CN113527988A - Self-cleaning powder coating for household appliances and preparation method thereof - Google Patents
Self-cleaning powder coating for household appliances and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a self-cleaning powder coating for household appliances and a preparation method thereof, belonging to the technical field of powder coatings and comprising the following raw materials: modified resin, mixed powder, aluminum phosphate binder, curing agent, flatting agent and pigment; the fluorine-containing polyaryletherketone has the chemical stability, high heat resistance and mechanical strength of common polyaryletherketone, and modified SiO2Modified TiO 22The mixed powder prepared by mixing the carbon nano tube can increase the thermal stability and the chemical property of the coatingStability and self-cleaning function; the related silane coupling agent is prepared by a one-pot method, so that the operation is simple and easy to control; the corrosion resistance of the coating can be improved by adding the aluminum phosphate binder; after the powder coating is sprayed on the surfaces of household appliances or furniture, the powder coating has good adhesiveness, high uniformity, attractive and elegant appearance, long retention time, and can prevent stains from attaching and facilitate the cleaning of the household appliances and other articles, and orange peels are not easy to fall off.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a self-cleaning powder coating for home appliances and furniture and a preparation method thereof.
Background
The self-cleaning powder coating is an environment-friendly high-efficiency coating, is commonly used on the surface of metal or plastic devices, can play a certain antifouling role, and has good research prospect.
The existing self-cleaning powder coating generally takes the existing resin material as a substrate, and after the nano material is added, the coating has a hydrophobic antifouling effect, but the added nano material has poor matching degree with the substrate, and after the coating is used for a long time, the coating on the surface of a sprayed object is easy to peel off, so that the attractiveness and antifouling effect are influenced.
Disclosure of Invention
The invention aims to provide a self-cleaning powder coating for household appliances and a preparation method thereof, and aims to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme: the self-cleaning powder coating for the household appliances comprises the following raw materials in parts by mass: 25-30 parts of modified resin, 12.5-15 parts of mixed powder, 2-4 parts of aluminum phosphate binder, 0.65-0.75 part of curing agent, 0.55-0.7 part of flatting agent and 0.08-0.25 part of pigment;
wherein the modified resin is prepared by the following steps:
step S1: preparing a dissolving solution, slowly adding hexafluoropropylene oxide into the dissolving solution at the temperature of-40 ℃, reducing the temperature to-60 ℃ to-50 ℃ after the hexafluoropropylene oxide is added, adding alkali metal fluorotitanate serving as a catalyst, carrying out magnetic stirring reaction for 72-90 hours, then raising the temperature to normal temperature, and carrying out distillation separation on the reaction solution to obtain an intermediate product 1; the dosage ratio of the dissolving solution, the hexafluoropropylene oxide and the alkali metal fluotitanate is 300 mL: 48mL of: 2.5-4.5 g; the alkali metal fluorotitanate is any one of sodium fluorotitanate, lithium fluorotitanate and potassium fluorotitanate;
the preparation method of the dissolving solution comprises the steps of adding acetonitrile and dimethyl ether into sodium hypochlorite solution with the mass fraction of 18%, stirring and mixing to obtain aprotic dissolving solution; wherein the dosage ratio of the sodium hypochlorite solution to the acetonitrile to the dimethyl ether is 100 mL: 35mL of: 20 mL; the prepared intermediate product 1 is perfluoropolyether acyl fluoride with the relative molecular mass of more than 3000;
step S2: mixing the intermediate product 1 with a methanol solution with the mass fraction of 70%, and reacting under the action of a catalyst to generate an intermediate product 2; the dosage ratio of the intermediate product 1 to the methanol solution is 20 mL: 350 mL; the intermediate product 2 is perfluoropolyether methyl carboxylate, and the catalyst is solid acid catalyst resin produced by Kahaisi (Beijing) science and technology limited company, and the model is T-63 MP; dissolving the intermediate product 2 with THF, adding sodium borohydride as catalyst, refluxing for 7-8h to obtain intermediate product 3, wherein the end of the intermediate product 3 is provided with-CH2OH-hydroxyl perfluoropolyethers; the dosage ratio of the intermediate product 2, THF and sodium borohydride is 18 mL: 100mL of: 1.5-3.5 g;
step S3: adding the intermediate product 3, terephthalic acid, isophthalic acid, adipic acid, a catalyst and an initiator into a high-pressure reaction kettle, gradually heating to 210 ℃ under the protection of nitrogen for dehydration and esterification, then heating to 240 ℃ for continuous dehydration and esterification, and when the acid value of a reactant is less than 10, reducing pressure for continuous reaction and removing low-boiling point substances; when the temperature of the reactant is reduced to 190-210 ℃, adding trimellitic anhydride and phthalic anhydride, and reacting for 1-1.5h at 190 ℃ to prepare modified resin; wherein the initiator is benzoylated terphenyl; the catalyst is formed by mixing sodium hydroxide and hydrophilic potassium oxide according to the mass ratio of 1: 1;
the amount ratio of intermediate 3, terephthalic acid, isophthalic acid, adipic acid, catalyst, initiator, trimellitic anhydride, and phthalic anhydride was 12.6 mL: 1.5 g: 1.35 g: 0.75 g: 0.35-0.4 g: 0.06-0.08 g: 4-5 g: 4-5 g;
further, the mixed powder is prepared by the following steps:
step a: adding silane coupling agent into deionized water, hydrolyzing for 30min, adding anhydrous ethanol and TiO2Mixing the powders, and stirring at 80 deg.C for 35 min; adding TiO into the mixture2Separating, cleaning with anhydrous ethanol, cleaning with distilled water, air drying, drying in an electric heating constant temperature blast drying oven at 50 deg.C for 20-24 hr, and grinding into fine modified TiO2Powder, and reserving for later use; silane coupling agent, deionized water, absolute ethyl alcohol and TiO2The dosage ratio of the components is 0.3 g: 8mL of: 600 mL: 20g of the total weight of the mixture;
step b: adding silane coupling agent into deionized water, hydrolyzing for 30min, adding anhydrous ethanol and SiO2Mixing the powders, and stirring at 80 deg.C for 35 min; mixing SiO2Separating, cleaning with anhydrous ethanol, cleaning with distilled water, air drying, drying in an electric heating constant temperature blast drying oven at 50 deg.C for 20-24 hr, and grinding into fine modified SiO2Powder, and reserving for later use; silane coupling agent, deionized water, absolute ethyl alcohol and SiO2The dosage ratio of the components is 0.12 g: 4 g: 300 mL: 8g of the total weight of the mixture;
step c: dissolving 4, 4-difluorobenzophenone and hexafluorobisphenol A in N-methylpyrrolidone, carrying out polymerization reaction under the protection of argon by taking anhydrous cesium fluoride as a catalyst, and adding a certain amount of calcium hydride as a water removal agent; after the reaction is finished, carrying out post-treatment to obtain an intermediate product a; the post-treatment step is to pour the obtained pink viscous liquid into deionized water to separate out fibrous solid, dissolve the fibrous solid in dichloromethane after filtering and drying, then separate out the fibrous solid in methanol, filter and collect the precipitate and dry the precipitate in a vacuum oven;
the dosage ratio of 4, 4-difluorobenzophenone, hexafluorobisphenol A, N-methylpyrrolidone, anhydrous cesium fluoride and calcium hydride is 1.475 g: 2.236 g: 10.26 g: 5 g: 0.5-0.8 g; the intermediate product a is fluorine-containing polyaryletherketone;
step d: adding the intermediate product a into N-methyl pyrrolidone, magnetically stirring for 1.5-2.5h to form a uniform solution, and modifying the SiO2Modified TiO 22Adding the carbon nano tube into the solution, magnetically stirring to form a suspension, and removing the solvent under reduced pressure; intermediate product a, N-methyl pyrrolidone and modified SiO2Modified TiO 22And the dosage ratio of the carbon nano tube is 0.4 g: 14 g: 0.5 g: 0.8 g: 0.7 g; carbon nanotubes having a diameter of 8 to 15nm and a length of 50 μm and purchased from Aladdin reagent (Shanghai) Co., Ltd;
wherein, the silane coupling agent is prepared by the following steps:
adding 4-vinyl epoxy cyclohexane, methanol and 2-chloroethyl trichlorosilane into a high-pressure reaction kettle, and reacting for 1.5-2.5h at 85-100 ℃ under the condition that chloroplatinic acid is used as a catalyst; the dosage ratio of the 4-vinyl epoxy cyclohexane to the methanol to the 2-chloroethyl trichlorosilane is 1 mol: 3 mol: 1 mol;
the reaction process is as follows:
further, the aluminum phosphate binder is prepared by the steps of:
deionized water and phosphoric acid were added to the flask, and after heating to 80 ℃ with stirring, aluminum hydroxide was added in portions so that n (p): n (Al) is 3:1.3, the temperature is increased to 95 ℃ after the stirring is evenly carried out, and the reaction is continuously carried out for 120 minutes; the obtained product is white viscous solution; the dosage ratio of the deionized water, the phosphoric acid and the aluminum hydroxide is 28 mL: 40 g: 11.73 g;
further, the curing agent is a beta-hydroxyalkylamide;
further, the leveling agent is any one of a fluorine modified acrylic leveling agent and a phosphate modified acrylic leveling agent;
furthermore, the pigment is any one or a mixture of several of inorganic pigments with good heat resistance, such as fast scarlet, fast brilliant red, permanent red and mauve, which are mixed in proportion;
a preparation method of self-cleaning powder coating for home appliances comprises the following steps:
adding the modified resin, the mixed powder, the aluminum phosphate binder, the curing agent, the flatting agent and the pigment into a high-speed mixer, uniformly mixing, heating and melting, extruding the mixture by using a double-screw extruder, cooling and tabletting the mixture to prepare a ribbon with the thickness of 15-20cm, and crushing the ribbon into fine fragments by using a crusher; grinding the fragments into fine powder, and sieving.
The invention has the beneficial effects that: the self-cleaning powder coating is mainly prepared from resin modified by hydroxyl perfluoropolyether, has high toughness, and contains fluorine which can improve the resistance of the coatingAlkali properties; the modified mixed powder contains modified SiO2And modified TiO2The coating has a regularly raised microstructure after being sprayed, so that the hydrophobicity of the coating is increased, and the attachment of stains is further prevented; after the silane coupling agent is treated, the bonding strength between the silane coupling agent and the fluorine-containing polyaryletherketone is increased, the compatibility of a mixed material is facilitated, and the orange peel phenomenon of the coating after spraying is prevented; the fluorine-containing polyaryletherketone has the chemical stability, high heat resistance and mechanical strength of common polyaryletherketone, and modified SiO2Modified TiO 22The mixed powder prepared from the carbon nano tube can improve the thermal stability, the chemical stability and the self-cleaning function of the coating; the related silane coupling agent is prepared by a one-pot method, so that the operation is simple and easy to control; the corrosion resistance of the coating can be improved by adding the aluminum phosphate binder; after the powder coating is sprayed on the surfaces of household appliances or furniture, the powder coating has good adhesiveness, high uniformity, attractive and elegant appearance, long retention time, and can prevent stains from attaching and facilitate the cleaning of the household appliances and other articles, and orange peels are not easy to fall off.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a modified resin, comprising the steps of:
step S1: the preparation method of the dissolving solution comprises the steps of adding 70mL of acetonitrile and 40mL of dimethyl ether into 200mL of sodium hypochlorite solution with the mass fraction of 18%, and stirring and mixing to obtain the aprotic dissolving solution; slowly adding 48mL of hexafluoropropylene oxide into 300mL of solution at-40 ℃, reducing the temperature to-60 ℃ after the hexafluoropropylene oxide is completely added, adding 2.5 alkali metal fluorotitanate as a catalyst, performing magnetic stirring reaction for 72 hours, raising the temperature to normal temperature, and performing distillation separation on the reaction liquid to obtain an intermediate product 1; the alkali metal fluotitanate is sodium fluotitanate;
step S2: mixing 20mL of the intermediate product 1 with 350mL of a methanol solution with the mass fraction of 70%, and reacting under the action of T-63MP solid acid catalyst resin to generate an intermediate product 2; dissolving 18mL of intermediate product 2 with 100mL of THF, adding 1.5g of sodium borohydride serving as a catalyst, and carrying out reflux reaction for 7h to obtain an intermediate product 3;
step S3: adding 12.6mL of intermediate product 3, 1.5g of terephthalic acid, 1.35g of isophthalic acid, 0.75g of adipic acid, 0.35-0.4g of catalyst and 0.06g of initiator into a high-pressure reaction kettle, gradually heating to 210 ℃ under the protection of nitrogen for dehydration esterification, then heating to 240 ℃ for continuous dehydration esterification, and when the acid value of a reactant is less than 10, reducing pressure for continuous reaction and removing low-boiling-point substances; when the temperature of the reactant is reduced to 190 ℃, 4g of trimellitic anhydride and 4-5g of phthalic anhydride are added to react for 1h at 190 ℃ to prepare modified resin; wherein the initiator is benzoylated terphenyl; the catalyst is prepared by mixing sodium hydroxide and hydrophilic potassium oxide according to the mass ratio of 1: 1.
Example 2
Preparing a modified resin, comprising the steps of:
step S1: the preparation method of the dissolving solution comprises the steps of adding 70mL of acetonitrile and 40mL of dimethyl ether into 200mL of sodium hypochlorite solution with the mass fraction of 18%, and stirring and mixing to obtain the aprotic dissolving solution; slowly adding 48mL of hexafluoropropylene oxide into 300mL of solution at-40 ℃, reducing the temperature to-55 ℃ after the hexafluoropropylene oxide is completely added, adding 3.5g of alkali metal fluorotitanate as a catalyst, performing magnetic stirring reaction for 80 hours, raising the temperature to normal temperature, and performing distillation separation on the reaction liquid to obtain an intermediate product 1; the alkali metal fluotitanate is sodium fluotitanate;
step S2: mixing 20mL of the intermediate product 1 with 350mL of a methanol solution with the mass fraction of 70%, and reacting under the action of T-63MP solid acid catalyst resin to generate an intermediate product 2; dissolving 18mL of intermediate product 2 with 100mL of THF, adding 2.5g of sodium borohydride serving as a catalyst, and carrying out reflux reaction for 7.5h to obtain an intermediate product 3;
step S3: adding 12.6mL of intermediate product 3, 1.5g of terephthalic acid, 1.35g of isophthalic acid, 0.75g of adipic acid, 0.38g of catalyst and 0.07g of initiator into a high-pressure reaction kettle, gradually raising the temperature to 210 ℃ under the protection of nitrogen for dehydration esterification, then raising the temperature to 240 ℃ for continuous dehydration esterification, and when the acid value of a reactant is less than 10, reducing the pressure for continuous reaction and removing low-boiling-point substances; when the temperature of the reactant is reduced to 200 ℃, 4.5g of trimellitic anhydride and 4.5g of phthalic anhydride are added to react for 1.5h at 190 ℃ to prepare modified resin; wherein the initiator is benzoylated terphenyl; the catalyst is prepared by mixing sodium hydroxide and hydrophilic potassium oxide according to the mass ratio of 1: 1.
Example 3
Preparing a modified resin, comprising the steps of:
step S1: the preparation method of the dissolving solution comprises the steps of adding 70mL of acetonitrile and 40mL of dimethyl ether into 200mL of sodium hypochlorite solution with the mass fraction of 18%, and stirring and mixing to obtain the aprotic dissolving solution; slowly adding 48mL of hexafluoropropylene oxide into 300mL of solution at-40 ℃, reducing the temperature to-50 ℃ after the hexafluoropropylene oxide is completely added, adding 4.5g of alkali metal fluorotitanate as a catalyst, performing magnetic stirring reaction for 90 hours, raising the temperature to normal temperature, and performing distillation separation on the reaction liquid to obtain an intermediate product 1; the alkali metal fluotitanate is sodium fluotitanate;
step S2: mixing 20mL of the intermediate product 1 with 350mL of a methanol solution with the mass fraction of 70%, and reacting under the action of T-63MP solid acid catalyst resin to generate an intermediate product 2; dissolving 18mL of intermediate product 2 with 100mL of THF, adding 3.5g of sodium borohydride serving as a catalyst, and carrying out reflux reaction for 8h to obtain an intermediate product 3;
step S3: adding 12.6mL of intermediate product 3, 1.5g of terephthalic acid, 1.35g of isophthalic acid, 0.75g of adipic acid, 0.4g of catalyst and 0.08g of initiator into a high-pressure reaction kettle, gradually raising the temperature to 210 ℃ under the protection of nitrogen for dehydration esterification, then raising the temperature to 240 ℃ for continuous dehydration esterification, and when the acid value of a reactant is less than 10, reducing the pressure for continuous reaction and removing low-boiling-point substances; when the temperature of the reactant is reduced to 210 ℃, 5g of trimellitic anhydride and 5g of phthalic anhydride are added to react for 1.5h at 190 ℃ to prepare modified resin; wherein the initiator is benzoylated terphenyl; the catalyst is prepared by mixing sodium hydroxide and hydrophilic potassium oxide according to the mass ratio of 1: 1.
Example 4
The preparation of the silane coupling agent comprises the following steps:
adding 4-vinyl epoxy cyclohexane, methanol and 2-chloroethyl trichlorosilane into a high-pressure reaction kettle, and reacting for 1.5h at 85 ℃ under the condition that chloroplatinic acid is used as a catalyst; the dosage ratio of the 4-vinyl epoxy cyclohexane to the methanol to the 2-chloroethyl trichlorosilane is 1 mol: 3 mol: 1 mol.
Example 5
Adding 4-vinyl epoxy cyclohexane, methanol and 2-chloroethyl trichlorosilane into a high-pressure reaction kettle, and reacting for 2 hours at 90 ℃ under the condition that chloroplatinic acid is used as a catalyst; the dosage ratio of the 4-vinyl epoxy cyclohexane to the methanol to the 2-chloroethyl trichlorosilane is 1 mol: 3 mol: 1 mol.
Example 6
Adding 4-vinyl epoxy cyclohexane, methanol and 2-chloroethyl trichlorosilane into a high-pressure reaction kettle, and reacting for 2.5h at 100 ℃ under the condition that chloroplatinic acid is used as a catalyst; the dosage ratio of the 4-vinyl epoxy cyclohexane to the methanol to the 2-chloroethyl trichlorosilane is 1 mol: 3 mol: 1 mol.
Example 7
Preparing mixed powder, comprising the following steps:
step a: 0.3g of the silane coupling agent obtained in example 5 was added to 8mL of deionized water, and after hydrolysis for 30min, 600mL of absolute ethanol and 20g of TiO were added2Mixing the powders, and stirring at 80 deg.C for 35 min; adding TiO into the mixture2Separating, washing with anhydrous ethanol, washing with distilled water, air drying, drying in an electrothermal constant temperature blast drying oven at 50 deg.C for 20 hr, and grinding into fine modified TiO2Powder, and reserving for later use;
step b: adding 0.12g of silane coupling agent into 4g of deionized water, hydrolyzing for 30min, and adding 300mL of absolute ethyl alcohol and 8g of SiO2Mixing the powders, and stirring at 80 deg.C for 35 min; mixing SiO2Separating, cleaning with anhydrous ethanol, cleaning with distilled water, air drying, drying in an electric heating constant temperature blast drying oven at 50 deg.C for 20 hr, and grinding into fine modified SiO2Powder, and reserving for later use;
step c: 1.475g of 4, 4-difluorobenzophenone and 2.236g of hexafluorobisphenol A are dissolved in 10.26g of N-methylpyrrolidone, 5g of anhydrous cesium fluoride is used as a catalyst, a polymerization reaction is carried out under the protection of argon, and 0.5g of calcium hydride is added as a water removal agent; after the reaction is finished, pouring the obtained pink viscous liquid into deionized water to separate out fibrous solid, dissolving the fibrous solid in dichloromethane after filtering and drying, then separating out the fibrous solid in methanol, filtering and collecting the precipitate, and drying the precipitate in a vacuum oven to obtain an intermediate product a;
step d: adding 0.4g of the intermediate product a into 14g of N-methylpyrrolidone, and magnetically stirring for 1.5h to form a uniform solution; 0.5g of modified SiO20.8g of modified TiO2And 0.7 carbon nanotube, magnetically stirring to form suspension, and decompression to eliminate solvent.
Example 8
Step a: 0.3g of the silane coupling agent obtained in example 5 was added to 8mL of deionized water, and after hydrolysis for 30min, 600mL of absolute ethanol and 20g of TiO were added2Mixing the powders, and stirring at 80 deg.C for 35 min; adding TiO into the mixture2Separating, washing with anhydrous ethanol, washing with distilled water, air drying, drying in an electrothermal constant temperature blast drying oven at 50 deg.C for 22 hr, and grinding into fine modified TiO2Powder, and reserving for later use;
step b: adding 0.12g of silane coupling agent into 4g of deionized water, hydrolyzing for 30min, and adding 300mL of absolute ethyl alcohol and 8g of SiO2Mixing the powders, and stirring at 80 deg.C for 35 min; mixing SiO2Separating, cleaning with anhydrous ethanol, cleaning with distilled water, air drying, drying in an electric heating constant temperature blast drying oven at 50 deg.C for 22 hr, and grinding into fine modified SiO2Powder, and reserving for later use;
step c: 1.475g of 4, 4-difluorobenzophenone and 2.236g of hexafluorobisphenol A are dissolved in 10.26g of N-methylpyrrolidone, 5g of anhydrous cesium fluoride is used as a catalyst, a polymerization reaction is carried out under the protection of argon, and 0.6g of calcium hydride is added as a water removal agent; after the reaction is finished, pouring the obtained pink viscous liquid into deionized water to separate out fibrous solid, dissolving the fibrous solid in dichloromethane after filtering and drying, then separating out the fibrous solid in methanol, filtering and collecting the precipitate, and drying the precipitate in a vacuum oven to obtain an intermediate product a;
step d: adding 0.4g of the intermediate product a into 14g of N-methyl pyrrolidone, and magnetically stirring for 2 hours to form a uniform solution; 0.5g of modified SiO20.8g of modified TiO2And 0.7 carbon nanotube, magnetically stirring to form suspension, and decompression to eliminate solvent.
Example 9
Step a: 0.3g of the silane coupling agent obtained in example 5 was added to 8mL of deionized water, and after hydrolysis for 30min, 600mL of absolute ethanol and 20g of TiO were added2Mixing the powders, and stirring at 80 deg.C for 35 min; adding TiO into the mixture2Separating, washing with anhydrous ethanol, washing with distilled water, air drying, drying in an electrothermal constant temperature blast drying oven at 50 deg.C for 24 hr, and grinding into fine modified TiO2Powder, and reserving for later use;
step b: adding 0.12g of silane coupling agent into 4g of deionized water, hydrolyzing for 30min, and adding 300mL of absolute ethyl alcohol and 8g of SiO2Mixing the powders, and stirring at 80 deg.C for 35 min; mixing SiO2Separating, cleaning with anhydrous ethanol, cleaning with distilled water, air drying, drying in an electric heating constant temperature blast drying oven at 50 deg.C for 24 hr, and grinding into fine modified SiO2Powder, and reserving for later use;
step c: 1.475g of 4, 4-difluorobenzophenone and 2.236g of hexafluorobisphenol A are dissolved in 10.26g of N-methylpyrrolidone, 5g of anhydrous cesium fluoride is used as a catalyst, a polymerization reaction is carried out under the protection of argon, and 0.8g of calcium hydride is added as a water removal agent; after the reaction is finished, pouring the obtained pink viscous liquid into deionized water to separate out fibrous solid, dissolving the fibrous solid in dichloromethane after filtering and drying, then separating out the fibrous solid in methanol, filtering and collecting the precipitate, and drying the precipitate in a vacuum oven to obtain an intermediate product a;
step d: adding 0.4g of the intermediate product a into 14g of N-methylpyrrolidone, and magnetically stirring for 2.5 hours to form a uniform solution; 0.5g of modified SiO20.8g of modified TiO2And 0.7 carbon nanotube, magnetically stirring to form suspension, and decompression to eliminate solvent.
Example 10
Preparing an aluminum phosphate binder comprising the steps of:
adding 28mL of deionized water and 40g of phosphoric acid into a flask, stirring and heating to 80 ℃, continuously adding 11.73g of aluminum hydroxide in batches, uniformly stirring, raising the temperature to 95 ℃, and continuously reacting for 120 minutes; the product obtained was a white viscous solution,
example 11
The preparation method of the self-cleaning powder coating for the household appliances comprises the following steps:
adding 30g of the modified resin prepared in the embodiment 2, 15g of the mixed powder prepared in the embodiment 8, 2.5g of the aluminum phosphate binder prepared in the embodiment 10, 0.65g of beta-hydroxyalkylamide, 0.55g of fluorine modified acrylic acid leveling agent and 0.1g of permanent red into a high-speed mixer, uniformly mixing, heating and melting, extruding the mixture by using a double-screw extruder, cooling and tabletting the mixture to prepare a ribbon with the thickness of 15cm, and crushing the ribbon into fine fragments by using a crusher; grinding the fragments into fine powder, and sieving.
Comparative example 1: in comparison with example 2, a powder coating was prepared by the procedure of example 11, except that no intermediate 3 was added.
Comparative example 2: in comparison with example 8, TiO2And SiO2A mixed powder was directly prepared without being treated with a silane coupling agent, and a powder coating was prepared by the procedure of example 11.
Comparative example 3: compared with example 11, the powder coating is prepared without adding aluminum phosphate binder and the rest steps.
The performance test was carried out for example 11 and comparative examples 1 to 3, different kinds of powder coatings were sprayed on different aluminum plates with a 0.3 mm-diameter spray gun at a distance of 15cm from each other, and finally the coating was dried at 80 ℃ for 2 hours, the different aluminum plates were respectively soaked with muddy water, and after taking out, whether or not sludge was adhered was observed, the different aluminum plates were placed in an outdoor environment for 30 days, and whether or not orange peel was peeled off was observed (filling yes/no results), and the results are shown in table 1:
TABLE 1
| Item | Example 11 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Whether or not the sludge is adhered to | Whether or not | Is that | Is that | Whether or not |
| Whether or not to peel off orange peel | Whether or not | Whether or not | Is that | Is that |
As can be seen from Table 1, the silane coupling agent and the aluminum phosphate binder in the powder coating prepared by the method have good orange peel resistance effect on the coating, and the modified SiO2The materials increase the self-cleaning ability of the powder coating.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The self-cleaning powder coating for the household appliances is characterized by comprising the following raw materials in parts by mass: 25-30 parts of modified resin, 12.5-15 parts of mixed powder, 2-4 parts of aluminum phosphate binder, 0.65-0.75 part of curing agent, 0.55-0.7 part of flatting agent and 0.08-0.25 part of pigment; wherein the mixed powder is prepared by the following steps:
dissolving 4, 4-difluorobenzophenone and hexafluorobisphenol A in N-methylpyrrolidone, adding a catalyst for polymerization reaction, and taking calcium hydride as a water removal agent; after the reaction is finished, carrying out post-treatment to obtain an intermediate product a; adding the intermediate product a into N-methyl pyrrolidone, magnetically stirring for 1.5-2.5h to form a uniform solution, and modifying the SiO2Modified TiO 22And carbon nanotubes were added to the solution, magnetically stirred and the solvent removed under reduced pressure.
2. The self-cleaning powder coating for household appliances according to claim 1, wherein the modified TiO is2Is prepared by the following steps:
adding silane coupling agent into deionized water, hydrolyzing for 30min, adding anhydrous ethanol and TiO2Powder is evenly mixed; adding TiO into the mixture2Separating, cleaning with anhydrous ethanol, and cleaning with distilled waterWashed, dried and ground into fine modified TiO2And (3) powder.
3. The self-cleaning powder coating for household appliances according to claim 2, characterized in that the silane coupling agent is prepared by the following steps:
adding 4-vinyl epoxy cyclohexane, methanol and 2-chloroethyl trichlorosilane into a high-pressure reaction kettle, and reacting for 1.5-2.5h at 85-100 ℃ under the condition of taking chloroplatinic acid as a catalyst.
4. The self-cleaning powder coating for household appliances according to claim 1, wherein the aluminum phosphate binder is prepared by the following steps:
deionized water and phosphoric acid were added to the flask, and after heating to 80 ℃ with stirring, aluminum hydroxide was added in portions so that n (p): n (al) 3:1.3, stirring well, raising the temperature and continuing the reaction for 120 minutes.
5. The self-cleaning powder coating for household appliances according to claim 1, characterized in that the modified resin is prepared by the following steps:
step S1: preparing a dissolving solution, slowly adding hexafluoropropylene oxide into the dissolving solution at the temperature of-40 ℃, reducing the temperature to-60 ℃ to-50 ℃, adding alkali metal fluorotitanate, carrying out magnetic stirring reaction for 72-90h, then heating to normal temperature, and carrying out distillation separation to obtain an intermediate product 1;
step S2: mixing the intermediate product 1 with a methanol solution with the mass fraction of 70%, and reacting under the action of a catalyst to generate an intermediate product 2; dissolving the intermediate product 2 with THF, adding sodium borohydride, and carrying out reflux reaction for 7-8h to obtain an intermediate product 3;
step S3: adding the intermediate product 3, terephthalic acid, isophthalic acid, adipic acid, a catalyst and an initiator, heating to 210 ℃ for dehydration and esterification, heating to 240 ℃ for continuous dehydration and esterification, and reducing pressure for continuous reaction and removing low-boiling-point substances; reducing the temperature, adding trimellitic anhydride and phthalic anhydride, and reacting for 1-1.5 h.
6. The self-cleaning powder coating for household appliances according to claim 5, wherein the dissolving solution is prepared by adding acetonitrile and dimethyl ether into a sodium hypochlorite solution with a mass fraction of 18%, and stirring and mixing.
7. The self-cleaning powder coating for household appliances according to claim 1, wherein the curing agent is β -hydroxyalkylamide.
8. The self-cleaning powder coating for household appliances according to claim 1, wherein the leveling agent is any one of a fluorine modified acrylic leveling agent and a phosphate modified acrylic leveling agent.
9. The self-cleaning powder coating for household appliances according to claim 1, wherein the pigment is any one or a mixture of several of inorganic pigments with good heat resistance, namely fast scarlet, fast brilliant red, permanent red and mauve.
10. The preparation method of the self-cleaning powder coating for household appliances according to claim 1, characterized by comprising the following steps:
uniformly mixing the modified resin, the mixed powder, the aluminum phosphate binder, the curing agent, the flatting agent and the pigment, performing melt extrusion, cooling and tabletting to prepare a strip with the thickness of 15-20cm, and crushing the strip into fine fragments; grinding the fragments into fine powder, and sieving.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850388A (en) * | 2011-06-29 | 2013-01-02 | 中国蓝星（集团）股份有限公司 | A preparation method of silane coupling agent |
| US20130059942A1 (en) * | 2010-05-21 | 2013-03-07 | Nippon Soda Co., Ltd. | Curable powder coating composition, and cured product of same |
| CN104403525A (en) * | 2014-12-26 | 2015-03-11 | 任成生 | Polyester resin powder coating |
| CN106085070A (en) * | 2016-07-11 | 2016-11-09 | 复旦大学 | A kind of low-surface-energy micro nano-coatings material and preparation method thereof |
| CN106397753A (en) * | 2016-08-31 | 2017-02-15 | 黄山市向荣新材料有限公司 | Polyester resin for high-temperature-resistant powder coating and preparation method thereof |
-
2021
- 2021-08-12 CN CN202110926945.6A patent/CN113527988B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130059942A1 (en) * | 2010-05-21 | 2013-03-07 | Nippon Soda Co., Ltd. | Curable powder coating composition, and cured product of same |
| CN102850388A (en) * | 2011-06-29 | 2013-01-02 | 中国蓝星（集团）股份有限公司 | A preparation method of silane coupling agent |
| CN104403525A (en) * | 2014-12-26 | 2015-03-11 | 任成生 | Polyester resin powder coating |
| CN106085070A (en) * | 2016-07-11 | 2016-11-09 | 复旦大学 | A kind of low-surface-energy micro nano-coatings material and preparation method thereof |
| CN106397753A (en) * | 2016-08-31 | 2017-02-15 | 黄山市向荣新材料有限公司 | Polyester resin for high-temperature-resistant powder coating and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| 何丽红等: "硅烷偶联剂表面改性二氧化钛粒子超疏水性能", 《精细化工》 * |
| 冯瑞华等: "《中国科学院科学传播系列丛书 新材料》", 30 June 2015, 北京：科学普及出版社 * |
| 张亨: "三聚磷酸二氢铝的生产及应用", 《现代盐化工》 * |
| 张辉等: "功能性粉末涂料的研究现状与发展", 《化学工业与工程》 * |
| 张鹏等: "新型可溶性含氟聚芳醚酮的合成、表征及性能", 《高等学校化学学报》 * |
| 李站铁等: "全氟聚醚改性聚酯粉末涂料的研究", 《上海涂料》 * |
| 王维等: "疏水性可调型纳米二氧化硅的制备", 《中国粉体技术》 * |
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