CN118772749B - Thick paste type composite stone-like paint and preparation method thereof - Google Patents
Thick paste type composite stone-like paint and preparation method thereof Download PDFInfo
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- CN118772749B CN118772749B CN202410995734.1A CN202410995734A CN118772749B CN 118772749 B CN118772749 B CN 118772749B CN 202410995734 A CN202410995734 A CN 202410995734A CN 118772749 B CN118772749 B CN 118772749B
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/63—Additives non-macromolecular organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
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Abstract
The invention relates to the technical field of stone-like paint research and development, and discloses a thick paste type composite stone-like paint and a preparation method thereof, wherein the thick paste type composite stone-like paint consists of composite base coat, stone-like paint main paint and finish coat, and the preparation method of the finish coat comprises the steps of synthesizing light stable coupling monomer and light stabilizer; the preparation method comprises the steps of modifying titanium dioxide nano particles by using a photo-stable coupling monomer and/or a light stabilizer to obtain photo-stable titanium dioxide nano particles, carrying out composite treatment on trimethoxy (2-phenethyl) silane modified graphene nano sheets by the photo-stable titanium dioxide nano particles based on pi-pi stacking effect to obtain a graphene-titanium dioxide composite material, and carrying out modification treatment on finish paint by the graphene-titanium dioxide composite material to obtain the composite finish paint. The present invention provides a process for preparing a finish and a finish having excellent weatherability is prepared.
Description
Technical Field
The invention relates to the technical field of stone-like paint research and development, in particular to a thick paste type composite stone-like paint and a preparation method thereof.
Background
The stone-like paint has the decorative effect which is comparable to that of stone, is easier to mould various arts than the stone, has rich texture, high hardness and economic manufacturing cost, and can be widely applied. The common problems of the traditional stone-like paint standard construction procedures (comprising mortar, putty, primer, middle paint, stone-like paint main paint and finish paint) and the traditional process (comprising interfacial agent, anti-cracking mortar, gridding cloth, flexible putty, primer, middle paint, stone-like paint main paint and finish paint) for renewing old walls such as ceramic tile mosaic and the like are that the construction procedures are more.
The stone-like paint is exposed to the outside and is easily influenced by environmental factors and physical factors, such as ultraviolet rays, weathering, water vapor, mechanical abrasion and the like, so that the surface is subjected to phenomena of falling, cracking, chromatic aberration and the like. In order to protect the surface of stone-like paints and to increase the weatherability, it is recommended to use a finish for protection after painting the stone-like paint.
The main way to increase the weather resistance of stone-like paint is to add antiseptic auxiliary agent and light stabilizing auxiliary agent into the finish paint, for example, china patent with publication No. CN115340776A discloses that 2 '-dihydroxy-5, 5' -dichloro diphenyl methane is used as antiseptic to prepare a water-based, colorful and high-imitation granite colored stone paint texture paint, so as to realize mildew-proof and corrosion-proof performance, china patent with publication No. CN113444414A discloses a stone-like high-weather-resistance antibacterial paint and a preparation method thereof, and inorganic ultraviolet light shielding agents such as nano zinc oxide, nano titanium dioxide and the like are added to remarkably improve the weather resistance of the paint. In addition, there are reports in the prior art on improving the weather resistance of the paint by using graphene.
Disclosure of Invention
The invention provides thick slurry type composite stone-like paint, which is composed of composite base coat, stone-like paint main paint and finish paint, wherein the thick slurry type composite stone-like paint is used for new and old walls, and only needs to be used as mortar, composite base coat, stone-like paint main paint and finish paint, so that the technical defects of whiskering, insufficient thickness, obvious thick stone-like feeling, poor weather resistance, high manufacturing cost for achieving the same effect and the like are overcome, the composite base coat provides the functions of leveling base treatment, adhesion to a substrate, product thickness, modeling, cracking resistance, water resistance, coloring and the like, the stone-like paint main paint provides the functions of stone-like color, stone texture, weather resistance, water resistance, cracking resistance and the like, the finish paint provides the functions of weather resistance, water resistance, stain resistance and the like, and the weather resistance of the finish paint is further developed, and the finish paint with excellent weather resistance is provided.
The thick paste type composite stone-like paint consists of composite base coat, stone-like paint main paint and finish paint, wherein the preparation method of the finish paint comprises the following steps:
step one, synthesizing a photostable coupling monomer;
The light stable coupling monomer is light stable coupling monomer M1, and the chemical structural formula is as follows:
Modifying the titanium dioxide nano particles by using a photostable coupling monomer or modifying the titanium dioxide nano particles by using the photostable coupling monomer and a light stabilizer to prepare the photostable titanium dioxide nano particles; based on pi-pi stacking effect, the photo-stable titanium dioxide nano particles are subjected to composite treatment on the graphene nano sheet modified by trimethoxy (2-phenethyl) silane to prepare a graphene-titanium dioxide composite material, namely the weather-resistant modifier;
Preparing finish paint, wherein the finish paint is prepared by uniformly mixing 55-75wt% of base paint, 5-15wt% of protection glue solution and 10-40wt% of continuous phase, and the base paint contains weather-proof modifier with the dosage of 3-8wt%.
Preferably, the light stable coupling monomer is a light stable coupling monomer M2, and the chemical structural formula is:
Preferably, the chemical structural formula of the light stabilizer is:
preferably, the preparation method of the light stable coupling monomer M1 comprises the following steps:
step S4-1, generating 1, 3-sodium malonate through acid-base neutralization reaction of 1, 3-sodium malonate and sodium hydroxide;
S4-2, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 3-sodium malonate and 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol with the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiopropyl UV-326-based mercaptan;
And S4-3, catalyzing a mercapto functional group of the thiopropyl UV-326-based mercaptan and an alkenyl functional group of the silane coupling agent YDH-171 to generate a nucleophilic addition reaction by an alkaline substance to generate the light-stable coupling monomer M1.
Preferably, the preparation method of the light stable coupling monomer M2 comprises the following steps:
S5-1, generating 1, 4-dimethyl sodium sulfide through acid-base neutralization reaction of 1, 4-dimethyl mercaptan and sodium hydroxide;
S5-2, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 4-dimethyl sodium mercaptide and 2- (5-chloro-2-benzotriazole) -6-tertiary butyl-p-cresol by using the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiophenyl UV-326-based mercaptan;
and S5-3, catalyzing a mercapto functional group of thiophenyl UV-326-based mercaptan and an alkenyl functional group of a silane coupling agent YDH-171 to generate a nucleophilic addition reaction by an alkaline substance to generate the light-stable coupling monomer M2.
Preferably, the inorganic protonic acid is one of hydrochloric acid, sulfuric acid and phosphoric acid;
Preferably, the alkaline substance is one of sodium hydroxide, sodium carbonate and sodium ethoxide.
Preferably, the light stabilizer is prepared by nucleophilic substitution reaction of 1 molar equivalent of 1, 3-sodium malonate and 2 molar equivalents of 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol by utilizing a Williamson ether synthesis reaction mechanism.
Preferably, the base paint comprises 10-20wt% of deionized water, 10-20wt% of resin, 5-10wt% of cellulose, 20-40wt% of filler, 1-5wt% of heat insulating agent, 3-8wt% of weather-resistant modifier, 0.1-1wt% of antifreezing agent, 0.1-1wt% of film forming auxiliary agent, 0.1-1wt% of pH regulator, 0.1-1wt% of dispersing agent, 0.1-1wt% of wetting agent, 10-30wt% of base paint emulsion and 1-3wt% of toner;
The resin is organosilicon modified polyester resin emulsion;
the cellulose is one or two of hydroxyethyl cellulose and hydroxyethyl methyl cellulose;
the filler is one or a combination of a plurality of kaolin, quartz sand, talcum powder and calcium carbonate;
the heat insulating agent is one or a combination of more of titanium dioxide, mica sheets and boron nitride;
The antifreezing agent is one or a combination of more of propylene glycol, ethylene glycol, polyethylene glycol and polypropylene glycol;
The film forming auxiliary agent is alcohol ester twelve;
The pH regulator is one or two of 2-amino-2-methyl-1-propanol and N, N-dimethylethanolamine;
The dispersing agent is a polyacrylic acid ammonium salt dispersing agent;
The wetting agent is octyl phenol polyoxyethylene ether;
the base paint emulsion is silicone-acrylic emulsion;
the toner is iron oxide red.
Preferably, the formula of the protective glue solution comprises 90-95wt% of deionized water, 3-8wt% of protective glue and 0.1-2wt% of protective glue auxiliary agent;
The protective adhesive is one or two of magnesium aluminum silicate and lithium magnesium silicate;
the protective adhesive auxiliary agent is one or two of inorganic bentonite and xanthan gum.
Preferably, the continuous phase comprises 20-40wt% of deionized water, 1-5wt% of weather-resistant modifier, 0.5-2wt% of thickener, 1-5wt% of cross-linking agent, 1-5wt% of defoamer and 50-70wt% of continuous phase emulsion;
The thickener is polyacrylate;
the cross-linking agent is one or two of polycarbodiimide and N, N-methylene bisacrylamide.
The defoaming agent is an organosilicon defoaming agent;
the continuous phase emulsion is an acrylic emulsion.
The base paint comprises, by weight, 10-20wt% of deionized water, 10-20wt% of an organosilicon modified polyester resin emulsion, 2-5wt% of hydroxyethyl cellulose, 2-5wt% of hydroxyethyl methyl cellulose, 5-15wt% of kaolin, 15-25wt% of quartz sand, 1-5wt% of titanium dioxide, 3-8wt% of a graphene-titanium dioxide composite material, 0.1-1wt% of propylene glycol, 0.1-1wt% of alcohol ester twelve, 0.1-1wt% of 2-amino-2-methyl-1-propanol, 0.1-1wt% of a polyacrylic acid ammonium salt dispersing agent, 0.1-1wt% of octylphenol polyoxyethylene ether, 10-30wt% of silicone acrylic emulsion and 1-3wt% of iron oxide red.
Preferably, the formula of the protective glue solution comprises 90-95wt% of deionized water, 3-8wt% of magnesium aluminum silicate and 0.1-2wt% of inorganic bentonite.
Preferably, the continuous phase comprises 20-40wt% of deionized water, 1-5wt% of graphene-titanium dioxide composite material, 0.5-2wt% of polyacrylate, 1-5wt% of polycarbodiimide, 1-5wt% of organic silicon defoamer and 50-70wt% of acrylic emulsion.
The beneficial effects are that:
According to the invention, two novel light stable coupling monomers and a novel light stabilizer are synthesized, graphene and titanium dioxide are modified by using the light stable coupling monomers and/or the novel light stabilizer to obtain a graphene-titanium dioxide composite material, and the graphene-titanium dioxide composite material is introduced into finish paint to obtain the finish paint with excellent weather resistance.
Drawings
FIG. 1 is a synthetic route to a photostable coupling monomer M1;
FIG. 2 is a hydrogen diagram of a photostable coupling monomer M1;
FIG. 3 is a hydrogen diagram of a photostable coupling monomer M2;
FIG. 4 is a synthetic route for light stabilizers;
FIG. 5 is a hydrogen spectrum of a light stabilizer;
FIG. 6 shows the results of performance experiments for the finish.
Detailed Description
The invention combines the performances of graphene and nano titanium dioxide through a newly developed photo-stable coupling monomer and/or a novel light stabilizer to prepare the graphene-titanium dioxide (GO-TiO 2) composite material, which is used for improving the weather resistance in finish paint.
Experimental example 1:
The preparation of the photostable coupling monomer M1, as shown in FIG. 1, comprises the following synthetic steps:
Step one, acid-base neutralization reaction is carried out on 1, 3-propanedithiol and sodium hydroxide to generate 1, 3-propanedithiol sodium;
Step two, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 3-sodium malonate and 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol (ultraviolet absorbent UV-326) with the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiopropyl UV-326 mercaptan;
Wherein, the inorganic protonic acid is one of hydrochloric acid, sulfuric acid and phosphoric acid, and hydrochloric acid is selected to be used in the experimental example;
Step three, a sulfhydryl functional group of thiopropyl UV-326-based mercaptan and an alkenyl functional group of a silane coupling agent YDH-171 (vinyl trimethoxy silane) are subjected to nucleophilic addition reaction to generate a light stable coupling monomer M1;
Wherein, the alkaline substance is one of sodium hydroxide, sodium carbonate and sodium ethoxide, and sodium ethoxide is selected and used in the experimental example;
The specific experimental procedure for the photostable coupling monomer M1 is as follows:
(1) 1.3g of 1, 3-propanedithiol and 40mL of 0.5mol/L sodium hydroxide aqueous solution are added into a three-mouth bottle, and under the action of mechanical stirring, the temperature is raised to 40 ℃ for reaction for 2 hours, the solvent is removed by rotary evaporation, and the 1, 3-propanedithiol sodium is obtained by drying;
(2) Adding 0.8g of 1, 3-sodium malonate and 20mL of absolute ethyl alcohol into a three-port bottle, stirring at room temperature until the sodium malonate and the absolute ethyl alcohol are completely dissolved under the action of mechanical stirring, then dropwise adding 30mL of 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol solution (prepared from 1.6g of 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol and 30mL of absolute ethyl alcohol) into the three-port bottle, heating to 80 ℃ for reflux reaction for 6 hours, cooling to room temperature, adding 20mL of 0.1mol/L hydrochloric acid aqueous solution into the three-port bottle, stirring at room temperature for reaction for 1 hour, washing with deionized water, extracting with diethyl ether, drying with anhydrous magnesium sulfate, removing diethyl ether by rotary evaporation, and vacuum drying to obtain thiopropyl UV-326-based mercaptan;
(3) 1.0g of thiopropyl UV-326-based mercaptan, 0.5g of sodium ethoxide and 30mL of absolute ethyl alcohol are added into a three-necked flask, stirred at room temperature until the solution is completely dissolved, then 20mL of silane coupling agent YDH-171 solution (prepared from 0.4g of silane coupling agent YDH-171 and 20mL of absolute ethyl alcohol) is dropwise added into the three-necked flask, the temperature is raised to 65 ℃ and stirred for reaction for 4 hours, the reaction product is cooled to the room temperature, washed by deionized water, dried by anhydrous magnesium sulfate, the solvent is removed by rotary evaporation, and the photostable coupling monomer M1 is obtained by vacuum drying, and the chemical structure and hydrogen spectrum (test conditions: 400Hz and CDCl 3) characterization results are shown in FIG. 2.
Experimental example 2:
the preparation of the photostable coupling monomer M2 comprises the following synthetic steps:
Step one, generating 1, 4-dimethyl sodium sulfide through acid-base neutralization reaction of 1, 4-dimethyl mercaptan and sodium hydroxide;
Step two, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 4-dimethyl sodium mercaptan and 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol by using the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiophenyl UV-326-based mercaptan;
Wherein, the inorganic protonic acid is one of hydrochloric acid, sulfuric acid and phosphoric acid, and hydrochloric acid is selected to be used in the experimental example;
Step three, an alkaline substance catalyzes a sulfhydryl functional group of thiophenyl UV-326 thiol and an alkenyl functional group of a silane coupling agent YDH-171 to generate a nucleophilic addition reaction to generate a light stable coupling monomer M2;
Wherein, the alkaline substance is one of sodium hydroxide, sodium carbonate and sodium ethoxide, and sodium ethoxide is selected and used in the experimental example;
the specific experimental steps of the light stable coupling monomer M2 are that only 1.9g of 1, 4-xylylene mercaptan is used for replacing 1.3g of 1, 3-propanediol in the light stable coupling monomer M1, and the rest parts are the same, so that the light stable coupling monomer M2 is prepared, and the chemical structure and hydrogen spectrum (test conditions are 400Hz and CDCl 3) characterization results are shown in figure 3.
Experimental example 3:
The preparation of the light stabilizer, as shown in FIG. 4, comprises the following steps of performing nucleophilic substitution reaction on 1 molar equivalent of 1, 3-sodium malonate and 2 molar equivalents of 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol by using a Williamson ether synthesis reaction mechanism, and obtaining the light stabilizer, wherein the specific experimental steps are that 0.4g of 1, 3-sodium malonate and 20mL of absolute ethyl alcohol are added into a three-necked flask, the solution is stirred at room temperature until the solution is completely dissolved under the action of mechanical stirring, 30mL of 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol solution (prepared from 1.6g of 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol and 30mL of absolute ethyl alcohol) is dropwise added into the three-necked flask, the solution is heated to 80 ℃ for reflux reaction for 6 hours, and the light stabilizer is obtained by washing with deionized water, extracting with diethyl ether, drying with anhydrous magnesium sulfate, removing by rotary evaporation, and vacuum drying, wherein the chemical structure and hydrogen spectrum (test conditions are shown in FIG. 5: 400Hz and CDCl 3).
Example 1:
(1) The preparation of modified titanium dioxide I comprises the steps of modifying titanium dioxide nano particles by using a light stable coupling monomer M1 to obtain modified titanium dioxide I, wherein the specific experimental steps are that 1g of titanium dioxide nano particles, 80mL of absolute ethyl alcohol and 20mL of deionized water are added into a beaker, ultrasonic treatment is carried out for 10min, 2g of light stable coupling monomer M1 is added into the beaker after the temperature is raised to 40 ℃, stirring reaction is carried out for 8h, centrifugation is carried out, absolute ethyl alcohol and deionized water are sequentially utilized for repeated centrifugal washing, and vacuum drying is carried out to obtain modified titanium dioxide I;
Preparing a graphene-titanium dioxide composite material I, namely modifying graphene nano sheets modified by a silane coupling agent TMPES by utilizing pi-pi stacking effect and modified titanium dioxide I to obtain the graphene-titanium dioxide composite material I, wherein the specific experimental steps are that 3g of modified titanium dioxide I, 5g of graphene nano sheets modified by the silane coupling agent TMPES and 100mL of absolute ethyl alcohol are added into a beaker, ultrasonic treatment is carried out for 30min, heating is carried out to 60 ℃ for stirring reaction for 5h, centrifugation is carried out, repeated centrifugal washing is carried out by sequentially utilizing absolute ethyl alcohol and deionized water, and vacuum drying is carried out to obtain the graphene-titanium dioxide composite material I;
(2) The preparation of modified titanium dioxide II comprises the steps of modifying titanium dioxide nano particles by using a photostable coupling monomer M2 to obtain modified titanium dioxide II, wherein the specific experimental steps are that the photostable coupling monomer M2 is used for replacing a photostable coupling monomer M1 in photostable modified titanium dioxide I, and the rest parts are the same, so that modified titanium dioxide II is prepared;
Preparing a graphene-titanium dioxide composite material II, namely modifying a graphene nano sheet modified by a silane coupling agent TMPES by utilizing pi-pi stacking effect through modified titanium dioxide II to obtain the graphene-titanium dioxide composite material II, wherein the specific experimental steps are that only modified titanium dioxide II is used for replacing modified titanium dioxide I in the graphene-titanium dioxide composite material I, and the rest parts are the same, so that the graphene-titanium dioxide composite material II is prepared;
(3) The preparation of modified titanium dioxide III comprises the steps of modifying titanium dioxide nano particles by using a photostable coupling monomer M1 and a light stabilizer together to obtain modified titanium dioxide III, wherein the specific experimental steps are that only 1g of the photostable coupling monomer M1 and 1g of the light stabilizer are used for replacing 2g of the photostable coupling monomer M1 in the photostable modified titanium dioxide I, and the rest parts are the same, so that modified titanium dioxide III is prepared;
Preparing a graphene-titanium dioxide composite material III, namely modifying a graphene nano sheet modified by a silane coupling agent TMPES by utilizing pi-pi stacking effect through modified titanium dioxide III to obtain the graphene-titanium dioxide composite material III, wherein the specific experimental steps are that only the modified titanium dioxide III is used for replacing modified titanium dioxide I in the graphene-titanium dioxide composite material I, and the rest parts are the same, so that the graphene-titanium dioxide composite material III is prepared;
(4) The preparation of the graphene-titanium dioxide blending material comprises the following steps of physically mixing titanium dioxide nano particles and graphene nano sheets to obtain the graphene-titanium dioxide blending material, wherein the specific experimental steps are that 1g of titanium dioxide nano particles, 3g of graphene nano sheets and 100mL of absolute ethyl alcohol are added into a beaker, ultrasonic treatment is carried out for 30min, and the graphene-titanium dioxide blending material is obtained through centrifugation and vacuum drying;
The preparation method of the graphene nano sheet modified by the silane coupling agent TMPES comprises the steps of adding 3g of graphene nano sheet, 80mL of absolute ethyl alcohol and 20mL of deionized water into a beaker, carrying out ultrasonic treatment for 10min, heating to 40 ℃, adding 2g of alkane coupling agent TMPES (trimethoxy (2-phenethyl) silane) into the beaker, stirring for reaction for 6h, centrifuging, repeatedly centrifuging and washing by sequentially utilizing absolute ethyl alcohol and deionized water, and carrying out vacuum drying to obtain the graphene nano sheet modified by the silane coupling agent TMPES.
Example 2:
Preparing a composite finish paint, comprising the following steps:
Preparing base paint, namely putting deionized water, organosilicon modified polyester resin emulsion, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, kaolin, astragal sand, titanium pigment, graphene-titanium dioxide composite material, propylene glycol, alcohol ester twelve, 2-amino-2-methyl-1-propanol, a polyacrylic acid ammonium salt dispersing agent, octyl phenol polyoxyethylene ether and silicone acrylic emulsion into a dispersing machine according to the formula of the base paint in the table 1, mixing the components in the dispersing machine, stirring the components for 60min at 1000r/min, adding iron oxide red, keeping the stirring for 30min continuously at 1000r/min, and preparing the base paint;
Preparing a protective glue solution, namely placing deionized water, magnesium aluminum silicate and inorganic bentonite into a dispersing machine for mixing according to the formula of the protective glue solution in table 2, and stirring for 30min at 200r/min to prepare the protective glue solution;
Preparing a continuous phase, namely placing deionized water, a graphene-titanium dioxide composite material, polyacrylate, polycarbodiimide, an organosilicon defoamer and acrylic emulsion into a dispersing machine for mixing according to the formula of the continuous phase in table 3, and stirring for 60min at 800r/min to prepare the continuous phase;
Mixing the base paint and the protective glue solution, stirring for 60min at 800r/min, adding a continuous phase, and keeping stirring for 60min at 800r/min to prepare the composite finish paint;
wherein the mass ratio of the base paint to the protective glue solution to the continuous phase is 6:1:3;
Table 1 formulation of base paint
Table 2 formulation of protective glue
| Raw material composition | Feed quality (%) |
| Deionized water | 93 |
| Magnesium aluminum silicate | 6 |
| Inorganic bentonite | 1 |
Table 3 formulation of continuous phase
| Raw material composition | Feed quality (%) |
| Deionized water | 31 |
| Graphene-titanium dioxide composite material | 4 |
| Polyacrylate esters | 1 |
| Polycarbodiimide | 2 |
| Organosilicon defoamer | 2 |
| Acrylic emulsion | 60 |
The preparation method comprises the steps of preparing a composite finish paint I, a composite finish paint II and a composite finish paint III respectively when the graphene-titanium dioxide composite material is a graphene-titanium dioxide composite material I, a graphene-titanium dioxide composite material II and a graphene-titanium dioxide composite material III respectively, preparing a composite finish paint a when the graphene-titanium dioxide composite material is replaced by a graphene-titanium dioxide blending material, and preparing a finish paint when the graphene-titanium dioxide composite material is not used, wherein the composite finish paint is taken as a comparison example.
Performance test:
The paint was sprayed using a PT871A type adjustable spray gun, and after curing at normal temperature, a stone-like paint coating was formed, and performance test was performed, and the results are shown in table 4 and fig. 6.
TABLE 4 results of Performance experiments on finishes
By comprehensively analyzing the experimental results, the following conclusion can be obtained:
(1) The improvement effect of the graphene and the nano titanium dioxide on the finish paint is far lower than that of a graphene-titanium dioxide composite material modified by the photo-stable coupling monomer under the condition that the photo-stable coupling monomer is not used for modification;
(2) The light stability coupling monomer M1 and the light stability coupling monomer M2 are used as modifier, and the prepared graphene-titanium dioxide composite material has almost no obvious difference in weather resistance;
(3) The graphene-titanium dioxide composite material modified by the light stability coupling monomer and the novel light stabilizer can further effectively improve the weather resistance.
Claims (10)
1. The thick paste type composite stone-like paint consists of composite base coat, stone-like paint main paint and finish paint, and is characterized in that the preparation method of the finish paint is as follows:
step one, synthesizing a photostable coupling monomer;
The light stable coupling monomer is light stable coupling monomer M1, and the chemical structural formula is as follows:
Modifying the titanium dioxide nano particles by using a photostable coupling monomer or modifying the titanium dioxide nano particles by using the photostable coupling monomer and a light stabilizer to prepare the photostable titanium dioxide nano particles; based on pi-pi stacking effect, the photo-stable titanium dioxide nano particles are subjected to composite treatment on the graphene nano sheet modified by trimethoxy (2-phenethyl) silane to prepare a graphene-titanium dioxide composite material, namely the weather-resistant modifier;
Preparing finish paint, wherein the finish paint is prepared by uniformly mixing 55-75wt% of base paint, 5-15wt% of protection glue solution and 10-40wt% of continuous phase, and the base paint contains weather-proof modifier with the dosage of 3-8wt%.
2. The thick paste type composite stone-like paint according to claim 1, wherein the light-stable coupling monomer is a light-stable coupling monomer M2, and has a chemical structural formula:
3. the thick paste type composite stone-like paint according to claim 1, wherein the light stabilizer has a chemical structural formula:
4. The thick paste type composite stone-like paint according to claim 1, wherein the preparation method of the light stable coupling monomer M1 is as follows:
step S4-1, generating 1, 3-sodium malonate through acid-base neutralization reaction of 1, 3-sodium malonate and sodium hydroxide;
S4-2, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 3-sodium malonate and 2- (5-chloro-2-benzotriazole) -6-tert-butyl-p-cresol with the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiopropyl UV-326-based mercaptan;
And S4-3, catalyzing a mercapto functional group of the thiopropyl UV-326-based mercaptan and an alkenyl functional group of the silane coupling agent YDH-171 to generate a nucleophilic addition reaction by an alkaline substance to generate the light-stable coupling monomer M1.
5. The thick paste type composite stone-like paint according to claim 2, wherein the preparation method of the light stable coupling monomer M2 is as follows:
S5-1, generating 1, 4-dimethyl sodium sulfide through acid-base neutralization reaction of 1, 4-dimethyl mercaptan and sodium hydroxide;
S5-2, utilizing a Williamson ether synthesis reaction mechanism, carrying out nucleophilic substitution reaction on 1, 4-dimethyl sodium mercaptide and 2- (5-chloro-2-benzotriazole) -6-tertiary butyl-p-cresol by using the same molar equivalent, and then acidizing by inorganic protonic acid to generate thiophenyl UV-326-based mercaptan;
and S5-3, catalyzing a mercapto functional group of thiophenyl UV-326-based mercaptan and an alkenyl functional group of a silane coupling agent YDH-171 to generate a nucleophilic addition reaction by an alkaline substance to generate the light-stable coupling monomer M2.
6. The thick paste type composite stone-like paint according to claim 4 or 5, wherein the inorganic protonic acid is one of hydrochloric acid, sulfuric acid and phosphoric acid;
The alkaline substance is one of sodium hydroxide, sodium carbonate and sodium ethoxide.
7. A thick paste type composite stone-like paint according to claim 3, wherein the light stabilizer is prepared by nucleophilic substitution reaction of 1 molar equivalent of 1, 3-sodium malonate and 2 molar equivalents of 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol by utilizing a Williamson ether synthesis reaction mechanism.
8. The thick paste type composite stone-like paint according to claim 1 is characterized in that the base paint comprises, by weight, 10-20wt% of deionized water, 10-20wt% of an organosilicon modified polyester resin emulsion, 2-5wt% of hydroxyethyl cellulose, 2-5wt% of hydroxyethyl methylcellulose, 5-15wt% of kaolin, 15-25wt% of quartz sand, 1-5wt% of titanium dioxide, 3-8wt% of graphene-titanium dioxide composite material, 0.1-1wt% of propylene glycol, 0.1-1wt% of alcohol ester twelve, 0.1-1wt% of 2-amino-2-methyl-1-propanol, 0.1-1wt% of a polyacrylic acid ammonium salt dispersing agent, 0.1-1wt% of octyl phenol polyoxyethylene ether, 10-30wt% of silicone-acrylic emulsion and 1-3wt% of iron red.
9. The thick paste type composite stone-like paint according to claim 1, wherein the formula of the protection glue solution comprises 90-95wt% of deionized water, 3-8wt% of magnesium aluminum silicate and 0.1-2wt% of inorganic bentonite.
10. The thick paste type composite stone-like paint according to claim 1, wherein the continuous phase comprises 20-40 wt% of deionized water, 1-5 wt% of graphene-titanium dioxide composite material, 0.5-2 wt% of polyacrylate, 1-5 wt% of polycarbodiimide, 1-5 wt% of organosilicon defoamer and 50-70 wt% of acrylic emulsion.
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| CN112048231A (en) * | 2020-09-18 | 2020-12-08 | 四川臻先科技股份有限公司 | Weather-resistant wear-resistant antifouling paint and preparation method thereof |
| CN114423742A (en) * | 2019-09-18 | 2022-04-29 | 三井化学株式会社 | Benzotriazole compound, light absorber, and resin composition |
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| CN114940732A (en) * | 2022-06-15 | 2022-08-26 | 扬州实嘉电缆材料有限公司 | Anti-ultraviolet titanium dioxide modified polyvinyl chloride plastic and preparation method thereof |
| CN116693790A (en) * | 2023-06-27 | 2023-09-05 | 益丰新材料股份有限公司 | Composition for optical material and optical material |
| CN118325203B (en) * | 2024-04-08 | 2024-12-10 | 南京奥瑞斯安全技术有限公司 | A wear-resistant sole material and preparation method thereof |
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| CN114423742A (en) * | 2019-09-18 | 2022-04-29 | 三井化学株式会社 | Benzotriazole compound, light absorber, and resin composition |
| CN112048231A (en) * | 2020-09-18 | 2020-12-08 | 四川臻先科技股份有限公司 | Weather-resistant wear-resistant antifouling paint and preparation method thereof |
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