CN116574425A - Finished product water-based paint and preparation method thereof - Google Patents
Finished product water-based paint and preparation method thereof Download PDFInfo
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- CN116574425A CN116574425A CN202310671034.2A CN202310671034A CN116574425A CN 116574425 A CN116574425 A CN 116574425A CN 202310671034 A CN202310671034 A CN 202310671034A CN 116574425 A CN116574425 A CN 116574425A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003973 paint Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 86
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000004132 cross linking Methods 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 43
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 41
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 29
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- BAZWHTBQKJXGBY-UHFFFAOYSA-N 4-ethenylpyridin-2-amine Chemical compound NC1=CC(C=C)=CC=N1 BAZWHTBQKJXGBY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 110
- 238000001035 drying Methods 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 17
- 229910000077 silane Inorganic materials 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- RROAJOQUFRGVRG-UHFFFAOYSA-L dichlorozinc;ethanol Chemical compound [Cl-].[Cl-].[Zn+2].CCO RROAJOQUFRGVRG-UHFFFAOYSA-L 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a finished water-based paint and a preparation method thereof, and relates to the technical field of coating materials. When the invention is used for preparing finished water paint, methyl methacrylate and hydroxylamine hydrochloride react firstly and then react with acetic anhydride to prepare a temperature-controlled crosslinking monomer; bisphenol A epoxy resin and polyethylene glycol monomethyl ether react to prepare an active emulsifier; after the nano calcium carbonate and triethoxysilane react, the nano calcium carbonate reacts with dimethylallylsilane and 2-amino-4-vinyl-pyridine in sequence to prepare modified nano calcium carbonate, a temperature control crosslinking monomer, methyl methacrylate and butyl acrylate are emulsified by an active emulsifier, azodiisobutyronitrile is used for initiating crosslinking, and then the modified nano calcium carbonate is added for mixing to prepare the finished product water paint. The finished water paint prepared by the invention has excellent hardness and wear resistance.
Description
Technical Field
The invention relates to the technical field of coating materials, in particular to a finished product water-based paint and a preparation method thereof.
Background
The organic paint is a paint which is composed of polymer compound as main film forming component. The coating is coated on the surface of the product or object to form a layer of coating which is firmly attached, and plays a role in protecting the internal object from physical and chemical damages. Compared with the replacement of damaged products, the coating for coating the surface of an object with the protective film is more energy-saving, convenient and attractive, so that the coating is widely applied to various fields of automobiles, ships, ornaments, buildings, furniture and the like. In early days of application, organic solvents were generally used to dissolve polymeric compounds, also known as paints, in order to facilitate coating film by controlling the viscosity of the paint. This causes emission of volatile organic compounds, which pollute the environment.
In order to adapt to the current trend of green development, development of environment-friendly paint to replace traditional oil paint becomes an important point and a hot spot of material worker research. The characteristic of cleaning and environmental protection of the water-based paint by taking water as a solvent attracts the hot attention of researchers, but compared with the traditional oil-based paint, the water-based paint has the defects of low hardness and poor mechanical property. The defects make the surface of the water-based coating more easily generate scratch and crack under the action of external force, so that the coating loses the protection effect or the appearance of the whole device is influenced, and the service life is shortened and the use value is lost. Therefore, the water-based paint has good hardness and mechanical property and has great research value.
Disclosure of Invention
The invention aims to provide a finished water-based paint and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a finished water paint is prepared by emulsifying a temperature-control crosslinking monomer, methyl methacrylate and butyl acrylate with an active emulsifier, initiating crosslinking with azodiisobutyronitrile, and then adding modified nano calcium carbonate to mix.
The temperature control crosslinking monomer is prepared by reacting methyl methacrylate and hydroxylamine hydrochloride and then reacting with acetic anhydride.
The active emulsifier is prepared by reacting bisphenol A epoxy resin and polyethylene glycol monomethyl ether.
As optimization, the modified nano calcium carbonate is prepared by reacting nano calcium carbonate with triethoxysilane, and then sequentially reacting with dimethylallylsilane and 2-amino-4-vinyl-pyridine.
The preparation method of the finished water paint comprises the following preparation steps:
(1) Uniformly mixing the intermediate and methylene dichloride according to the mass ratio of 1:12-16, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 6-8% and the mass fraction of 5-6 times of the intermediate at a constant speed within 30-40 min under the stirring condition of 200-300 r/min at the temperature of 10-30 ℃, continuously stirring for 8-10 min after the dropwise adding, adding acetic anhydride with the mass of 1-1.2 times of the intermediate, continuously stirring and reacting for 20-24 h, stirring and washing with pure water, extracting for 3-5 times with methylene dichloride, and drying for 8-10 h at the temperature of 75-80 ℃ to obtain the temperature-controlled crosslinking monomer;
(2) Uniformly mixing epoxy resin and polyethylene glycol monomethyl ether according to the ratio of the number of epoxy groups on the epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 10-12 times of that of the epoxy resin, adding triphenylphosphine with the mass of 0.04-0.06 times of that of the epoxy resin at a constant speed within 3-5 min under the stirring condition of 200-300 r/min at the temperature of 55-65 ℃ in a nitrogen atmosphere, continuously stirring for 4-5 h, and drying for 6-8 h at the temperature of 40-50 ℃ and 1-2 kPa to obtain an active emulsifier;
(3) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to the mass ratio of 1:2-3:8-10, stirring for 20-25 min at 20-30 ℃ at 600-800 r/min, adding nano calcium carbonate with the mass of 1-1.2 times of that of the triethoxysilane, carrying out ultrasonic treatment for 1-2 h at 20-30 ℃ at 25-35 kHz, carrying out centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, drying for 6-8 h at 60-70 ℃, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:6-8:0.03-0.05, stirring and refluxing for 3-4 h at 70-80 ℃ at 300-500 r/min in nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.3-0.4 times of that of dimethyl allyl silane, continuing stirring and reacting for 3-4 h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, and drying for 6-8 h at 60-70 ℃ to obtain modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to the mass ratio of 1:3:3:0.4-0.5:35-45, adding azodiisobutyronitrile with the mass of 0.03-0.04 times of the temperature-controlled crosslinking monomer, heating to 60-65 ℃ in a nitrogen atmosphere, stirring at 300-500 r/min for reacting for 10-12 h, adding modified nano calcium carbonate with the mass of 4-6 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 6-8 min at 20-30 ℃ at 25-35 kHz to obtain the finished water-based paint.
As an optimization, the preparation method of the intermediate in the step (1) comprises the following steps: methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:4-6 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:4-6, uniformly dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 20-25% and 3-4 times that of the hydroxylamine hydrochloride in 30-40 min under the stirring condition of 0-5 ℃ and 200-300 r/min in a nitrogen atmosphere, continuously stirring for 3-5 min after the dropwise adding is finished, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5-6 times that of the hydroxylamine hydrochloride in 30-40 min at a uniform speed, heating to 25-30 ℃ after the dropwise adding is finished, continuously stirring for 20-24 h, drying for 8-10 h at 60-70 ℃, regulating the pH value to 5-6 with a hydrochloric acid aqueous solution with a mass fraction of 4-6%, drying for 8-10 h at 60-70 ℃, extracting for 3-5 times with ethyl acetate, and drying for 8-10 h at 75-80 ℃ to prepare the aqueous solution.
Preferably, the epoxy resin in the step (2) is bisphenol A type epoxy resin.
As optimization, the model of the polyethylene glycol monomethyl ether in the step (2) is polyethylene glycol monomethyl ether MPEG2000.
As optimization, the use method of the finished water paint comprises the following steps: the viscosity of the finished water paint is regulated by adding or evaporating pure water, measured by a coating-4 viscosimeter, regulated to 20-30 s, sprayed on the surface to be sprayed according to the required amount, sequentially kept stand at room temperature for 25-30 min, kept stand at 60-65 ℃ for 2-3 h, kept at 90-100 ℃ for 2-3 h, kept at 130-140 ℃ for 10-12 h, cooled to room temperature, sprayed with zinc chloride ethanol solution with the mass fraction of 6-8% on the finished water paint solidified coating according to the same spraying amount of the finished water paint, dried for 20-24 h at 60-65 ℃ after the spraying is finished, cleaned on the surface by pure water for 3-5 times, and naturally dried.
Compared with the prior art, the invention has the following beneficial effects:
when the invention is used for preparing finished water paint, methyl methacrylate and hydroxylamine hydrochloride react and then react with acetic anhydride to prepare a temperature-controlled crosslinking monomer; bisphenol A epoxy resin and polyethylene glycol monomethyl ether react to prepare an active emulsifier; emulsifying the temperature-controlled crosslinking monomer, methyl methacrylate and butyl acrylate with an active emulsifier, initiating crosslinking with azodiisobutyronitrile, and then adding modified nano calcium carbonate to mix to obtain the finished water-based paint.
Firstly, after the temperature control crosslinking monomer used in the invention participates in copolymerization, the temperature control crosslinking monomer can be rearranged at high temperature to generate isocyanate groups, and the isocyanate groups are crosslinked with hydroxyl groups and amino groups in other components to form a crosslinking network structure, so that the crosslinking network structure has a more stable mechanical structure, and the wear resistance is improved; the self-made active emulsifier not only can play a role in emulsification, but also can react with other components to ensure that the structure is more compact and stable, thereby improving the wear resistance.
Secondly, after nano calcium carbonate and triethoxysilane react, modified nano calcium carbonate is prepared by sequentially reacting with dimethyl allyl silane and 2-amino-4-vinyl-pyridine, polysilane branched chains are formed on the surface of the nano calcium carbonate, amino pyridine groups are arranged at the side ends, the dispersibility of the nano calcium carbonate is improved, metal coordination structures can be formed among the amino pyridine groups through metal ions, so that the hardness is improved, and amino groups can be combined with epoxy groups on an active emulsifier and isocyanate groups generated by rearrangement of a temperature control crosslinking monomer, so that the wear resistance is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:4 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:4, uniformly dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 20% and 3 times that of the hydroxylamine hydrochloride in 40min under the stirring condition of 200r/min at the temperature of 0 ℃ in a nitrogen atmosphere, continuously stirring for 5min after the completion of the dropwise adding, keeping the stirring condition unchanged, continuously uniformly dropwise adding a methyl methacrylate solution with a mass fraction of 5 times that of the hydroxylamine hydrochloride in 30min, heating to 25 ℃ after the completion of the dropwise adding, continuously stirring for 24h, drying for 10h at 60 ℃, regulating the pH value to 5 by using a hydrochloric acid aqueous solution with a mass fraction of 4%, drying for 10h at 60 ℃, extracting for 3 times by using ethyl acetate, and drying for 10h at 75 ℃ to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:12, uniformly dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 6% and 5 times that of the intermediate at a constant speed within 40min under the stirring condition of 200r/min at the temperature of 10 ℃, continuously stirring for 10min after the dropwise adding is finished, adding acetic anhydride with the mass fraction of 1 time that of the intermediate, continuously stirring and reacting for 24h, stirring and washing with pure water, extracting with dichloromethane for 3 times, and drying at the temperature of 75 ℃ for 10h to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass 10 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass 0.04 times that of the bisphenol A epoxy resin at a constant speed within 3min under the stirring condition of 200r/min at the temperature of 55 ℃ in a nitrogen atmosphere, continuously stirring for 5h, and drying for 8h at the temperature of 40 ℃ under the pressure of 1kPa to obtain an active emulsifier;
(3) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to a mass ratio of 1:2:8, stirring at 20 ℃ for 25min at 600r/min, adding nano calcium carbonate with the mass of 1 time of the triethoxysilane, carrying out ultrasonic treatment at 20 ℃ and 25kHz for 2h, centrifugally separating, washing with absolute ethyl alcohol for 3 times, drying at 60 ℃ for 8h, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to a mass ratio of 1:1:6:0.03, stirring and refluxing at 70 ℃ for 4h at 300r/min in a nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.3 time of the dimethyl allyl silane, continuously stirring and reacting for 4h, centrifugally separating, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 8h to obtain modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 1:3:3:0.4:35, adding azodiisobutyronitrile with the mass of 0.03 times of the temperature-controlled crosslinking monomer, heating to 60 ℃ in a nitrogen atmosphere, stirring at 300r/min for reaction for 10 hours, adding modified nano calcium carbonate with the mass of 4 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 8 minutes at 20 ℃ at 25kHz to obtain the finished water-based paint.
Example 2
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:5 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:5, dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 22% and 3.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min under the stirring condition of 2 ℃ and 250r/min in nitrogen atmosphere, continuously stirring for 4min after the dropwise adding is finished, keeping the stirring condition unchanged, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min, heating to 28 ℃ after the dropwise adding is finished, continuously stirring for 22h, drying for 9h at 65 ℃, regulating the pH value to 5.5 by using a hydrochloric acid aqueous solution with a mass fraction of 5%, drying for 9h at 65 ℃, extracting for 4 times by using ethyl acetate, and drying for 9h at 78 ℃ to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:14, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 7% which is 5.5 times that of the intermediate at a constant speed within 35min under the stirring condition of 250r/min at 20 ℃, continuously stirring for 9min after the dropwise adding is finished, adding acetic anhydride with the mass of 1.1 times that of the intermediate, continuously stirring and reacting for 22h, stirring and washing with pure water, extracting with dichloromethane for 4 times, and drying for 9h at 78 ℃ to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 11 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass of 0.05 times that of the bisphenol A epoxy resin at a constant speed within 4min under the stirring condition of 60 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 4.5h, and drying for 7h at 45 ℃ and 1.5kPa to obtain an active emulsifier;
(3) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to the mass ratio of 1:2.5:9, stirring at 25 ℃ for 22min at 700r/min, adding nano calcium carbonate with the mass of 1.1 times of that of the triethoxysilane, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 1-2 h, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7h, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:7:0.04, stirring at 75 ℃ for reflux for 3.5h at 400r/min in a nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.35 times of that of the dimethyl allyl silane, continuously stirring for 3.5h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7h to obtain modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 1:3:3:0.45:40, adding azodiisobutyronitrile with a mass of 0.035 times that of the temperature-controlled crosslinking monomer, heating to 62 ℃ in a nitrogen atmosphere, stirring at 400r/min for reaction for 11h, adding modified nano calcium carbonate with a mass of 5 times that of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 7min at 25 ℃ and 30kHz to obtain the finished water-based paint.
Example 3
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:6 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:6, uniformly dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 25% and with a mass fraction of 4 times that of the hydroxylamine hydrochloride in 30min under a stirring condition of 5 ℃ and 300r/min in a nitrogen atmosphere, continuously stirring for 5min after the completion of the dropwise adding, keeping the stirring condition unchanged, continuously uniformly dropwise adding a methyl methacrylate solution with a mass fraction of 6 times that of the hydroxylamine hydrochloride in 40min, heating to 30 ℃ after the completion of the dropwise adding, continuously stirring for 20h, drying at 70 ℃ for 8h, regulating the pH value to 5 by using a hydrochloric acid aqueous solution with a mass fraction of 6%, drying at 70 ℃ for 8h, extracting for 5 times by using ethyl acetate, and drying at 80 ℃ for 8h to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:16, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 8% and with the mass of 6 times that of the intermediate at a constant speed within 30 minutes under the stirring condition of 300r/min at 30 ℃, continuously stirring for 8 minutes after the dropwise adding is finished, adding acetic anhydride with the mass of 1.2 times that of the intermediate, continuously stirring and reacting for 20 hours, stirring and washing with pure water, extracting with dichloromethane for 5 times, and drying at 80 ℃ for 8 hours to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 12 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass of 0.06 times that of the bisphenol A epoxy resin at a constant speed within 5min under the stirring condition of 300r/min at 65 ℃ in nitrogen atmosphere, continuously stirring for 5h, and drying for 6h at 50 ℃ and 2kPa to obtain an active emulsifier;
(3) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to a mass ratio of 1:3:10, stirring at 30 ℃ for 20min at 800r/min, adding nano calcium carbonate with the mass of 1.2 times of that of the triethoxysilane, carrying out ultrasonic treatment at 30 ℃ and 35kHz for 1h, centrifugally separating, washing with absolute ethyl alcohol for 5 times, drying at 70 ℃ for 6h, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to a mass ratio of 1:1:8:0.05, stirring and refluxing at 80 ℃ for 3h at 500r/min in a nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.4 times of that of the dimethyl allyl silane, continuously stirring and reacting for 3h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 5 times, and drying at 70 ℃ for 6h to obtain modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 1:3:3:0.5:45, adding azodiisobutyronitrile with the mass of 0.04 times of the temperature-controlled crosslinking monomer, heating to 65 ℃ in a nitrogen atmosphere, stirring at 500r/min for reaction for 10 hours, adding modified nano calcium carbonate with the mass of 6 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 6 minutes at 30 ℃ and 35kHz to obtain the finished water-based paint.
Comparative example 1
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 11 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass of 0.05 times that of the bisphenol A epoxy resin at a constant speed within 4min under the stirring condition of 60 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 4.5h, and drying for 7h at 45 ℃ and 1.5kPa to obtain an active emulsifier;
(2) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to the mass ratio of 1:2.5:9, stirring at 25 ℃ for 22min at 700r/min, adding nano calcium carbonate with the mass of 1.1 times of that of the triethoxysilane, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 1-2 h, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7h, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:7:0.04, stirring at 75 ℃ for reflux for 3.5h at 400r/min in a nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.35 times of that of the dimethyl allyl silane, continuously stirring for 3.5h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7h to obtain modified nano calcium carbonate;
(3) Uniformly mixing methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 4:3:0.45:40, adding azodiisobutyronitrile with a mass of 0.035 times of a temperature-controlled crosslinking monomer, heating to 62 ℃ in a nitrogen atmosphere, stirring at 400r/min for reaction for 11h, adding modified nano calcium carbonate with a mass of 5 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 7min at 25 ℃ and 30kHz to obtain the finished product water-based paint.
Comparative example 2
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:5 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:5, dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 22% and 3.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min under the stirring condition of 2 ℃ and 250r/min in nitrogen atmosphere, continuously stirring for 4min after the dropwise adding is finished, keeping the stirring condition unchanged, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min, heating to 28 ℃ after the dropwise adding is finished, continuously stirring for 22h, drying for 9h at 65 ℃, regulating the pH value to 5.5 by using a hydrochloric acid aqueous solution with a mass fraction of 5%, drying for 9h at 65 ℃, extracting for 4 times by using ethyl acetate, and drying for 9h at 78 ℃ to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:14, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 7% which is 5.5 times that of the intermediate at a constant speed within 35min under the stirring condition of 250r/min at 20 ℃, continuously stirring for 9min after the dropwise adding is finished, adding acetic anhydride with the mass of 1.1 times that of the intermediate, continuously stirring and reacting for 22h, stirring and washing with pure water, extracting with dichloromethane for 4 times, and drying for 9h at 78 ℃ to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to the mass ratio of 1:2.5:9, stirring at 25 ℃ for 22min at 700r/min, adding nano calcium carbonate with the mass of 1.1 times of that of the triethoxysilane, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 1-2 h, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7h, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:7:0.04, stirring at 75 ℃ for reflux for 3.5h at 400r/min in a nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.35 times of that of the dimethyl allyl silane, continuously stirring for 3.5h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7h to obtain modified nano calcium carbonate;
(3) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, AEO-9 and pure water according to a mass ratio of 1:3:3:0.45:40, adding azodiisobutyronitrile with the mass of 0.035 times of the temperature-controlled crosslinking monomer, heating to 62 ℃ in a nitrogen atmosphere, stirring at 400r/min for reaction for 11h, adding modified nano calcium carbonate with the mass of 5 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 7min at 25 ℃ and 30kHz to obtain the finished water-based paint.
Comparative example 3
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:5 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:5, dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 22% and 3.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min under the stirring condition of 2 ℃ and 250r/min in nitrogen atmosphere, continuously stirring for 4min after the dropwise adding is finished, keeping the stirring condition unchanged, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min, heating to 28 ℃ after the dropwise adding is finished, continuously stirring for 22h, drying for 9h at 65 ℃, regulating the pH value to 5.5 by using a hydrochloric acid aqueous solution with a mass fraction of 5%, drying for 9h at 65 ℃, extracting for 4 times by using ethyl acetate, and drying for 9h at 78 ℃ to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:14, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 7% which is 5.5 times that of the intermediate at a constant speed within 35min under the stirring condition of 250r/min at 20 ℃, continuously stirring for 9min after the dropwise adding is finished, adding acetic anhydride with the mass of 1.1 times that of the intermediate, continuously stirring and reacting for 22h, stirring and washing with pure water, extracting with dichloromethane for 4 times, and drying for 9h at 78 ℃ to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 11 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass of 0.05 times that of the bisphenol A epoxy resin at a constant speed within 4min under the stirring condition of 60 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 4.5h, and drying for 7h at 45 ℃ and 1.5kPa to obtain an active emulsifier;
(3) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 1:3:3:0.45:40, adding azodiisobutyronitrile with the mass of 0.035 times of the temperature-controlled crosslinking monomer, heating to 62 ℃ in a nitrogen atmosphere, stirring at 400r/min for reaction for 11h, adding nano calcium carbonate with the mass of 5 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 7min at 25 ℃ and 30kHz to obtain the finished product water-based paint.
Comparative example 4
The preparation method of the finished water-based paint comprises the following preparation steps:
(1) Methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:5 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:5, dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 22% and 3.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min under the stirring condition of 2 ℃ and 250r/min in nitrogen atmosphere, continuously stirring for 4min after the dropwise adding is finished, keeping the stirring condition unchanged, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5.5 times of the hydroxylamine hydrochloride at a uniform speed within 35min, heating to 28 ℃ after the dropwise adding is finished, continuously stirring for 22h, drying for 9h at 65 ℃, regulating the pH value to 5.5 by using a hydrochloric acid aqueous solution with a mass fraction of 5%, drying for 9h at 65 ℃, extracting for 4 times by using ethyl acetate, and drying for 9h at 78 ℃ to obtain an intermediate; uniformly mixing the intermediate and dichloromethane according to the mass ratio of 1:14, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 7% which is 5.5 times that of the intermediate at a constant speed within 35min under the stirring condition of 250r/min at 20 ℃, continuously stirring for 9min after the dropwise adding is finished, adding acetic anhydride with the mass of 1.1 times that of the intermediate, continuously stirring and reacting for 22h, stirring and washing with pure water, extracting with dichloromethane for 4 times, and drying for 9h at 78 ℃ to obtain a temperature-controlled crosslinking monomer;
(2) Uniformly mixing bisphenol A epoxy resin and polyethylene glycol monomethyl ether MPEG2000 according to the ratio of the number of epoxy groups on the bisphenol A epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether MPEG2000 of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 11 times that of the bisphenol A epoxy resin, adding triphenylphosphine with the mass of 0.05 times that of the bisphenol A epoxy resin at a constant speed within 4min under the stirring condition of 60 ℃ and 250r/min in a nitrogen atmosphere, continuously stirring for 4.5h, and drying for 7h at 45 ℃ and 1.5kPa to obtain an active emulsifier;
(3) Uniformly mixing nano calcium carbonate, dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:7:0.04, stirring and refluxing at the temperature of 75 ℃ for 3.5 hours in a nitrogen atmosphere at the speed of 400r/min, adding 2-amino-4-vinyl-pyridine with the mass of 0.35 times that of the dimethyl allyl silane, continuously stirring and reacting for 3.5 hours, centrifugally separating, washing for 4 times by using absolute ethyl alcohol, and drying at the temperature of 65 ℃ for 7 hours to prepare modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to a mass ratio of 1:3:3:0.45:40, adding azodiisobutyronitrile with a mass of 0.035 times that of the temperature-controlled crosslinking monomer, heating to 62 ℃ in a nitrogen atmosphere, stirring at 400r/min for reaction for 11h, adding modified nano calcium carbonate with a mass of 5 times that of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 7min at 25 ℃ and 30kHz to obtain the finished water-based paint.
Test example 1
Hardness and wear resistance test
The preparation of the coating comprises the steps of adding or evaporating pure water, adjusting the viscosity of the finished water-based paint, measuring by a coating-4 viscosimeter, adjusting to 25s, spraying the surface to be sprayed according to the required amount for forming the coating with the thickness of 1mm, sequentially standing at room temperature for 28min after spraying, standing at 63 ℃ for 2.5h, standing at 100 ℃ for 2h, standing at 140 ℃ for 10h, cooling to room temperature, spraying a zinc chloride ethanol solution with the mass fraction of 7% on the finished water-based paint cured coating according to the same spraying amount of the finished water-based paint, drying at 63 ℃ for 22h after the spraying is finished, cleaning the surface with pure water for 4 times, and naturally drying to obtain the cured coating to be tested.
Hardness: the pencil hardness test of the cured coating was carried out according to the specifications of GB/T6739-1996. And judging the pencil hardness grade of the coating by judging whether the surface of the cured coating is scratched or not. The pencil for test is a mitsubishi pencil.
Wear resistance: the abrasion resistance of the coating film was measured according to GB/T1768-2006 using a reciprocating abrasion test, the surface abrasion resistance of the cured coating was measured with 60-mesh sandpaper, and the cured coating was rubbed back and forth under a pressure of 4kPa, and a total of 10 back and forth were abraded, and the mass loss rate was calculated from the mass change before and after abrasion, mass loss rate=1-mass after abrasion/mass before abrasion. The results are shown in Table 1.
TABLE 1
| Hardness of | Mass loss rate | Hardness of | Mass loss rate | ||
| Example 1 | 4H | 0.114％ | Comparative example 1 | 4H | 0.195％ |
| Example 2 | 4H | 0.112％ | Comparative example 2 | 4H | 0.152％ |
| Example 3 | 4H | 0.117％ | Comparative example3 | H | 0.281％ |
| Comparative example 4 | 2H | 0.178％ |
As can be seen from the comparison of the experimental data of examples 1-3 and comparative examples 1-4 in Table 1, the finished water-based paint prepared by the invention has good hardness and wear resistance.
By comparison, examples 1, 2 and 3 have high mass loss rate compared with comparative example 1, and demonstrate that the use of temperature-controlled crosslinking monomers for copolymerization can rearrange at high temperature to produce isocyanate groups, crosslink with hydroxyl groups and amino groups in other components to form a crosslinked network structure, and have a more stable mechanical structure, so that the wear resistance is improved.
By comparison, examples 1, 2 and 3 have high mass loss rate compared with comparative example 2, and the use of the active emulsifier not only can play a role in emulsification, but also can react with other components by the active groups on the active emulsifier, so that the structure is more compact and stable, and the wear resistance is improved.
By contrast, examples 1, 2 and 3 compared with comparative examples 3 and 4 have high hardness and high mass loss rate, the nano calcium carbonate is modified, polysilocarb branched chains are formed on the surface of the nano calcium carbonate, amino pyridine groups are arranged at the edge ends, the dispersibility of the nano calcium carbonate is improved, metal coordination structures can be formed among the amino pyridine groups through metal ions, so that the hardness is improved, and amino groups can be combined with epoxy groups on an active emulsifier and isocyanate groups generated by rearrangement of a temperature control crosslinking monomer, so that the wear resistance is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. A finished water paint is characterized by being prepared by emulsifying a temperature-control crosslinking monomer, methyl methacrylate and butyl acrylate by an active emulsifier, initiating crosslinking by azodiisobutyronitrile, and then adding modified nano calcium carbonate to mix.
2. The finished water paint as claimed in claim 1, wherein the temperature-controlled crosslinking monomer is prepared by reacting methyl methacrylate with hydroxylamine hydrochloride and then reacting with acetic anhydride.
3. The finished water paint as claimed in claim 1, wherein the reactive emulsifier is prepared by reacting bisphenol a type epoxy resin with polyethylene glycol monomethyl ether.
4. A finished water paint according to claim 3, wherein the modified nano calcium carbonate is prepared by reacting nano calcium carbonate with triethoxysilane, and then sequentially reacting with dimethylallylsilane and 2-amino-4-vinyl-pyridine.
5. The preparation method of the finished water paint is characterized by comprising the following preparation steps:
(1) Uniformly mixing the intermediate and methylene dichloride according to the mass ratio of 1:12-16, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 6-8% and the mass fraction of 5-6 times of the intermediate at a constant speed within 30-40 min under the stirring condition of 200-300 r/min at the temperature of 10-30 ℃, continuously stirring for 8-10 min after the dropwise adding, adding acetic anhydride with the mass of 1-1.2 times of the intermediate, continuously stirring and reacting for 20-24 h, stirring and washing with pure water, extracting for 3-5 times with methylene dichloride, and drying for 8-10 h at the temperature of 75-80 ℃ to obtain the temperature-controlled crosslinking monomer;
(2) Uniformly mixing epoxy resin and polyethylene glycol monomethyl ether according to the ratio of the number of epoxy groups on the epoxy resin to the number of hydroxyl groups on the polyethylene glycol monomethyl ether of 2:1, adding the mixture into N, N-dimethylformamide with the mass of 10-12 times of that of the epoxy resin, adding triphenylphosphine with the mass of 0.04-0.06 times of that of the epoxy resin at a constant speed within 3-5 min under the stirring condition of 200-300 r/min at the temperature of 55-65 ℃ in a nitrogen atmosphere, continuously stirring for 4-5 h, and drying for 6-8 h at the temperature of 40-50 ℃ and 1-2 kPa to obtain an active emulsifier;
(3) Uniformly mixing triethoxysilane, pure water and absolute ethyl alcohol according to the mass ratio of 1:2-3:8-10, stirring for 20-25 min at 20-30 ℃ at 600-800 r/min, adding nano calcium carbonate with the mass of 1-1.2 times of that of the triethoxysilane, carrying out ultrasonic treatment for 1-2 h at 20-30 ℃ at 25-35 kHz, carrying out centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, drying for 6-8 h at 60-70 ℃, uniformly mixing with dimethyl allyl silane, n-hexane and chloroplatinic acid according to the mass ratio of 1:1:6-8:0.03-0.05, stirring and refluxing for 3-4 h at 70-80 ℃ at 300-500 r/min in nitrogen atmosphere, adding 2-amino-4-vinyl-pyridine with the mass of 0.3-0.4 times of that of dimethyl allyl silane, continuing stirring and reacting for 3-4 h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, and drying for 6-8 h at 60-70 ℃ to obtain modified nano calcium carbonate;
(4) Uniformly mixing a temperature-controlled crosslinking monomer, methyl methacrylate, butyl acrylate, an active emulsifier and pure water according to the mass ratio of 1:3:3:0.4-0.5:35-45, adding azodiisobutyronitrile with the mass of 0.03-0.04 times of the temperature-controlled crosslinking monomer, heating to 60-65 ℃ in a nitrogen atmosphere, stirring at 300-500 r/min for reacting for 10-12 h, adding modified nano calcium carbonate with the mass of 4-6 times of the temperature-controlled crosslinking monomer after the reaction is finished, and performing ultrasonic dispersion for 6-8 min at 20-30 ℃ at 25-35 kHz to obtain the finished water-based paint.
6. The method for preparing a finished water paint according to claim 5, wherein the method for preparing the intermediate in the step (1) comprises the following steps: methyl methacrylate and methanol are uniformly mixed according to the mass ratio of 1:4-6 to prepare methyl methacrylate solution; uniformly mixing hydroxylamine hydrochloride and pure water according to a mass ratio of 1:4-6, uniformly dropwise adding a sodium hydroxide aqueous solution with a mass fraction of 20-25% and 3-4 times that of the hydroxylamine hydrochloride in 30-40 min under the stirring condition of 0-5 ℃ and 200-300 r/min in a nitrogen atmosphere, continuously stirring for 3-5 min after the dropwise adding is finished, continuously dropwise adding a methyl methacrylate solution with a mass fraction of 5-6 times that of the hydroxylamine hydrochloride in 30-40 min at a uniform speed, heating to 25-30 ℃ after the dropwise adding is finished, continuously stirring for 20-24 h, drying for 8-10 h at 60-70 ℃, regulating the pH value to 5-6 with a hydrochloric acid aqueous solution with a mass fraction of 4-6%, drying for 8-10 h at 60-70 ℃, extracting for 3-5 times with ethyl acetate, and drying for 8-10 h at 75-80 ℃ to prepare the aqueous solution.
7. The method of claim 5, wherein the epoxy resin in step (2) is bisphenol A type epoxy resin.
8. The method for preparing a finished water paint according to claim 5, wherein the type of the polyethylene glycol monomethyl ether in the step (2) is polyethylene glycol monomethyl ether MPEG2000.
9. The method for preparing the finished water paint according to claim 5, wherein the method for using the finished water paint is as follows: the viscosity of the finished water paint is regulated by adding or evaporating pure water, measured by a coating-4 viscosimeter, regulated to 20-30 s, sprayed on the surface to be sprayed according to the required amount, sequentially kept stand at room temperature for 25-30 min, kept stand at 60-65 ℃ for 2-3 h, kept at 90-100 ℃ for 2-3 h, kept at 130-140 ℃ for 10-12 h, cooled to room temperature, sprayed with zinc chloride ethanol solution with the mass fraction of 6-8% on the finished water paint solidified coating according to the same spraying amount of the finished water paint, dried for 20-24 h at 60-65 ℃ after the spraying is finished, cleaned on the surface by pure water for 3-5 times, and naturally dried.
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