours to obtain sol, and performing reduced pressure concentration and centrifugal separation on the sol to obtain microspheres coated with aluminum sol; and then roasting the microspheres for 3 hours at 1100 ℃, and removing the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
Comparative example 1
The differences from example 1 are: no hardening and wear-resisting assistant is added into the floor paint.
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | AEH-20 Dow chemical | 61 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 1 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.5 |
| Aqueous leveling agent | 4100 digao | 0.2 |
| Surface active agent | OF Chengdu chemical engineering | 0.2 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.1 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 3 |
| Titanium white powder | R996 | 8 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 11 |
| Film forming aid | PDGA Dow | 2 |
| Cosolvent | Ethylene glycol monobutyl ether | 3 |
| Amine neutralizing agents | Ethylene diamine | 0.3 |
| Deionized water | Self-made | 8.7 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Comparative example 2
The differences from example 1 are: no graphene slurry was added.
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | AEH-20 Dow chemical | 61 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 1 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.5 |
| Aqueous leveling agent | 4100 digao | 0.2 |
| Surface active agent | OF Chengdu chemical engineering | 0.2 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.1 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 3 |
| Titanium white powder | R996 | 8 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 11 |
| Hardening wear-resistant auxiliary | MT801 Chongqing Mai Diagram | 1 |
| Film forming aid | PDGA Dow | 2 |
| Cosolvent | Ethylene glycol monobutyl ether | 3 |
| Amine neutralizing agents | Ethylene diamine | 0.3 |
| Deionized water | Self-made | 8.7 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
The preparation method comprises the following steps of:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding phthalocyanine green, titanium dioxide, precipitated barium sulfate, a hardening and wear-resisting agent and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value to 8-8.5 by using a coating neutralizer.
Comparative example 3
The differences from example 6 are: the commercial alumina powder is adopted as the hardening and wear-resisting auxiliary agent.
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | Self-made | 72 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.5 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.3 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.4 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 5 |
| Titanium white powder | R996 | 4 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 2 |
| Hardening wear-resistant auxiliary | Zibojiarun alumina powder | 2 |
| Film forming aid | PDGA Dow | 3 |
| Cosolvent | Ethylene glycol monobutyl ether | 5 |
| Amine neutralizing agents | Ethylene diamine | 0.4 |
| Deionized water | Self-made | 3.9 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
S1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3.2: 4.2: 0.9 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 1h at 86 ℃ in the presence of dibutyltin dilaurate, adding neopentyl glycol, and continuing to react for 1.2h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 2 hours at 85 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end-capping reaction for 1.2 hours, adding sodium bicarbonate for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, E44 epoxy resin, ethyl methacrylate, tung oil, vinyl-terminated polymethylphenyl siloxane to deionized water is 1.8: 9: 1.3: 0.6: 0.5: 22;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 2 wt% of polyvinyl alcohol and 0.6 wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 4, heating to 84 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 3, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 6, after the dropwise addition is finished, continuously reacting for 1.2h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
Comparative example 4
The differences from example 6 are: vinyl groups were not used for the modified epoxy resin emulsion.
The raw materials are adopted according to the mixture ratio shown in the following table:
| weight ratio of | ||
| Aqueous acrylic acid hybrid epoxy resin emulsion | Self-made | 72 |
| Aqueous polyamide wax slurry | BYK-420 BYK | 0.5 |
| Aqueous dispersant | SW-AD-F-053 Jiangsu Tensong | 0.3 |
| Aqueous leveling agent | 4100 digao | 0.3 |
| Surface active agent | OF Chengdu chemical engineering | 0.4 |
| Aqueous defoaming agent | XP-01 Chengdou Alder | 0.2 |
| Pigment (I) | Philadelphia glauca G Jiangsu Shuangle | 5 |
| Titanium white powder | R996 | 4 |
| Precipitated barium sulfate | Zibo Xin Fu hong Yi De | 2 |
| Hardening wear-resistant auxiliary | Self-made | 2 |
| Film forming aid | PDGA Dow | 3 |
| Cosolvent | Ethylene glycol monobutyl ether | 5 |
| Amine neutralizing agents | Ethylene diamine | 0.4 |
| Deionized water | Self-made | 3.9 |
| 10 percent of graphene slurry | B111 Jiangsu high-pass technology | 1 |
| Total up to | 100 | |
| Waterborne modified alicyclic amine epoxy curing agent | 2849 Cyanolide | 10 |
S1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3.2: 4.2: 0.9 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 1h at 86 ℃ in the presence of dibutyltin dilaurate, adding neopentyl glycol, and continuing to react for 1.2h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 2 hours at 85 ℃ in a nitrogen atmosphere, adding sodium bicarbonate for neutralization, adding deionized water, and violently stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, the E44 epoxy resin, the ethyl methacrylate, the tung oil and the deionized water is 1.8: 9: 1.3: 0.6: 22;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 2 wt% of polyvinyl alcohol and 0.6 wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 4, heating to 84 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 3, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 6, after the dropwise addition is finished, continuously reacting for 1.2h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1.1: 0.25, uniformly mixing 45 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator potassium persulfate accounting for 0.4 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 80 ℃ in a nitrogen atmosphere, and dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer sodium p-vinylbenzene sulfonate, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 4: 3: 0.6, the adding amount of the mixed monomer is 11 percent of the weight of the mixed reaction liquid, after 8 hours of reaction, the product is centrifugally separated and washed, and the anionic polymer microspheres are obtained;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.3: 6: 28, mixing the anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent methylcellulose and 65 vol.% of ethanol aqueous solution, heating to 92 ℃ for reaction for 3 hours, adjusting the pH to 3-4 by using dilute nitric acid, aging at 25 ℃ for 35 hours to obtain sol, and performing reduced pressure concentration and centrifugal separation on the sol to obtain microspheres coated with aluminum sol; and then roasting the microspheres for 2 hours at 1080 ℃, and removing the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
Comparative example 5
The differences from example 6 are: in the process of preparing the floor paint, the hardening wear-resistant auxiliary agent is directly added together with the filler.
The raw materials are adopted according to the mixture ratio shown in the following table:
s1: adding the aqueous acrylic acid hybrid epoxy resin emulsion into a production cylinder;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate, water-based polyamide wax slurry and hardening and wear-resisting agent, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
Comparative example 6
The differences from example 6 are: cationic monomer methacryloyloxyethyl trimethyl ammonium chloride is adopted when synthesizing the polymer microspheres.
The raw materials are adopted according to the mixture ratio shown in the following table:
s1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: the fineness was ground to 30 μm using a sand mill.
S5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
The preparation method of the water-based acrylic acid hybrid epoxy resin emulsion comprises the following steps:
step 1, preparing a modified epoxy resin emulsion: according to a molar ratio of 3.2: 4.2: 0.9 preparing polyol, isocyanate and a chain extender, mixing ethylene glycol and toluene diisocyanate, reacting for 1h at 86 ℃ in the presence of dibutyltin dilaurate, adding neopentyl glycol, and continuing to react for 1.2h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 2 hours at 85 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenyl siloxane, continuing to perform reaction and end-capping reaction for 1.2 hours, adding sodium bicarbonate for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, E44 epoxy resin, ethyl methacrylate, tung oil, vinyl-terminated polymethylphenyl siloxane to deionized water is 1.8: 9: 1.3: 0.6: 0.5: 22;
step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 2 wt% of polyvinyl alcohol and 0.6 wt% of emulsifier polyoxyethylene octylphenol ether-10, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 4, heating to 84 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate in a volume ratio of 1: 3, and the volume ratio of the monomer mixed solution to the modified epoxy resin emulsion is 1: and 6, after the dropwise addition is finished, continuously reacting for 1.2h, and then adding sodium bicarbonate for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
The preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing cationic polymer microspheres: according to the volume ratio of 1: 1.1: 0.25, uniformly mixing 45 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator potassium persulfate accounting for 0.4 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 80 ℃ in a nitrogen atmosphere, and dropwise adding a mixed monomer consisting of styrene, acrylic acid and a cationic monomer methacryloyloxyethyl trimethyl ammonium chloride, wherein the weight ratio of the styrene to the acrylic acid to the cationic monomer is 4: 3: 0.6, adding 11% of the mixed monomer by weight of the mixed reaction solution, reacting for 8 hours, and then centrifugally separating and washing the product to obtain the cationic polymer microspheres;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.3: 6: 28, mixing cationic polymer microspheres, aluminum isopropoxide, a pore-forming agent methylcellulose and 65 vol.% of ethanol aqueous solution, heating to 92 ℃ for reaction for 3 hours, adjusting the pH to 3-4 by using dilute nitric acid, aging at 25 ℃ for 35 hours to obtain sol, and performing reduced pressure concentration and centrifugal separation on the sol to obtain microspheres coated with aluminum sol; and then roasting the microspheres for 2 hours at 1080 ℃, and removing the polymer and the pore-forming agent to obtain the hollow porous alumina microspheres.
And (3) dry plate realization: and (2) component A: the component B is prepared according to the proportion of 100:10, deionized distilled water is adopted for adjusting the viscosity, the blade coating viscosity is adjusted to 60-80KU, the roller coating viscosity is adjusted to 50-60KU, and the blade coating and the roller coating are carried out once. And meanwhile, adjusting the viscosity to 30-40S (T-4 cup) according to the proportion, spraying the plate, and detecting the physical properties. And (3) placing the physical dry plate in a constant temperature oven at 25 ℃ for air drying for 48 hours to detect the conventional performance, and testing the wear resistance, the water resistance, the chemical resistance and the weather resistance after curing for 7 days. Terrace template operation process: cleaning the ground → coating the seal primer → coating the waterborne epoxy intermediate paint → coating the waterborne acrylic acid hybrid epoxy floor paint, wherein the total thickness is controlled to be 2-2.5 mm.
Examples 1-8 Dry plate Properties
Comparative examples 1 to 6 Dry plate Properties
As can be seen from the above table, the thick-coating type waterborne acrylic acid hybrid epoxy floor paint prepared by the waterborne acrylic acid hybrid epoxy resin emulsion and the waterborne modified alicyclic amine epoxy curing agent has very excellent quick-drying property, the surface drying is only 60min under the environment that the humidity is more than 90%, no bubble phenomenon and no cracking phenomenon occur when the thickness reaches more than 120 micrometers (dry film thickness), the chemical resistance of the paint film is very excellent, the hardness can reach 2H, more importantly, the room-temperature drying and the humid environment drying are carried out, and the influence on the gloss of the paint film is very small. As can be seen from the example 1 and the comparative example 1, after the hardening and wear-resisting assistant is added, the wear resistance of the coating can reach 0.002; as can be seen from the examples 1 and the comparative examples 2, after the graphene is modified, the hardness of the graphene can be improved by 1H, the wear resistance is obviously improved, the hardness is 750g/500R which is only 0.0001, and the chemical resistance is obviously improved; as can be seen from the examples 6 and the comparative examples 3, when the common alumina sold in the market is used as the wear-resistant material, the fusion property of the common alumina and the waterborne acrylic acid hybrid epoxy emulsion is poor, so that the wear resistance cannot be improved; as can be seen from the examples 6 and the comparative examples 4, when the vinyl-terminated epoxy resin is not adopted, the epoxy resin can not form crosslinking with an acrylate monomer, so that the wear resistance and the weather resistance of the coating can not be improved; it can be seen from the examples 6 and the comparative examples 5 that when the hardening wear-resistant filler is directly mixed with other fillers, the epoxy emulsion and the hollow microsphere wear-resistant filler cannot be well fused, so that the wear resistance of the cured paint layer is poor; it can be seen from example 6 and comparative example 6 that, the cationic monomer is used in the preparation of the polymer microsphere, and the alumina particles in the alumina sol are positively charged, and the charges of the alumina particles and the alumina sol are the same, so that the alumina sol cannot be well fused with the polymer microsphere, and the prepared microsphere has poor wear resistance.
The technology has super excellent construction performance and durability in the field of floor coatings. The paint can be widely applied to various places such as buildings, garages, gymnasiums, court, markets, factories, airports, railway stations, exhibition halls, warehouses, swimming pools and the like, and has excellent appearance effect and comprehensive performance. Low cost, long service life and wide application.
Claims (7)
1. A water-based thick-coating water-based acrylic acid hybrid epoxy floor paint is composed of a component A and a component B; the composition is characterized in that the component A comprises the following components in percentage by weight: 60-72% of water-based acrylic acid hybridized epoxy resin emulsion, 3-5% of pigment, 2-8% of titanium dioxide, 2-15% of precipitated barium sulfate, 1-2% of hardening and wear-resisting agent, 0.3-0.5% of water-based dispersant, 0.1-0.2% of water-based defoamer, 0.2-0.3% of water-based flatting agent, 0.2-0.4% of surfactant, 0.5-1% of water-based polyamide wax slurry, 7-10% of deionized water, 2-3% of film-forming assistant, 3-5% of cosolvent, 0.3-0.6% of paint neutralizer and 1-2% of water-based graphene slurry; wherein the component B is an epoxy curing agent; the hardening and wear-resisting agent is alumina-based wear-resisting particles;
the preparation method of the alumina-based wear-resistant particles comprises the following steps:
step 1, preparing anionic polymer microspheres: according to the volume ratio of 1: 1-1.2: 0.2-0.3, uniformly mixing 40-55 wt% of polyethylene glycol aqueous solution, absolute ethyl alcohol and deionized water to obtain mixed reaction liquid, adding an initiator accounting for 0.3-0.5 wt% of the weight of the mixed reaction liquid, heating the mixed reaction liquid to 75-85 ℃ in a nitrogen atmosphere, dropwise adding a mixed monomer consisting of styrene, acrylic acid and an anionic monomer, wherein the weight ratio of the styrene to the acrylic acid to the anionic monomer is 3-5: 2-4: 0.4-0.8, wherein the adding amount of the mixed monomer is 10-12% of the weight of the mixed reaction solution, and after the reaction is finished, the product is subjected to centrifugal separation and washing to obtain the anionic polymer microspheres; the initiator is potassium persulfate; the anionic monomer is sodium p-vinylbenzene sulfonate, and the reaction time in the step 1 is 6-10 hours;
step 2, preparing the hollow porous alumina microspheres: according to the weight ratio of 1: 1.2-1.5: 5-7: mixing 25-30 anionic polymer microspheres, aluminum isopropoxide, a pore-forming agent and 60-70 vol.% of ethanol aqueous solution, heating to 90-95 ℃, reacting for 2-4 h, adjusting the pH to 3-4 with dilute nitric acid, aging for 30-40 h at 20-30 ℃ to obtain sol, concentrating the sol under reduced pressure, and performing centrifugal separation to obtain microspheres coated with aluminum sol; then roasting the microspheres to remove the polymer and the pore-forming agent to obtain hollow porous alumina microspheres; the pore-foaming agent is methyl cellulose; the roasting is carried out at 1050-1100 ℃ for 1-3 h.
2. The aqueous thick-coating aqueous acrylic hybrid epoxy floor paint according to claim 1, wherein the weight ratio of the component A to the component B is 100: 5 to 15.
3. The water-based thick-coating water-based acrylic hybrid epoxy floor paint as claimed in claim 1, wherein the pigment is one or more of phthalocyanine green G, titanium nickel yellow, titanium chromium brown, cobalt green, cobalt blue, iron chromium black, iron zinc chromium brown, copper chromium black or bismuth yellow.
4. The aqueous thick-coat aqueous acrylic hybrid epoxy floor paint according to claim 1, wherein the cosolvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol ether, propylene glycol monomethyl ether acetate, ethanol, n-butanol or isopropanol.
5. The water-based thick-coating water-based acrylic hybrid epoxy floor paint according to claim 1, wherein the preparation of the modified epoxy resin emulsion in step 1: according to a molar ratio of 3-3.5: 4-4.5: 0.8-1.0, preparing polyol, isocyanate and a chain extender, mixing the polyol and the isocyanate, reacting for 0.5-2 h at 84-90 ℃ in the presence of an organic tin catalyst, adding the chain extender, and continuing to react for 1-1.5 h to obtain a polyurethane prepolymer; mixing the polyurethane prepolymer, E44 epoxy resin, ethyl methacrylate and tung oil, adding an initiator potassium persulfate, reacting for 1-3 h at 82-88 ℃ in a nitrogen atmosphere, then adding vinyl-terminated polymethylphenylsiloxane, continuing to react for 1-1.5 h, adding a neutralizing agent for neutralization, and then adding deionized water for vigorous stirring to obtain a modified epoxy resin emulsion; wherein the weight ratio of the prepolymer, E44 epoxy resin, ethyl methacrylate, tung oil, vinyl-terminated polymethylphenyl siloxane to deionized water is 1.5-2: 8-10: 1.2-1.5: 0.5-0.7: 0.4-0.8: 20-24; step 2, preparing the water-based acrylic acid hybrid epoxy resin emulsion: preparing an aqueous solution containing 1-5 wt% of polyvinyl alcohol and 0.5-1 wt% of an emulsifier, adding an initiator potassium persulfate, and mixing the aqueous solution and the modified epoxy resin emulsion according to a volume ratio of 1: 3-5, heating to 80-85 ℃, and then dropwise adding a mixture of butyl acrylate and methyl methacrylate according to a volume ratio of 1: 2-4, wherein the volume ratio of the monomer mixed liquid to the modified epoxy resin emulsion is 1: and 5-8, after the dropwise addition is finished, continuously reacting for 1-1.5 h, and then adding a neutralizing agent for neutralization to obtain the water-based acrylic acid hybrid epoxy resin emulsion.
6. The aqueous thick-coat aqueous acrylic hybrid epoxy floor paint according to claim 5, wherein the polyol is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butyl diethylene glycol, glycerin or polyethylene glycol; the isocyanate is toluene diisocyanate; the emulsifier is polyoxyethylene octyl phenol ether-10; the organic tin catalyst is dibutyltin dilaurate; the chain extender is one or a mixture of more of l, 4-butanediol, neopentyl glycol, ethylene glycol, diethylene glycol, glycerol, maleic anhydride, trimethylolpropane, ethylenediamine, diethylenetriamine, triethylene tetramine or dimethylolpropionic acid; the neutralizer is sodium bicarbonate, triethylamine, methylamine or triethanolamine.
7. The preparation method of the aqueous thick-coating type aqueous acrylic hybrid epoxy floor paint of claim 1, characterized by comprising the following steps:
s1: adding the water-based acrylic acid hybrid epoxy resin emulsion and the hardening and wear-resisting agent into a production cylinder, and then carrying out vacuum-pumping and defoaming treatment;
s2: diluting the water-based dispersing agent, the water-based defoaming agent, the water-based leveling agent and the surfactant by using deionized water, adding the diluted materials into a production cylinder, and stirring the materials at 300-400 rpm for 5-10 minutes;
s3: adding pigment, titanium dioxide, precipitated barium sulfate and water-based polyamide wax slurry, and stirring for 15-20 minutes at 800-1000 rpm;
s4: grinding the fineness to 30 microns by a sand mill;
s5: adding a film forming aid, a cosolvent and water-based graphene slurry, uniformly stirring, and adjusting the pH value by using a paint neutralizer.
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| CN110812687A (en) * | 2019-11-18 | 2020-02-21 | 山东君合春医药科技有限公司 | Preparation method of porous polymer microneedle |
| CN110885616B (en) * | 2019-12-18 | 2021-11-05 | 株洲市九华新材料涂装实业有限公司 | Thick-coating type water-based epoxy finish paint for rail transit vehicles and preparation method thereof |
| CN112680058B (en) * | 2020-12-14 | 2021-12-14 | 无锡中油瑞德防腐科技有限公司 | Polyamide-imide cured epoxy resin water-based paint and preparation method thereof |
| CN113698837B (en) * | 2021-08-11 | 2023-01-13 | 浙江省产品质量安全科学研究院 | Preparation method of single-component water-based hybrid electromagnetic shielding coating |
| CN114196282A (en) * | 2021-11-28 | 2022-03-18 | 安徽朗凯奇建材有限公司 | Water-based acrylic acid hybrid epoxy floor paint and preparation method thereof |
| CN114672206B (en) * | 2022-03-11 | 2023-03-14 | 山东高速交通科技有限公司 | Aqueous bi-component road marking paint |
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