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CN112608626A - Waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint and preparation method thereof - Google Patents

Waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint and preparation method thereof Download PDF

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Publication number
CN112608626A
CN112608626A CN202011392023.3A CN202011392023A CN112608626A CN 112608626 A CN112608626 A CN 112608626A CN 202011392023 A CN202011392023 A CN 202011392023A CN 112608626 A CN112608626 A CN 112608626A
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polyacrylic acid
parts
waterborne polyurethane
agent
real stone
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Inventor
胡先海
高先银
张静
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Anhui Kechuangmei Coating Technology Co ltd
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Anhui Kechuangmei Coating Technology Co ltd
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Priority to CN202011392023.3A priority Critical patent/CN112608626A/en
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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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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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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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65—Additives macromolecular

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Abstract

The invention discloses a waterborne polyurethane-polyacrylic acid group self-repairing real stone paint and a preparation method thereof, wherein a polyurethane prepolymer containing disulfide bonds and acylhydrazone bonds is synthesized firstly, hydroxyethyl acrylate is utilized to seal end to prepare a polyurethane prepolymer with double bonds, then the polyurethane prepolymer and acrylic acid are subjected to free radical copolymerization to obtain carboxyl-containing polyurethane, finally, the polyurethane prepolymer is emulsified and salified to prepare a waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, and then an auxiliary agent, a dispersing agent, a film forming aid, an antifreezing agent, a defoaming agent, a bactericide, a water repellent, a thickening agent, deionized water and colored sand are sequentially added and uniformly mixed to obtain the waterborne polyurethane-polyacrylic acid group self-repairing real stone paint; the stone-like paint prepared by the invention realizes multiple times of repair of damage by utilizing reversible chemical bonds of disulfide bonds and acylhydrazone bonds and the hydrogen bonding action of polyurethane-polyacrylic acid, and has strong self-repairing force, self-healing cracks and damaged coatings; the product has excellent wear resistance, low temperature resistance, mildew resistance, antibacterial property, impact resistance and other properties.

Description

Waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint and preparation method thereof
Technical Field
The invention relates to the technical field of stone-like paint coatings, in particular to a waterborne polyurethane-polyacrylic acid-based self-repairing stone-like paint and a preparation method thereof.
Background
The stone-like paint is a polymer emulsion sand wall-shaped thick paste type paint system which is prepared by taking polymer emulsion as a base material, adding a small amount of film-forming auxiliary agent as a binding material, taking natural color sand with different colors and mesh grading as aggregate, quantitatively adding a series of auxiliary agents and deionized water, and physically and uniformly blending.
The real stone paint is usually damaged by machinery and slightly moves on a wall body in the using process, and a paint film cracks, so that the decorative effect, the functionality and the service life of the exterior wall paint are influenced.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of the waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint, which comprises the following steps:
s1, stirring and dispersing the deionized water for 8-10 min, adjusting the pH to 8.0-10.0, and stirring and dispersing again for 5-10 min;
s2, adding the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond into the solution obtained in the step S1, and stirring and dispersing for 5-10 min;
s3, sequentially adding the aqueous multifunctional additive, the dispersant, the film-forming additive, the antifreeze, the aqueous defoamer, the bactericide, the water repellent and the deionized water into the solution obtained in the step S2, stirring and dispersing for 5-10 min;
s4, adding a thickening agent into the solution obtained in the step S3, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 5-10 min;
and S5, adding colored sand into the solution obtained in the step S4, mixing, and uniformly stirring to obtain the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint.
Preferably, the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following raw materials in parts by weight: 10-20 parts of the waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, 0.3-0.5 part of the waterborne multifunctional auxiliary agent, 0.05-0.2 part of the dispersing agent, 0.6-1.5 parts of the film forming auxiliary agent, 0.1-0.2 part of the antifreezing agent, 0.1-0.2 part of the waterborne defoaming agent, 0.2-0.4 part of the bactericide, 0.2-0.8 part of the water repellent, 0.1-0.5 part of the thickening agent, 10-15 parts of deionized water and 60-80 parts of the colored sand.
Preferably, the preparation method of the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond comprises the following steps of:
a1, heating 60-120 parts of polymer polyol to 100-130 ℃, and dehydrating in vacuum for 1-2 h;
a2, carrying out nitrogen protection on the solution obtained in the step A1, cooling to 60-90 ℃, adding 30-60 parts of polyisocyanate and 0.01-0.03 part of catalyst, reacting for 1-3 h, and adding 30-60 parts of organic solvent to adjust viscosity;
a3, adding 5-10 parts of hydrophilic chain extender into the solution obtained in the step A2, and reacting for 1-3 h at 50-90 ℃;
a4, adding 5-10 parts of disulfide bond compounds and 5-10 parts of acylhydrazone bond compounds into the solution obtained in the step A3, and reacting at 40-90 ℃ for 1-3 h;
a5, adding 0.5-1.0 part of end-capping reagent into the solution obtained in the step A4, and keeping the temperature at 80-90 ℃;
a6, adding 8-15 parts of acrylic acid and 40-60 parts of acrylate monomers into the solution obtained in the step A5, adding initiators in batches, wherein the interval is 10 min-20 min each time, and after 0.01-0.02 part of the initiators is added, keeping the temperature at 70-80 ℃ and continuously reacting for 5 h-6 h;
a7, cooling the solution obtained in the step A6 to 30-50 ℃, adding 10-15 parts of a salt forming agent, and reacting for 10-30 min;
a8, cooling the solution obtained in the step A7 to 30-50 ℃, adding 200-400 parts of deionized water, and dispersing at high speed for 10-30 min;
a9, desolventizing the solution obtained in the step A8 under vacuum degree to obtain the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond.
Preferably, the aqueous multifunctional auxiliary agent is AMP-95 multifunctional auxiliary agent; the dispersant is a sodium polycarboxylate dispersant; the film-forming auxiliary agent is one or a mixture of more than two of alcohols, alcohol esters, alcohol ethers and alcohol ether esters; the antifreezing agent is one or a mixture of more than two of methanol, ethanol, ethylene glycol, propylene glycol and glycerol; the water-based defoaming agent is one or a mixture of more than two of organic matters, silicon dioxide and organic silicon; the bactericide is one or more of DODOWEICIL (TM) 75, DOWEICIL (TM) 96, DOWEICILTMQK-20, BIOBANTMBP-30 and dialdehyde 50%; the water repellent is one or a mixture of more than two of silane group powder water repellent and organic silicon water repellent powder.
Preferably, the polymer polyol is one or two of polyether polyol and polyester polyol; the polyisocyanate is one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate; the catalyst is one or two of organic tin and tertiary amine; the organic solvent is one or more of acetone, butanone, methyl ethyl ketone, dioxane, N-dimethyl amide, N-methyl pyrrolidone and ethyl acetate.
Preferably, the hydrophilic chain extender is one or more of sodium N- (2-aminoethyl) -2-aminoethane sulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethane sulfonate, sodium ethylene diaminoethane sulfonate, sodium 1, 4-butanediol-2-sulfonate and derivatives thereof.
Preferably, the disulfide bond compound is one or two of 4, 4 '-diaminodiphenyl sulfide, 3' -dihydroxydiphenyl disulfide, 4 '-dihydroxydiphenyl sulfide, 2-aminodiphenyl sulfide, 2' -dithiodiethanol and dihydroxyethyl diethyl thiuram disulfide; the acylhydrazone bond compound is one or two of quinoxalin hydrazone and diflufenzopyr.
Preferably, the salt forming agent is one or more of triethylamine, ammonia water and sodium hydroxide; the end capping agent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate.
Preferably, the acrylate monomer is one or more of acrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate.
Preferably, the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint is prepared by the preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint.
Compared with the prior art, the invention has the beneficial effects that: the stone-like paint prepared by the invention realizes multiple times of repair of damage by utilizing reversible chemical bonds of disulfide bonds and acylhydrazone bonds and the hydrogen bonding action of polyurethane-polyacrylic acid, and has strong self-repairing force, self-healing cracks and damaged coatings; the product has excellent wear resistance, low temperature resistance, mildew resistance, antibacterial property, impact resistance and other properties.
Drawings
FIG. 1 is a flow chart of a preparation method of the waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
As shown in fig. 1, fig. 1 is a flow chart of a preparation method of the waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following steps:
s1, adding deionized water into a drawing cylinder, starting a dispersion machine, stirring and dispersing for 8-10 min, adjusting the pH to 8.0-10.0, and stirring and dispersing for 5-10 min;
s2, adding the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond into the solution obtained in the step S1, and stirring and dispersing for 5-10 min;
s3, sequentially adding the aqueous multifunctional additive, the dispersant, the film-forming additive, the antifreeze, the aqueous defoamer, the bactericide, the water repellent and the deionized water into the solution obtained in the step S2, stirring and dispersing for 5-10 min;
s4, adding a thickening agent into the solution obtained in the step S3, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 5-10 min;
and S5, adding colored sand into the solution obtained in the step S4, mixing, and uniformly stirring to obtain the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint.
Preferably, the raw material components by weight are as follows: 10-20 parts of the waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, 0.3-0.5 part of the waterborne multifunctional auxiliary agent, 0.05-0.2 part of the dispersing agent, 0.6-1.5 parts of the film forming auxiliary agent, 0.1-0.2 part of the antifreezing agent, 0.1-0.2 part of the waterborne defoaming agent, 0.2-0.4 part of the bactericide, 0.2-0.8 part of the water repellent, 0.1-0.5 part of the thickening agent, 10-15 parts of deionized water and 60-80 parts of the colored sand.
The waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond comprises the following raw materials in parts by mass:
a1, heating 60-120 parts of polymer polyol to 100-130 ℃, and dehydrating in vacuum for 1-2 h;
a2, carrying out nitrogen protection on the solution obtained in the step A1, cooling to 60-90 ℃, adding 30-60 parts of polyisocyanate and 0.01-0.03 part of catalyst, reacting for 1-3 h, and adding 30-60 parts of organic solvent to adjust viscosity;
a3, adding 5-10 parts of hydrophilic chain extender into the solution obtained in the step A2, and reacting for 1-3 h at 50-90 ℃;
a4, adding 5-10 parts of disulfide bond compounds and 5-10 parts of acylhydrazone bond compounds into the solution obtained in the step A3, and reacting at 40-90 ℃ for 1-3 h;
a5, adding 0.5-1.0 part of end-capping reagent into the solution obtained in the step A4, and keeping the temperature at 80-90 ℃;
a6, adding 8-15 parts of Acrylic Acid (AA) and 40-60 parts of acrylate monomers into the solution obtained in the step A5, adding initiators in batches at intervals of 10-20 min every time, and keeping the temperature at 70-80 ℃ after adding 0.01-0.02 part of initiators in total for continuous reaction for 5-6 h;
a7, cooling the solution obtained in the step A6 to 30-50 ℃, adding 10-15 parts of a salt forming agent, and reacting for 10-30 min;
a8, cooling the solution obtained in the step A7 to 30-50 ℃, adding 200-400 parts of deionized water, and dispersing at high speed for 10-30 min;
a9, desolventizing the solution obtained in the step A8 under vacuum degree to obtain the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond.
The polymer polyol is one or two of polyether polyol and polyester polyol.
The polyisocyanate is one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate.
The hydrophilic chain extender is one or more of N- (2-aminoethyl) -2-aminoethane sodium sulfonate, N-di (2-hydroxyethyl) -2-aminoethane sodium sulfonate, ethylene diaminoethane sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and derivatives thereof.
The disulfide bond compound is one or two of 4, 4 '-diaminodiphenyl sulfide, 3' -dihydroxydiphenyl disulfide, 4 '-dihydroxydiphenyl sulfide, 2-aminodiphenyl sulfide, 2' -dithiodiethanol (HEDS) and dihydroxyethyl diethyl thiuram disulfide (TDS glycol).
The acylhydrazone bond compound is one or two of quinoxalin hydrazone and diflufenzopyr.
The catalyst is one or two of organic tin and tertiary amine.
The organic solvent is one or more of acetone, butanone, methyl ethyl ketone, dioxane, N-dimethyl amide, N-methyl pyrrolidone and ethyl acetate.
The salt forming agent is one or more of triethylamine, ammonia water and sodium hydroxide.
The end capping agent is one or more of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl acrylate (HPA).
The acrylate monomer is one or more of acrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate.
The water-based multifunctional additive is AMP-95 multifunctional additive.
The dispersant is a polycarboxylic acid sodium salt dispersant (SokalanCP5, SokalanHP25, SokalanPA15, etc.).
The film-forming assistant is one or a mixture of more than two of alcohols, alcohol esters, alcohol ethers and alcohol ether esters.
The antifreezing agent is one or a mixture of more than two of methanol, ethanol, ethylene glycol, propylene glycol and glycerol.
The water-based defoaming agent is one or a mixture of more than two of organic matters, silicon dioxide and organic silicon.
The bactericide is one or more of DODOWEICIL (TM) 75, DOWEICIL (TM) 96, DOWEICILTMQK-20, BIOBANTMBP-30, and dialdehyde 50%.
The water repellent is one or a mixture of more than two of silane group powder water repellent (SHP-50) and organosilicon water repellent powder (FN 80).
The thickening agent is one or a mixture of more than two of organic clay, cellulose, association synthesis and non-association synthesis.
The color sand is one or a mixture of more than two of natural color sand, dyed color sand and quartz sand.
The invention overcomes the defects in the prior art and provides a preparation method of waterborne polyurethane-polyacrylic acid-based self-repairing stone-like paint. The chemical bond of reversible reaction of disulfide bond and acylhydrazone bond and the hydrogen bond action of polyurethane-polyacrylic acid are utilized to realize the multiple repair of the damage of the real stone paint. The stone-like paint prepared by the invention has the characteristics of wear resistance, low temperature resistance, chemical resistance, excellent oil resistance, excellent impact resistance and the like.
Example one
The preparation method of the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond comprises the following steps:
a1, adding 100 parts of polytetrahydrofuran diol into a reactor, and carrying out vacuum dehydration treatment for 2 hours at 120 ℃;
a2, cooling to 80 ℃ under the protection of N2, adding 44.5 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate, heating to 90 ℃ and reacting for 3 hours, and adjusting the viscosity by 40 parts of N-methyl pyrrolidone;
a3, cooling to 70 ℃, adding 8 parts of N- (2-aminoethyl) -2-aminoethane sodium sulfonate for reaction for 3 hours;
a4, cooling to 50 ℃, adding 10 parts of 4, 4' -diaminodiphenyl sulfide and 8 parts of quinoxime hydrazone to react for 2 hours;
a5, adding 10 parts of hydroxyethyl methacrylate (HEMA), and keeping the temperature at 90 ℃;
a6, adding 10 parts of Acrylic Acid (AA), 20 parts of acrylic ester and 30 parts of methyl methacrylate, adding 0.012 part of initiator in parts, each time with 10min interval, and keeping the temperature at 70 ℃ for reaction for 5 h;
a7, cooling to 30 ℃, adding 10 parts of sodium hydroxide, and reacting for 30 min;
a8, cooling to 30-50 ℃, adding 300 parts of deionized water, and dispersing at high speed for 30 min;
a9, removing the solvent in vacuum degree to obtain the aqueous polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds.
The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following steps:
s1, adding 12 parts of deionized water into a drawing cylinder, starting a dispersion machine, stirring and dispersing for 10min, adjusting the pH value to 9.0, and stirring and dispersing for 10 min;
s2, adding 12 parts of waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, and stirring and dispersing for 10 min;
s3, adding 0.3 part of AMP-95 multifunctional auxiliary agent, 0.1 part of dispersant SokalanCP5, 0.6 part of film-forming auxiliary agent Texanol, 0.1 part of glycerol antifreezing agent, 0.1 part of aqueous defoaming agent, 0.1 part of DOWEICIL (national antiseptic of agricultural chemical) 75 and 0.3 part of SHP-50 water repellent in sequence, and stirring and dispersing for 5-10 min;
s4, adding 0.8 part of thickening agent, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 5-10 min;
and S5, adding 74 parts of colored sand, mixing and uniformly stirring to obtain the stone-like paint.
The performance of the real stone paint is detected, the adopted standard is synthetic resin emulsion sand wall building coating (JG/T24-2000), and the performance detection result of the real stone paint is as follows:
1. drying for 1 h; 2. water resistance: no bulging, cracking and peeling are caused after 96 hours; 3. alkali resistance: no bulging, cracking and peeling are caused after 96 hours; 4. the temperature change resistance of the coating is as follows: the coating does not have pulverization, cracking, peeling and bulging after 10 times; 5. artificial aging resistance: the coating after 500 hours has no cracking, bulging, peeling, powdering grade 0 and discoloration grade 0.
Example two
The preparation method of the waterborne polyurethane emulsion containing the disulfide bond and the acylhydrazone bond comprises the following steps:
a1, adding 100 parts of polycaprolactone diol into a reactor, and carrying out vacuum dehydration treatment at 120 ℃ for 2 hours;
a2 at N2Under the protection, the temperature is reduced to 70 ℃, 50 parts of 4, 4-diphenylmethane diisocyanate (MDI) and 0.02 part of stannous octoate are added, and liter is addedReacting at 85 ℃ for 3h, and adjusting the viscosity by 40 parts of 20ml dioxane;
a3, cooling to 70 ℃, adding 10 parts of ethylene diaminoethane sodium sulfonate, and reacting for 3 hours;
a4, heating to 50 ℃, adding 10 parts of 4, 4' -dihydroxy diphenyl sulfide and 7-diflufenzopyr, and reacting for 3 hours;
a5, adding 10 parts of hydroxyethyl acrylate (HEA) and keeping the temperature at 90 ℃;
a6, adding 10 parts of Acrylic Acid (AA), 20 parts of methyl methacrylate and 20 parts of styrene, adding azodiisobutyronitrile in portions, wherein the total amount of the azodiisobutyronitrile is 0.010 part, and reacting for 5 hours at the temperature of 70 ℃ at intervals of 10 min;
a7, cooling to 30 ℃, adding 10 parts of sodium hydroxide, and reacting for 30 min;
a8, cooling to 30-50 ℃, adding 300 parts of deionized water, and dispersing at high speed for 30 min;
a9, removing the solvent in vacuum degree to obtain the aqueous polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds.
The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following steps:
s1, adding 12 parts of deionized water into a drawing cylinder, starting a dispersion machine, stirring and dispersing for 10min, adjusting the pH value to 9.0, and stirring and dispersing for 10 min;
s2, adding 14 parts of waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, and stirring and dispersing for 10 min;
s3, adding 0.3 part of AMP-95 multifunctional auxiliary agent, 0.1 part of dispersant SokalanCP5, 0.6 part of film-forming auxiliary agent Texanol, 0.1 part of glycerol antifreezing agent, 0.1 part of aqueous defoaming agent, 0.1 part of DOWEICIL (sodium formaldehyde) 75 bactericide and 0.3 part of SHP-50 water repellent in sequence, and stirring and dispersing for 10 min;
s4, adding 0.8 part of thickening agent, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 5-10 min;
and S5, adding 72 parts of colored sand, mixing and uniformly stirring to obtain the stone-like paint.
The performance of the real stone paint is detected, the adopted standard is synthetic resin emulsion sand wall building coating (JG/T24-2000), and the performance detection result of the real stone paint is as follows:
1. the drying time is 1.0 h; 2. water resistance: no bulging, cracking and peeling are caused after 96 hours; 3. alkali resistance: no bulging, cracking and peeling are caused after 96 hours; 4. the temperature change resistance of the coating is as follows: the coating does not have pulverization, cracking, peeling and bulging after 10 times; 5. artificial aging resistance: the coating after 500 hours has no cracking, bulging, peeling, powdering grade 0 and discoloration grade 0.
EXAMPLE III
The preparation method of the waterborne polyurethane emulsion containing the disulfide bond and the acylhydrazone bond comprises the following steps:
a1, adding 100 parts of polyoxypropylene glycol into a reactor, and carrying out vacuum dehydration treatment for 2h at 120 ℃;
a2 at N2Under protection, cooling to 70 ℃, adding 35 parts of Toluene Diisocyanate (TDI) and dropwise adding 0.02 part of stannous octoate, heating to 85 ℃, reacting for 3 hours, and adjusting 40 parts of 20ml butanone to adjust viscosity;
a3, cooling to 80 ℃, adding 12 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, and reacting for 3 hours;
a4, heating to 90 ℃, adding 15 parts of 2, 2' -dithiodiethanol and 5 parts of quinoxime hydrazone, and reacting for 3 hours;
a5, cooling to 30 ℃, adding 6 parts of acetic acid, and reacting for 130 min;
a6, adding 10 parts of Acrylic Acid (AA), 20 parts of acrylic ester and 25 parts of methyl methacrylate, adding 0.010 part of benzoyl oxide in batches, reacting for 5 hours at 70 ℃ at intervals of 10min each time;
a7, cooling to 30 ℃, and adding 10 parts of sodium hydroxide to react for 30 min.
A8, cooling to 30-50 ℃, adding 300 parts of deionized water, and dispersing at high speed for 30 min;
a9, removing the solvent in vacuum degree to obtain the disulfide bond aqueous polyurethane-polyacrylic acid emulsion.
The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following steps:
s1, adding 12 parts of deionized water into a drawing cylinder, starting a dispersion machine, stirring and dispersing for 10min, adjusting the pH value to 9.0, and stirring and dispersing for 10 min;
s2, adding 16 parts of waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, and stirring and dispersing for 10 min;
s3, adding 0.3 part of AMP-95 multifunctional auxiliary agent, 0.1 part of dispersant SokalanCP5, 0.6 part of film-forming auxiliary agent Texanol, 0.1 part of glycerol antifreezing agent, 0.1 part of aqueous defoaming agent, 0.1 part of DOWEICIL (sodium formaldehyde) 75 bactericide and 0.3 part of SHP-50 water repellent in sequence, and stirring and dispersing for 10 min;
s4, adding 0.8 part of thickening agent, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 10 min;
and S5, adding 70 parts of colored sand, mixing and uniformly stirring to obtain the stone-like paint.
The performance of the real stone paint is detected, the adopted standard is synthetic resin emulsion sand wall building coating (JG/T24-2000), and the performance detection result of the real stone paint is as follows:
1. the drying time is 1.5 h; 2. water resistance: no bulging, cracking and peeling are caused after 96 hours; 3. alkali resistance: no bulging, cracking and peeling are caused after 96 hours; 4. the temperature change resistance of the coating is as follows: the coating does not have pulverization, cracking, peeling and bulging after 10 times; 5. artificial aging resistance: the coating after 500 hours has no cracking, bulging, peeling, powdering grade 0 and discoloration grade 0.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint is characterized by comprising the following steps:
s1, stirring and dispersing the deionized water for 8-10 min, adjusting the pH to 8.0-10.0, and stirring and dispersing again for 5-10 min;
s2, adding the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond into the solution obtained in the step S1, and stirring and dispersing for 5-10 min;
s3, sequentially adding the aqueous multifunctional additive, the dispersant, the film-forming additive, the antifreeze, the aqueous defoamer, the bactericide, the water repellent and the deionized water into the solution obtained in the step S2, stirring and dispersing for 5-10 min;
s4, adding a thickening agent into the solution obtained in the step S3, adjusting the viscosity to 90 KU/25-110 KU/25 ℃, and stirring and dispersing for 5-10 min;
and S5, adding colored sand into the solution obtained in the step S4, mixing, and uniformly stirring to obtain the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint.
2. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 1, wherein the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint comprises the following raw materials in parts by weight: 10-20 parts of the waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds, 0.3-0.5 part of the waterborne multifunctional auxiliary agent, 0.05-0.2 part of the dispersing agent, 0.6-1.5 parts of the film forming auxiliary agent, 0.1-0.2 part of the antifreezing agent, 0.1-0.2 part of the waterborne defoaming agent, 0.2-0.4 part of the bactericide, 0.2-0.8 part of the water repellent, 0.1-0.5 part of the thickening agent, 10-15 parts of deionized water and 60-80 parts of the colored sand.
3. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 1, wherein the raw materials of the waterborne polyurethane-polyacrylic acid emulsion containing disulfide bonds and acylhydrazone bonds are calculated by mass parts, and the preparation method comprises the following steps:
a1, heating 60-120 parts of polymer polyol to 100-130 ℃, and dehydrating in vacuum for 1-2 h;
a2, carrying out nitrogen protection on the solution obtained in the step A1, cooling to 60-90 ℃, adding 30-60 parts of polyisocyanate and 0.01-0.03 part of catalyst, reacting for 1-3 h, and adding 30-60 parts of organic solvent to adjust viscosity;
a3, adding 5-10 parts of hydrophilic chain extender into the solution obtained in the step A2, and reacting for 1-3 h at 50-90 ℃;
a4, adding 5-10 parts of disulfide bond compounds and 5-10 parts of acylhydrazone bond compounds into the solution obtained in the step A3, and reacting at 40-90 ℃ for 1-3 h;
a5, adding 0.5-1.0 part of end-capping reagent into the solution obtained in the step A4, and keeping the temperature at 80-90 ℃;
a6, adding 8-15 parts of acrylic acid and 40-60 parts of acrylate monomers into the solution obtained in the step A5, adding an initiator in batches at intervals of 10-20 min every time, and keeping the temperature at 70-80 ℃ after 0.01-0.02 part of the initiator is added, and continuously reacting for 5-6 h;
a7, cooling the solution obtained in the step A6 to 30-50 ℃, adding 10-15 parts of a salt forming agent, and reacting for 10-30 min;
a8, cooling the solution obtained in the step A7 to 30-50 ℃, adding 200-400 parts of deionized water, and dispersing at high speed for 10-30 min;
a9, desolventizing the solution obtained in the step A8 under vacuum degree to obtain the waterborne polyurethane-polyacrylic acid emulsion containing the disulfide bond and the acylhydrazone bond.
4. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 1, wherein the waterborne multifunctional auxiliary is an AMP-95 multifunctional auxiliary; the dispersant is a sodium polycarboxylate dispersant; the film-forming auxiliary agent is one or a mixture of more than two of alcohols, alcohol esters, alcohol ethers and alcohol ether esters; the antifreezing agent is one or a mixture of more than two of methanol, ethanol, ethylene glycol, propylene glycol and glycerol; the water-based defoaming agent is one or a mixture of more than two of organic matters, silicon dioxide and organic silicon; the bactericide is one or more of DODOWEICIL (TM) 75, DOWEICIL (TM) 96, DOWEICILTMQK-20, BIOBANTMBP-30 and dialdehyde 50%; the water repellent is one or a mixture of more than two of silane group powder water repellent and organic silicon water repellent powder.
5. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 3, wherein the polymer polyol is one or two of polyether polyol and polyester polyol; the polyisocyanate is one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate; the catalyst is one or two of organic tin and tertiary amine; the organic solvent is one or more of acetone, butanone, methyl ethyl ketone, dioxane, N-dimethyl amide, N-methyl pyrrolidone and ethyl acetate.
6. The method for preparing the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 3, wherein the hydrophilic chain extender is one or more of N- (2-aminoethyl) -2-aminoethane sodium sulfonate, N-bis (2-hydroxyethyl) -2-aminoethane sodium sulfonate, ethylene diaminoethane sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and derivatives thereof.
7. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 3, wherein the disulfide bond compound is one or two of 4, 4 '-diaminodiphenyl sulfide, 3' -dihydroxydiphenyl disulfide, 4 '-dihydroxydiphenyl sulfide, 2-aminodiphenyl sulfide, 2' -dithiodiethanol and dihydroxyethyl diethyl thiuram disulfide; the acylhydrazone bond compound is one or two of quinoxalin hydrazone and diflufenzopyr.
8. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 3, wherein the salt forming agent is one or more of triethylamine, ammonia water and sodium hydroxide; the end capping agent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate.
9. The preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in claim 3, wherein the acrylate monomer is one or more of acrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate.
10. The waterborne polyurethane-polyacrylic acid based self-repairing real stone paint is characterized by being prepared by the preparation method of the waterborne polyurethane-polyacrylic acid based self-repairing real stone paint as claimed in any one of claims 1 to 9.
CN202011392023.3A 2020-12-01 2020-12-01 Waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint and preparation method thereof Pending CN112608626A (en)

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Application publication date: 20210406