CN110028631B - Organosilicon modified aqueous polyester dispersion, preparation method thereof and aqueous coating - Google Patents
Organosilicon modified aqueous polyester dispersion, preparation method thereof and aqueous coating Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6958—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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Abstract
The invention relates to an organosilicon modified aqueous polyester dispersion, a preparation method thereof and an aqueous coating, wherein the raw materials for preparing the organosilicon modified aqueous polyester dispersion comprise the following components in parts by weight: 10-18 parts of polyalcohol, 7.5-20 parts of organosilicon intermediate, 0.03-0.05 part of catalyst, 5-11 parts of dibasic acid, 1-3 parts of monomer with grafting active functional group, 7-13 parts of cosolvent, 3-10 parts of mixed monomer, 0.5-1.5 parts of initiator, 1-2 parts of organic amine and 40-60 parts of deionized water; the mixed monomer is an acrylic monomer. The end-capped functional group of the organosilicon modified aqueous polyester contains more hydroxyl and carboxyl by adopting 10-18 parts by weight of polyhydric alcohol and 5-15 parts by weight of dibasic acid, and the carboxyl and hydroxyl are crosslinked to form a film when the organosilicon modified aqueous polyester dispersion is cured to form a film at high temperature, so that the paint containing the organosilicon modified aqueous polyester dispersion does not need to be additionally added with a curing agent in the spraying process, and the obtained paint film has excellent adhesive force, water resistance and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of polyester resin materials, in particular to an organosilicon modified aqueous polyester dispersion, a preparation method thereof and an aqueous coating.
Background
Silicone resins and polyester resins are two extremely important types of resin materials, and these two types of resins have certain characteristics, but have certain drawbacks. The silicone resin has excellent heat resistance, weather resistance, electrical insulation and other properties, but has problems of poor mechanical strength, adhesion, solvent resistance and the like. The polyester resin has the characteristics of high fullness, high glossiness, good adhesive force, excellent chemical resistance and high coating hardness, but has the defects of poor high temperature resistance, poor workability and the like.
At present, strict environmental protection methods are formulated at home and abroad to limit the emission of Volatile Organic Compounds (VOC) to the atmosphere, and solvent-based coatings are gradually replaced by water-based coatings and powder coatings. However, almost all of the silicone-modified polyester resins in the market at present are solvent-type resins, and no silicone-modified aqueous polyester resin is found in the domestic market.
Disclosure of Invention
Based on the above, the invention provides an organosilicon modified aqueous polyester dispersion, which has proper viscosity and good storage stability, and an aqueous coating prepared from the resin can be diluted with water and has good heat resistance, water resistance and flexibility.
The raw materials for preparing the organosilicon modified aqueous polyester dispersion comprise the following components in parts by weight:
The mixed monomer is an acrylic monomer.
The organic silicon modified aqueous polyester dispersion is prepared by modifying the organic silicon intermediate by using the polyalcohol, then reacting the organic silicon intermediate with the dibasic acid containing double bond functional groups to prepare unsaturated polyester resin, and grafting to provide water-soluble and functional acrylic monomers, so that the branched chain of the unsaturated polyester resin is provided with a plurality of carboxyl groups, thus the unsaturated polyester resin has water solubility, and the structure has a certain protection effect on ester bonds, thereby enhancing the stability of the resin and the water resistance of a coating film, having good stability, and having no obvious problems of layering, precipitation and the like when stored for 6 months at normal temperature; in addition, 10-18 parts by weight of polyhydric alcohol and 5-15 parts by weight of dibasic acid are adopted, so that the end-capped functional group of the organosilicon modified water-based polyester contains more hydroxyl groups and carboxyl groups, and the carboxyl groups and the hydroxyl groups are crosslinked to form a film when the organosilicon modified water-based polyester dispersion is cured to form a film at a high temperature, so that the paint containing the organosilicon modified water-based polyester dispersion does not need to be additionally added with a curing agent in the spraying process, and the obtained paint film has excellent adhesive force, water resistance and high temperature resistance.
In one embodiment, the polyol is selected from one or more of neopentyl glycol, methylpropanediol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, ethylbutylpropanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, dipropylene glycol, trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.
In one embodiment, the silicone intermediate is one containing active SiOH or SiOR and has a weight average molecular weight of from 800 to 2000g/mol.
In one embodiment, the catalyst is a titanate-based catalyst.
In one embodiment, the dibasic acid is selected from one or more of terephthalic acid, isophthalic acid, adipic acid, azelaic acid, succinic acid, glutaric acid, 1, 4-cyclohexanedicarboxylic acid, phthalic anhydride, and hexahydrophthalic anhydride.
In one embodiment, the monomer having a grafted reactive functionality is selected from one or more of maleic anhydride, fumaric acid, itaconic acid, crotonic acid, and tetrahydrophthalic anhydride.
In one embodiment, the cosolvent is selected from one or more of isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether.
In one embodiment, the mixed monomer is selected from one or more of acrylic acid, methacrylic acid, styrene, methyl styrene, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and isobutyl methacrylate.
In one embodiment, the initiator is selected from one or more of t-butyl hydroperoxide, t-amyl hydroperoxide, di-t-butyl peroxide, azobisisobutyronitrile, t-butyl peroxybenzoate and benzoyl peroxide.
In one embodiment, the organic amine is selected from one or more of triethylamine, triethanolamine, diethanolamine, N-dimethylethanolamine, aqueous ammonia, and 2-amino-2 methyl-1-propanol.
The invention also provides a preparation method of the organic silicon modified aqueous polyester dispersion, which comprises the following steps:
S110: adding polyalcohol, organosilicon intermediate and catalyst into reaction equipment, and reacting at 115-200 ℃;
s210: adding dibasic acid and monomer with grafting functional group, heating slowly to 150-220 deg.c under nitrogen protection, reacting to acid value of 3-10mgKOH/g, cooling to 80-160 deg.c, adding cosolvent to form intermediate solution of polyester;
s310: the temperature is regulated to 100-190 ℃, and mixed monomers and partial initiator are added into the polyester intermediate solution dropwise under the stirring state for copolymerization reaction;
S410: adding the rest initiator, and stirring for 3-5 hours at the temperature of 100-190 ℃;
s510: adding organic amine for neutralization, and finally diluting with deionized water to obtain the organosilicon modified aqueous polyester dispersion.
The invention also provides an aqueous coating comprising the silicone modified aqueous polyester dispersion of any one of the above.
In one embodiment, the aqueous coating comprises the following components in parts by weight:
In one embodiment, the adjunct comprises a high temperature resistant pigment and a high temperature resistant filler; the high-temperature resistant pigment is one or more selected from titanium dioxide, carbon black, manganese black and cobalt blue; the high-temperature-resistant filler is selected from one or more of silicon dioxide, silicon carbide and mica powder.
In one embodiment, the auxiliary agent comprises an auxiliary agent commonly used in the paint field and has the functions of leveling, defoaming, pigment wetting, thickening and the like. The auxiliary is not particularly limited as long as it does not limit the object of the present invention.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides an organosilicon modified aqueous polyester dispersion, which is prepared from the following raw materials in parts by weight:
The mixed monomer is an acrylic monomer.
In one embodiment, the polyol is selected from one or more of neopentyl glycol, methylpropanediol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, ethylbutylpropanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, dipropylene glycol, trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.
In one embodiment, the organosilicon intermediate is an organosilicon intermediate containing active SiOH or SiOR, the organosilicon intermediate containing active SiOH or SiOR is firstly reacted with polyol to be modified, then is reacted with dibasic acid and dibasic acid containing double bond functional groups to prepare unsaturated polyester resin, and the organosilicon modification is finished preliminarily, so that the scratch resistance of the surface of the paint can be improved when the dispersion is applied to the paint. Preferably, the organosilicon intermediate is selected from organosilicon intermediates with low polymerization degree and weight average molecular weight of 800-2000g/mol, such as 3074 intermediate, 3037 intermediate, 6018 intermediate and the like sold by Dow Corning company.
In one embodiment, the catalyst is a titanate-based catalyst, such as tetrabutyl titanate, isobutyl titanate, and the like.
In one embodiment, the dibasic acid is selected from one or more of terephthalic acid, isophthalic acid, adipic acid, azelaic acid, succinic acid, glutaric acid, 1, 4-cyclohexanedicarboxylic acid, phthalic anhydride, and hexahydrophthalic anhydride.
In one embodiment, the monomer having a grafted reactive functionality is selected from one or more of maleic anhydride, fumaric acid, itaconic acid, crotonic acid, and tetrahydrophthalic anhydride.
In one embodiment, the cosolvent is selected from one or more of isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether.
In one embodiment, the mixed monomer is selected from one or more of acrylic acid, methacrylic acid, styrene, methyl styrene, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and isobutyl methacrylate.
In one embodiment, the initiator is selected from one or more of t-butyl hydroperoxide, t-amyl hydroperoxide, di-t-butyl peroxide, azobisisobutyronitrile, t-butyl peroxybenzoate and benzoyl peroxide.
In one embodiment, the organic amine is selected from one or more of triethylamine, triethanolamine, diethanolamine, dimethylethyleneglycol amine, N-dimethylethanolamine, aqueous ammonia, and 2-amino-2 methyl-1-propanol.
The organic silicon modified aqueous polyester dispersion is prepared by modifying the organic silicon intermediate by using the polyalcohol, then reacting the organic silicon intermediate with the dibasic acid containing double bond functional groups to prepare unsaturated polyester resin, and grafting to provide water-soluble and functional acrylic monomers, so that the branched chain of the unsaturated polyester resin is provided with a plurality of carboxyl groups, thus the unsaturated polyester resin has water solubility, and the structure has a certain protection effect on ester bonds, thereby enhancing the stability of the resin and the water resistance of a coating film, having good stability, and having no obvious problems of layering, precipitation and the like when stored for 6 months at normal temperature; in addition, 10-18 parts by weight of polyhydric alcohol and 5-15 parts by weight of dibasic acid are adopted, so that the end-capped functional group of the organosilicon modified water-based polyester contains more hydroxyl groups and carboxyl groups, and the carboxyl groups and the hydroxyl groups are crosslinked to form a film when the organosilicon modified water-based polyester dispersion is cured to form a film at a high temperature, so that the paint containing the organosilicon modified water-based polyester dispersion does not need to be additionally added with a curing agent in the spraying process, and the obtained paint film has excellent adhesive force, water resistance and high temperature resistance.
The invention also provides a preparation method of the organosilicon modified aqueous polyester dispersion, which comprises the following steps:
s110: adding the polyol, the organosilicon intermediate and the catalyst into a reaction device, and fully reacting the organosilicon intermediate with the polyol at the temperature of 115-200 ℃.
S210: adding dibasic acid and monomer with grafted functional group, heating slowly to 150-220 deg.c under nitrogen protection, reacting to acid value of 3-10mgKOH/g, cooling to 80-160 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 100-190 ℃, and dropwise adding mixed monomers and part of initiator into the polyester intermediate solution under the stirring state to carry out copolymerization reaction.
Preferably, the mixed monomer and a portion of the initiator form a mixed solution, and then the mixed solution is dropped into the polyester intermediate solution, and the initiator initiates the copolymerization reaction of the mixed monomer and the polyester intermediate solution.
Preferably, the initiator added in the step S310 accounts for 60-90% wt of the total amount of the initiator, and the mixed monomer and part of the initiator are completely dripped in 0.5-3 hours, so that the dripping speed is slower, the copolymerization reaction is fully facilitated, and the preset end group is obtained.
S410: adding the rest initiator, stirring at 100-190 deg.c for 3-5 hr to promote the complete reaction of the mixed monomer and the intermediate polyester solution.
S510: adding organic amine, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion, wherein the solid content of the organosilicon modified aqueous polyester dispersion is 30-50%. After the reaction of the polyester intermediate solution and the mixed monomer is completed, adding organic amine to neutralize and salify to obtain the water-dispersible organosilicon modified polyester resin. The organic amine is added in proper amount according to the acidity value of the solution after the reaction of the polyester intermediate solution and the mixed monomer, so as to neutralize completely.
According to the preparation method, according to the reaction characteristics of raw materials, the preset intermediate product is formed by reacting in a plurality of steps, the preset end group is obtained, and then the water-soluble organosilicon modified polyester dispersoid is prepared, so that the stability is good.
The invention also provides a water-based paint, which comprises the organosilicon modified water-based polyester dispersoid.
In one embodiment, the aqueous coating comprises the following components in parts by weight:
in one embodiment, the auxiliary material comprises a high temperature resistant pigment and a high temperature resistant filler, wherein the high temperature resistant pigment is mainly used for adjusting the color of the water-based paint, and the high temperature resistant filler is mainly used for adjusting the viscosity of the water-based paint.
Preferably, the high temperature resistant pigment is selected from one or more of titanium dioxide, carbon black, manganese black and cobalt blue; preferably, the high temperature resistant filler is selected from one or more of silica, silicon carbide and mica powder.
In one embodiment, the auxiliary agent comprises an auxiliary agent commonly used in the paint field and has the functions of leveling, defoaming, pigment wetting, thickening and the like. The auxiliary is not particularly limited as long as it does not limit the object of the present invention.
The following is an example.
Example 1
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 18 parts of polyol, 18 parts of organosilicon intermediate, 0.03 part of catalyst, 7.5 parts of dibasic acid, 1 part of monomer with grafting active functional group, 7.5 parts of cosolvent, 5.5 parts of mixed monomer, 0.5 part of initiator, 2 parts of organic amine and 40 parts of deionized water.
The polyol is neopentyl glycol and trimethylolethane, and the weight parts of the neopentyl glycol and the trimethylolethane are respectively as follows: 10 parts of neopentyl glycol and 8 parts of trimethylolethane.
The organosilicon intermediate is a corning 3074 intermediate.
The catalyst is tetrabutyl titanate.
The dibasic acid is isophthalic acid, adipic acid and phthalic anhydride, and the weight parts of the isophthalic acid, the adipic acid and the phthalic anhydride are respectively as follows: 3 parts of isophthalic acid, 4 parts of adipic acid and 0.5 part of phthalic anhydride.
The monomer having a graft active functional group is maleic anhydride.
The cosolvent is ethylene glycol monobutyl ether.
The mixed monomers are hydroxyethyl methacrylate and butyl acrylate, and the weight parts of the hydroxyethyl methacrylate and the butyl acrylate are respectively as follows: 2.5 parts of hydroxyethyl methacrylate, 2 parts of butyl acrylate, 1.5 parts of hydroxyethyl acrylate and 1.5 parts of acrylic acid.
The initiator is di-tert-butyl hydroperoxide.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
s110: polyol, silicone intermediate and catalyst are added to the reaction apparatus at a temperature of 140 ℃ until the silicone intermediate fully reacts with the polyol.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 180 deg.c under nitrogen protection, reacting to acid value of 10mgKOH/g, cooling to 100 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 130 ℃, dropwise adding the mixed solution of the mixed monomer and part of the initiator into the polyester intermediate solution under the stirring state, and carrying out copolymerization reaction.
In step S310, 0.3 parts by weight of initiator is added, and the mixed monomer and part of initiator are completely dripped within 1 hour, so that the dripping speed is slower, the copolymerization reaction is facilitated to be sufficient, and the preset end group is obtained.
S410: the remaining initiator was added and stirred at 130 ℃ for 3.5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding ammonia water of organic amine, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 50 parts of organosilicon modified aqueous polyester dispersion, 31.5 parts of auxiliary materials, 0.5 part of auxiliary agents and 18 parts of deionized water.
Wherein the auxiliary material is high temperature resistant pigment and high temperature resistant filler, the weight part content of the high temperature resistant pigment and the high temperature resistant filler is 16.5 parts of the high temperature resistant pigment, and the high temperature resistant pigment is titanium white; 15 parts of high-temperature-resistant filler, wherein the high-temperature-resistant filler is silicon dioxide.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 0.3 part; tego Twain 4000 is 0.2 parts.
Example 2
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 15 parts of polyol, 13 parts of organosilicon intermediate, 0.04 part of catalyst, 8 parts of dibasic acid, 2 parts of monomer with grafting active functional groups, 10 parts of cosolvent, 5 parts of mixed monomer, 1 part of initiator, 2 parts of organic amine and 49 parts of deionized water.
The polyol is neopentyl glycol and trimethylolpropane, and the weight content of the neopentyl glycol and the trimethylolpropane is 9 parts of neopentyl glycol and 6 parts of trimethylolpropane respectively.
The organosilicon intermediate is a dorcorning 3074 intermediate.
The catalyst is isobutyl titanate.
The dibasic acid is phthalic anhydride and azelaic acid, and the weight parts of the phthalic anhydride and the azelaic acid are respectively as follows: 3 parts of phthalic anhydride and 5 parts of azelaic acid.
The monomer having a graft active functional group is fumaric acid.
The cosolvent is diethylene glycol butyl ether.
The mixed monomers are methyl methacrylate, isobutyl methacrylate, hydroxyethyl acrylate and methacrylic acid, and the weight parts of the methyl methacrylate, isobutyl methacrylate, hydroxyethyl acrylate and methacrylic acid are respectively as follows: 0.5 part of methyl methacrylate, 2 parts of isobutyl methacrylate, 1 part of hydroxyethyl acrylate and 1.5 parts of methacrylic acid.
The initiator is tert-butyl peroxybenzoate.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
S110: polyol, silicone intermediate and catalyst are added to the reaction apparatus at 115 ℃ until the silicone intermediate fully reacts with the polyol.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 200 deg.c under nitrogen protection, reacting to acid value of 6mgKOH/g, cooling to 150 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 120 ℃, dropwise adding the mixed solution of the mixed monomer and part of the initiator into the polyester intermediate solution under the stirring state, and carrying out copolymerization reaction.
In step S310, 0.7 parts by weight of initiator is added, and the mixed monomer and part of initiator are completely dripped within 2 hours, so that the dripping speed is slower, the copolymerization reaction is facilitated to be sufficient, and the preset end group is obtained.
S410: the remaining initiator was added and stirred at 120℃for 5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding organic amine dimethyl diethanolamine, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 51 parts of organosilicon modified aqueous polyester dispersion, 25 parts of auxiliary materials, 0.5 part of auxiliary agent and 10 parts of deionized water.
The auxiliary material comprises high-temperature resistant pigment and high-temperature resistant filler, wherein the high-temperature resistant pigment and the high-temperature resistant filler respectively comprise the following components in parts by weight: 15 parts of high-temperature resistant pigment and 10 parts of high-temperature resistant filler; the high temperature resistant pigment is carbon black; the high-temperature-resistant filler is silicon dioxide and silicon carbide, and the weight parts of the silicon dioxide and the silicon carbide are respectively as follows: 6 parts of silicon dioxide and 4 parts of silicon carbide.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 0.3 part; tego Twain 4000 is 0.2 parts.
Example 3
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 15 parts of polyol, 14 parts of organosilicon intermediate, 0.03 part of catalyst, 6 parts of diacid, 1 part of monomer with grafting active functional group, 10 parts of cosolvent, 8 parts of mixed monomer, 0.5 part of initiator, 1 part of organic amine and 45.5 parts of deionized water.
The polyalcohol is pentaerythritol and 1, 4-cyclohexanedimethanol, and the weight parts of the methylpropanediol and the 1, 4-cyclohexanedimethanol are respectively 5 parts of pentaerythritol and 10 parts of 1, 4-cyclohexanedimethanol.
The organosilicon intermediate is a Dow Corning 6018 intermediate.
The catalyst is tetrabutyl titanate.
The dibasic acid is isophthalic acid and adipic acid, and the weight parts of isophthalic acid and adipic acid are respectively 3 parts of isophthalic acid and 3 parts of adipic acid.
The monomer with grafted active functional group is tetrahydrophthalic anhydride.
The cosolvent is diethylene glycol dimethyl ether.
The mixed monomers are acrylic acid, hydroxypropyl acrylate, methyl methacrylate and isobornyl methacrylate, the weight parts of acrylic acid, hydroxypropyl acrylate, methyl methacrylate and isobornyl methacrylate are respectively 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 3.5 parts of methyl methacrylate and 1 part of isobornyl methacrylate.
The initiator is di-tert-butyl peroxide and tert-amyl hydroperoxide, and the weight parts of the di-tert-butyl peroxide and the tert-amyl hydroperoxide are respectively as follows: 0.25 part of di-tert-butyl peroxide and 0.25 part of tert-amyl hydroperoxide.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
S110: polyol, silicone intermediate and catalyst are added to the reaction apparatus at a temperature of 150 ℃ until the silicone intermediate fully reacts with the polyol.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 220 deg.c under nitrogen protection, reacting to acid value of 4mgKOH/g, cooling to 120 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 150 ℃, and dropwise adding the mixed monomer and part of initiator into the polyester intermediate solution under the stirring state to carry out copolymerization reaction.
Mixing the monomer and part of the initiator to form a mixed solution, then dripping the mixed solution into the polyester intermediate solution, and initiating the copolymerization reaction of the mixed monomer and the polyester intermediate solution by the initiator.
In step S310, 0.33 parts by weight of initiator is added, and the mixed monomer and part of initiator are completely added within 1.5 hours, so that the adding speed is slow, the copolymerization reaction is facilitated to be sufficient, and the preset end group is obtained.
S410: the remaining initiator was added and stirred at 150 ℃ for 3.5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding organic amine dimethyl glycol amine, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 62 parts of organosilicon modified aqueous polyester dispersion, 24.8 parts of auxiliary materials, 1 part of auxiliary agent and 12.2 parts of deionized water.
The auxiliary material comprises high-temperature resistant pigment and high-temperature resistant filler, wherein the high-temperature resistant pigment comprises 1.3 parts by weight of titanium dioxide and 0.5 part by weight of cobalt blue; the high temperature resistant filler is 23 parts by weight of silicon dioxide.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 0.3 part; tego Twain 4000 is 0.7 parts.
Example 4
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 18 parts of polyol, 8 parts of organosilicon intermediate, 0.05 part of catalyst, 13 parts of diacid, 1.5 parts of monomer with grafting active functional groups, 8 parts of cosolvent, 8.5 parts of mixed monomer, 1.4 parts of initiator, 1.6 parts of organic amine and 60 parts of deionized water.
The polyol is trimethylolpropane.
The organosilicon intermediate is a Dow Corning 6018 intermediate.
The catalyst is titanate catalyst.
The dibasic acid is hexahydrophthalic anhydride.
The monomer having a grafting active functional group is itaconic acid.
The cosolvent is dipropylene glycol methyl ether.
The mixed monomers comprise acrylic acid, butyl acrylate, isobornyl methacrylate and hydroxyethyl acrylate, and the weight parts of the acrylic acid, the butyl acrylate, the isobornyl methacrylate and the hydroxyethyl acrylate are respectively as follows: 2 parts of acrylic acid, 2 parts of butyl acrylate, 2 parts of isobornyl methacrylate and 2.5 parts of hydroxyethyl acrylate.
The initiator is di-tert-butyl peroxide and azodiisobutyronitrile, and the weight parts of the di-tert-butyl peroxide and the azodiisobutyronitrile are respectively as follows: 1 part of di-tert-butyl peroxide and 0.4 part of azodiisobutyronitrile.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
S110: polyol, silicone intermediate and catalyst are added to the reaction apparatus at a temperature of 200 ℃ until the silicone intermediate fully reacts with the polyol.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 220 deg.c under nitrogen protection, reacting to acid value of 4mgKOH/g, cooling to 85 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 100 ℃, dropwise adding mixed solution of mixed monomers and partial initiator into the polyester intermediate solution under stirring, and carrying out copolymerization reaction.
1.05 Parts by weight of an initiator was added in step S310, and the mixed monomer and a part of the initiator were completely added dropwise within 3 hours.
S410: the remaining initiator was added and stirred at 100℃for 3.5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding organic amine diethanolamine, stirring until the temperature is lower than 100 ℃, adding deionized water, and uniformly stirring to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 65 parts of organosilicon modified aqueous polyester dispersion, 25 parts of auxiliary materials, 0.5 part of auxiliary agents and 9.5 parts of deionized water.
The auxiliary material comprises 3 parts by weight of high-temperature-resistant pigment and 22 parts by weight of high-temperature-resistant filler, wherein the high-temperature-resistant pigment comprises 1 part by weight of carbon black and 2 parts by weight of manganese black; the high-temperature resistant filler is mica powder.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 0.3 part; tego Twain 4000 is 0.2 parts.
Example 5
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 15 parts of polyol, 11 parts of organosilicon intermediate, 0.03 part of catalyst, 14.5 parts of dibasic acid, 2.8 parts of monomer with grafting active functional group, 10 parts of cosolvent, 5.5 parts of mixed monomer, 1 part of initiator, 1.5 parts of organic amine and 46 parts of deionized water.
The polyol is trimethylolethane.
The organosilicon intermediate is a Dow Corning 3037 intermediate.
The catalyst is isobutyl titanate.
The dibasic acid is terephthalic acid and succinic acid, and the weight parts of the terephthalic acid and the succinic acid are respectively as follows: 6 parts of terephthalic acid and 8.5 parts of succinic acid.
The monomer with grafted active functional group is butenoic acid.
The cosolvent is propylene glycol monobutyl ether and propylene glycol methyl ether, and the propylene glycol monobutyl ether and the propylene glycol methyl ether respectively comprise the following components in parts by weight: 8 parts of propylene glycol monobutyl ether and 2 parts of propylene glycol methyl ether.
The mixed monomers are styrene, hydroxypropyl methacrylate and acrylic acid, and the weight parts of the styrene, the hydroxypropyl methacrylate and the acrylic acid are respectively as follows: 2.0 parts of styrene, 3 parts of hydroxypropyl methacrylate and 0.5 part of acrylic acid.
The initiator is tertiary amyl hydroperoxide and benzoyl peroxide, and the contents of the tertiary amyl hydroperoxide and the benzoyl peroxide in parts by weight are respectively as follows: 0.5 part of tertiary amyl hydroperoxide and 0.5 part of benzoyl peroxide.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
S110: polyol, silicone intermediate and catalyst are added to the reaction apparatus at a temperature of 175 ℃ until the silicone intermediate fully reacts with the polyol.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 160 deg.c under nitrogen protection, reacting to acid value of 5mgKOH/g, cooling to 85 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 100 ℃, dropwise adding the mixed solution of the mixed monomer and part of the initiator into the polyester intermediate solution under the stirring state, and carrying out copolymerization reaction.
In step S310, 0.7 parts by weight of an initiator was added, and the mixed monomer and a part of the initiator were completely added dropwise within 2.5 hours.
S410: the remaining initiator was added and stirred at 100 ℃ for 5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding organic amine dimethyl glycol amine, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 60 parts of organosilicon modified aqueous polyester dispersion, 23 parts of auxiliary materials, 0.5 part of auxiliary agent and 16.5 parts of deionized water.
The auxiliary material comprises 5 parts by weight of high-temperature-resistant pigment and 18 parts by weight of high-temperature-resistant filler, wherein the high-temperature-resistant pigment is cobalt blue; the high-temperature resistant filler is silicon carbide.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 0.3 part; tego Twain 4000 is 0.2 parts.
Example 6
In this example, the raw materials for preparing the silicone-modified aqueous polyester dispersion comprise the following components in parts by weight: 13 parts of polyol, 20 parts of organosilicon intermediate, 0.03 part of catalyst, 10 parts of diacid, 1 part of monomer with grafting active functional group, 12 parts of cosolvent, 9.6 parts of mixed monomer, 1 part of initiator, 1 part of organic amine and 55 parts of deionized water.
The polyol is trimethylolpropane.
The organosilicon intermediate is a Dow Corning 3037 intermediate.
The catalyst is isobutyl titanate.
The dibasic acid is terephthalic acid.
The monomer having a graft active functional group is fumaric acid.
The cosolvent is isopropanol and isobutanol, and the weight parts of the isopropanol and the isobutanol are respectively as follows: 8 parts of isopropanol and 4 parts of isobutanol.
The mixed monomer is methacrylic acid.
The initiator is azobisisobutyronitrile.
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
s110: the polyol, the organosilicon intermediate and the catalyst are added into a reaction device to react at 145 ℃ until the organosilicon intermediate and the polyol are fully reacted.
S210: adding dibasic acid and monomer with grafting functional group, heating slowly to 195 deg.c under nitrogen protection, reacting to acid value of 3.5mgKOH/g, cooling to 105 deg.c, and adding cosolvent to form intermediate solution of polyester.
S310: and (3) regulating the temperature to 110 ℃, dropwise adding the mixed solution of the mixed monomer and part of the initiator into the polyester intermediate solution under the stirring state, and carrying out copolymerization reaction.
In step S310, 0.7 parts by weight of an initiator was added, and the mixed monomer and a part of the initiator were completely added dropwise within 3 hours.
S410: the remaining initiator was added and stirred at 110℃for 4.5 hours to promote complete reaction of the mixed monomer with the polyester intermediate solution.
S510: adding organic amine 2-amino-2-methyl-1-propanol, stirring until the temperature is lower than 100 ℃, adding deionized water, and stirring uniformly to obtain the organosilicon modified aqueous polyester dispersion.
The organosilicon modified aqueous polyester dispersion is taken to prepare an aqueous coating, and the aqueous coating of the embodiment comprises the following components in parts by weight: 70.5 parts of organosilicon modified aqueous polyester dispersion, 15.5 parts of auxiliary materials, 3 parts of auxiliary agents and 5 parts of deionized water.
The auxiliary material comprises 5.5 parts by weight of high-temperature-resistant pigment and 10 parts by weight of high-temperature-resistant filler, wherein the high-temperature-resistant pigment is manganese black; the high-temperature resistant filler is mica powder.
The auxiliary agents are Tego-260 and Tego Twain 4000, and Tego-260 is 2 parts; tego Twain 4000 is 1 part.
The aqueous paints obtained in examples 1 to 6 were subjected to film coating, and then the properties of the film coating were examined, and the examination results are shown in table 1.
TABLE 1
As is clear from Table 1, the silicone-modified aqueous polyester dispersions of examples 1 to 6, which have both the characteristics of silicone and polyester resins and the characteristics of acrylic resins, are used in aqueous paints, and the cured coating film thereof has excellent adhesion, heat resistance, water resistance, flexibility, and is not easily damaged when bent, and the coating film has a wide hardness coverage, can meet high hardness requirements, and can be selected to have a suitable hardness according to the requirements.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The organosilicon modified aqueous polyester dispersion is characterized in that the raw materials for preparing the organosilicon modified aqueous polyester dispersion comprise the following components in parts by weight:
The organosilicon intermediate contains active SiOH or SiOR and has a weight average molecular weight of 800-2000g/mol;
The monomer with grafted active functional groups is selected from one or more of maleic anhydride, fumaric acid, itaconic acid, butenoic acid and tetrahydrophthalic anhydride;
the mixed monomer is an acrylic monomer;
The preparation method of the organosilicon modified aqueous polyester dispersion comprises the following steps:
S110: adding polyalcohol, organosilicon intermediate and catalyst into reaction equipment, and reacting at 115-200 ℃;
s210: adding dibasic acid and monomer with grafting functional group, heating slowly to 150-220 deg.c under nitrogen protection, reacting to acid value of 3-10mgKOH/g, cooling to 80-160 deg.c, adding cosolvent to form intermediate solution of polyester;
s310: the temperature is regulated to 100-190 ℃, and mixed monomers and partial initiator are added into the polyester intermediate solution dropwise under the stirring state for copolymerization reaction;
S410: adding the rest initiator, and stirring for 3-5 hours at the temperature of 100-190 ℃;
s510: adding organic amine for neutralization, and finally diluting with deionized water to obtain the organosilicon modified aqueous polyester dispersion.
2. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the polyol is selected from one or more of neopentyl glycol, methylpropanediol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, ethylbutylpropanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, dipropylene glycol, trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.
3. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the catalyst is a titanate-based catalyst.
4. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the dibasic acid is one or more selected from terephthalic acid, isophthalic acid, adipic acid, azelaic acid, succinic acid, glutaric acid, 1, 4-cyclohexanedicarboxylic acid, phthalic anhydride and hexahydrophthalic anhydride.
5. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the cosolvent is selected from one or more of isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether, and dipropylene glycol methyl ether.
6. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the mixed monomer is one or more selected from the group consisting of acrylic acid, methacrylic acid, styrene, methylstyrene, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and isobutyl methacrylate.
7. The silicone-modified aqueous polyester dispersion according to claim 1, wherein the initiator is one or more selected from the group consisting of t-butyl hydroperoxide, t-amyl hydroperoxide, di-t-butyl peroxide, azobisisobutyronitrile, t-butyl peroxybenzoate and benzoyl peroxide.
8. An aqueous coating comprising the silicone-modified aqueous polyester dispersion according to any one of claims 1 to 7.
9. The water-based paint according to claim 8, wherein the water-based paint comprises the following components in parts by weight:
10. the water-based paint according to claim 9, wherein the auxiliary material comprises a high temperature resistant pigment and a high temperature resistant filler; the high-temperature resistant pigment is one or more selected from titanium dioxide, carbon black, manganese black and cobalt blue; the high-temperature-resistant filler is selected from one or more of silicon dioxide, silicon carbide and mica powder.
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