CN112694829A - Self-cleaning wear-resistant waterborne polyurethane exterior wall coating and preparation method thereof - Google Patents
Self-cleaning wear-resistant waterborne polyurethane exterior wall coating and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a self-cleaning wear-resistant waterborne polyurethane exterior wall coating and a preparation method thereof. The exterior wall coating consists of composite polyurethane resin, filler, light calcium carbonate, kaolin, titanium dioxide, a dispersing agent, a pH regulator, a defoaming agent, a film-forming agent surfactant, a wetting agent, a thickening agent and isocyanate. The composite polyurethane resin is formed by mixing eugenol modified polyurethane resin and fluorosilane modified polyurethane resin according to a certain mass ratio so as to improve the wear resistance and the lasting antibacterial property of the exterior wall coating; porous nano titanium dioxide nano treated by tetramethyldisiloxane is used as a filler to enhance the anti-fouling performance and the self-cleaning performance of the surface of the coating. The exterior wall coating prepared by the invention has lasting antifouling and antibacterial properties and strong wear resistance, and the coating is not easy to fall off and crack; the exterior wall coating can be widely used in the home decoration and building industries.
Description
Technical Field
The invention relates to the technical field of polyurethane coatings, in particular to a self-cleaning wear-resistant waterborne polyurethane exterior wall coating and a preparation method thereof.
Background
Polyurethane coatings are commonly used as architectural coatings, and have excellent stability, strength, chemical resistance and other mechanical properties, so that the polyurethane coatings are widely applied to various fields such as architectural coatings. In recent years, due to the influence of external industrial pollution, automobile exhaust emission, rainwater washing, haze and other environments, stains, spots and mildew appear on the outer wall of a building, the attractiveness of the building is seriously influenced, and troubles are brought to the cleaning of the outer wall of the building.
Therefore, how to provide a self-cleaning antifouling coating on the surface and a washing-resistant coating for the outer wall of a building to enhance the antifouling and wear-resistant washing performance of the outer wall of the building and reduce the cleaning frequency of the outer wall is particularly necessary.
Disclosure of Invention
The invention aims to provide a self-cleaning wear-resistant waterborne polyurethane exterior wall coating and a preparation method thereof, and aims to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a self-cleaning wear-resistant waterborne polyurethane exterior wall coating is characterized in that; the exterior wall coating comprises a component A and a component B;
the component A comprises the following raw materials, by weight, 60-70 parts of composite polyurethane resin, 10-15 parts of filler, 5-7 parts of light calcium carbonate, 5-7 parts of kaolin, 13-17 parts of titanium pigment, 0.3-0.5 part of dispersant, 0.1-0.2 part of pH regulator, 0.5-1 part of defoamer, 2-5 parts of film forming agent, 0.2-0.6 part of surfactant, 0.5-1 part of wetting agent and 2-5 parts of thickener;
the component B is 10-15 parts of isocyanate.
Further, the composite polyurethane resin comprises eugenol modified polyurethane resin and fluorosilane modified polyurethane resin.
Furthermore, the filler is mainly prepared from porous nano titanium dioxide and tetramethyl disiloxane.
Further, the eugenol modified polyurethane resin is mainly prepared by the reaction of polyether polyol, diisocyanate, eugenol and a catalyst;
the fluorosilane modified polyurethane resin is mainly prepared by the reaction of polyether polyol, diisocyanate, hydroxyl-terminated fluorine-containing siloxane, ethylenediamine and a catalyst.
Further, the mass ratio of the eugenol modified polyurethane resin to the fluorosilane modified polyurethane resin is 20-70: 20 to 70 parts by weight.
Further, the catalyst is azodiisobutyronitrile or dibutyltin dilaurate.
A preparation method of a self-cleaning wear-resistant waterborne polyurethane exterior wall coating comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 10-12h at 50-70 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; reacting under the protection of nitrogen; cooling, adding eugenol, and reacting under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating for reaction under the protection of nitrogen; adding hydroxyl-terminated fluorine-containing siloxane, stirring for reaction, cooling, adding ethylenediamine, and reacting under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and a 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution for reaction, carrying out heat preservation and aging, carrying out reduced pressure distillation to remove a solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 3-5 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (2); reducing stirring speed, adding thickener, defoamer and film forming agent, stirring for 10-15min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
Preferably, the preparation method of the self-cleaning wear-resistant waterborne polyurethane exterior wall coating comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 10-12h at 50-70 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; heating to 70-80 ℃ under the protection of nitrogen, and reacting for 3-5 h; cooling to 55-60 ℃, adding eugenol, and reacting for 2-3h under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating to 70-80 ℃ under the protection of nitrogen, and reacting for 3-5 h; adding hydroxyl-terminated fluorine-containing siloxane, stirring and reacting for 1-2h, cooling to 40-45 ℃, adding ethylenediamine, and reacting for 1-2h under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and the 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution at the temperature of 60-70 ℃, reacting for 1.5-2h, keeping the temperature at 60-70 ℃, aging for 20-24h, carrying out reduced pressure distillation to remove the solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating: s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 3-5 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (2); reducing stirring speed, adding thickener, defoamer and film forming agent, stirring for 10-15min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
In the preparation of the exterior wall coating, firstly, the eugenol modified polyurethane resin and the fluorosilane modified polyurethane resin are used in a mass ratio of 20-70: 20-70, mixing to obtain a composite polyurethane resin; the fluorosilane modified polyurethane resin can enhance the surface hydrophobic property of the polyurethane resin, increase the contact angle between the surface of the exterior wall coating and water and oil, and improve the anti-fouling property of the surface of the coating. In the processing process of the polyurethane resin, the molecular mass is reduced due to thermal degradation and hydrolysis, and the number of terminal hydroxyl groups is increased, so that the mechanical strength and the chemical performance of a polymer are reduced; the aromatic ring structure in the eugenol can improve the mechanical capacity and the thermal stability of the prepared polyester resin; in addition, the eugenol also has stronger bactericidal property and corrosion resistance, so that the antibacterial property of the exterior wall coating can be improved. However, eugenol molecules contain active carbon-carbon double bonds, and the carbon-carbon double bonds are easy to be oxidized, so that the mechanical property and the thermal stability of the polyurethane resin can be caused; in the scheme, the carbon-carbon double bond in the eugenol and the tetramethyldisiloxane on the surface of the modified porous nano titanium dioxide are used for carrying out hydrosilylation reaction under the action of chloroplatinic acid serving as a catalyst to form a bridging structure of the eugenol modified polyurethane resin-nano titanium dioxide-eugenol modified polyurethane resin, so that the mechanical property and the thermal stability of the eugenol modified polyurethane resin are improved.
According to the scheme, the nano particle filler is added into the coating, the porous nano titanium dioxide is used as an inorganic particle, and the nano titanium dioxide has an excellent photocatalytic self-cleaning effect; the internal porous structure has more photocatalytic active sites and better self-cleaning effect, and the self-cleaning performance of the coating can be improved by adding the coating into the coating. However, the nano titanium dioxide is not easy to disperse in an organic system and is easy to generate an agglomeration phenomenon; according to the scheme, the porous nano titanium dioxide is soaked in a tetramethyldisiloxane solution and is subjected to adsorption treatment, and tetramethyldisiloxane is attached to the inner control wall and the outer surface of the treated porous nano titanium dioxide, so that the dispersibility and compatibility of the porous nano titanium dioxide in a system are greatly improved.
Compared with the prior art, the invention has the following beneficial effects: 1. the composite polyurethane resin formed by the eugenol modified polyurethane resin and the fluorosilane modified polyurethane resin is adopted, so that the wear resistance of the exterior wall coating is improved; 2. according to the invention, porous nano titanium dioxide is used as a filler, so that the anti-fouling performance and self-cleaning capability of the surface of the coating are enhanced; 3. the eugenol group in the eugenol modified polyurethane resin can improve the antibacterial property of the coating.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A self-cleaning wear-resistant waterborne polyurethane exterior wall coating comprises a component A and a component B;
the component A comprises the following raw materials, by weight, 60 parts of composite polyurethane resin, 10 parts of filler, 5 parts of light calcium carbonate, 5 parts of kaolin, 13 parts of titanium pigment, 0.3 part of dispersant, 0.1 part of pH regulator, 0.5 part of defoamer, 2-5 parts of film-forming agent, 0.2 part of surfactant, 0.5 part of wetting agent and 2 parts of thickener; the component B is 10 parts of isocyanate.
The composite polyurethane resin comprises eugenol modified polyurethane resin and fluorosilane modified polyurethane resin; the mass ratio of the eugenol modified polyurethane resin to the fluorosilane modified polyurethane resin is 50: 50.
the preparation method comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 10 hours at the temperature of 50 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; heating to 70 ℃ under the protection of nitrogen, and reacting for 3 hours; cooling to 55 ℃, adding eugenol, and reacting for 2 hours under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating to 70 ℃ under the protection of nitrogen, and reacting for 3 hours; adding hydroxyl-terminated fluorine-containing siloxane, stirring and reacting for 1h, cooling to 40 ℃, adding ethylenediamine, and reacting for 1h under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and a 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution at the temperature of 60 ℃, reacting for 1.5h, keeping the temperature at 60 ℃, aging for 20h, carrying out reduced pressure distillation to remove a solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 3 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (2); reducing stirring speed, adding thickener, defoamer and film forming agent, and stirring for 10min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
Example 2
A self-cleaning wear-resistant waterborne polyurethane exterior wall coating comprises a component A and a component B;
the component A comprises the following raw materials, by weight, 63 parts of composite polyurethane resin, 13 parts of filler, 6 parts of light calcium carbonate, 6 parts of kaolin, 15 parts of titanium dioxide, 0.4 part of dispersant, 0.2 part of pH regulator, 0.7 part of defoamer, 3 parts of film-forming agent, 0.4 part of surfactant, 0.6 part of wetting agent and 4 parts of thickener;
the component B is 13 parts of isocyanate.
The composite polyurethane resin comprises eugenol modified polyurethane resin and fluorosilane modified polyurethane resin; the mass ratio of the eugenol modified polyurethane resin to the fluorosilane modified polyurethane resin is 50: 50.
the preparation method comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 11 hours at the temperature of 57 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; heating to 73 ℃ under the protection of nitrogen, and reacting for 4 hours; cooling to 56 ℃, adding eugenol, and reacting for 2.5 hours under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating to 75 ℃ under the protection of nitrogen, and reacting for 4 hours; adding hydroxyl-terminated fluorine-containing siloxane, stirring and reacting for 1.5h, cooling to 42 ℃, adding ethylenediamine, and reacting for 1.5h under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and a 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution at the temperature of 63 ℃, reacting for 1.5-2h, keeping the temperature at 65 ℃, aging for 22h, carrying out reduced pressure distillation to remove a solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 4 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (1); reducing stirring speed, adding thickener, defoamer and film-forming agent, stirring for 12min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
Example 3
A self-cleaning wear-resistant waterborne polyurethane exterior wall coating comprises a component A and a component B;
the component A comprises the following raw materials, by weight, 70 parts of composite polyurethane resin, 15 parts of filler, 7 parts of light calcium carbonate, 7 parts of kaolin, 17 parts of titanium dioxide, 0.5 part of dispersant, 0.2 part of pH regulator, 1 part of defoamer, 5 parts of film forming agent, 0.6 part of surfactant, 1 part of wetting agent and 5 parts of thickener; the component B is 15 parts of isocyanate.
The composite polyurethane resin comprises eugenol modified polyurethane resin and fluorosilane modified polyurethane resin; the mass ratio of the eugenol modified polyurethane resin to the fluorosilane modified polyurethane resin is 50: 50.
the preparation method comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 12 hours at the temperature of 70 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; heating to 80 ℃ under the protection of nitrogen, and reacting for 5 hours; cooling to 60 ℃, adding eugenol, and reacting for 3 hours under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating to 80 ℃ under the protection of nitrogen, and reacting for 5 hours; adding hydroxyl-terminated fluorine-containing siloxane, stirring and reacting for 2h, cooling to 45 ℃, adding ethylenediamine, and reacting for 2h under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and a 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution at the temperature of 70 ℃, reacting for 2 hours, keeping the temperature at 70 ℃, aging for 24 hours, carrying out reduced pressure distillation to remove a solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 5 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (1); reducing stirring speed, adding thickener, defoamer and film forming agent, stirring for 15min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
Comparative example 1
The same as in example 3 was repeated except that the composite polyurethane resin was replaced with a fluorosilane-modified polyurethane resin.
Comparative example 2
The same procedure as in example 3 was repeated except that the urethane resin was not modified and used instead of the syntactic urethane resin.
Comparative example 3
The filler used was nano titanium dioxide, and was not treated at all, and the rest was the same as in example 3.
Test examples
Taking the exterior wall coatings prepared in the examples 1-3 and the comparative examples 1-4, and carrying out performance detection; detecting the basic performance of the coating according to the requirement of GB/T9755-2009 synthetic resin emulsion exterior wall coating, and detecting the wear resistance according to the rotating rubber grinding wheel method for measuring the wear resistance of GB/T1768-; the detection results are shown in table 1;
TABLE 1
As can be seen from the data in Table 1, the exterior wall coatings prepared in examples 1-3 have good wear resistance, stain resistance and antibacterial property; compared with the example 3, the comparative example 1 lacks the eugenol modified polyurethane resin, so that the wear resistance and the antibacterial property of the coating film are slightly reduced; compared with example 3, in the case of the comparison document 2, in the absence of the fluorosilicone modified polyurethane resin and the eugenol modified polyurethane resin, the contact angle of the coating film with water is reduced, the anti-fouling ability is reduced, the antibacterial performance is reduced, and the wear resistance is reduced. Compared with the example 3, the antibacterial performance of the coating is slightly reduced due to the fact that no eugenol group exists in the polyurethane resin, no carbon-carbon double bond participates in hydrosilylation reaction in the preparation process, and the polyurethane resin and the nano porous titanium dioxide cannot be connected, so that the mechanical property of the coating is weakened, the adhesive force is reduced, and the wear resistance is reduced. In the comparison document 3, the nano titanium dioxide is directly added into the coating as a filler, so that the dispersibility is slightly poor, and the self-cleaning function is not fully exerted.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A self-cleaning wear-resistant waterborne polyurethane exterior wall coating is characterized in that; the exterior wall coating comprises a component A and a component B;
the component A comprises the following raw materials, by weight, 60-70 parts of composite polyurethane resin, 10-15 parts of filler, 5-7 parts of light calcium carbonate, 5-7 parts of kaolin, 13-17 parts of titanium pigment, 0.3-0.5 part of dispersant, 0.1-0.2 part of pH regulator, 0.5-1 part of defoamer, 2-5 parts of film forming agent, 0.2-0.6 part of surfactant, 0.5-1 part of wetting agent and 2-5 parts of thickener;
the component B is 10-15 parts of isocyanate.
2. The self-cleaning wear-resistant waterborne polyurethane exterior wall coating of claim 1, wherein: the composite polyurethane resin comprises eugenol modified polyurethane resin and fluorosilane modified polyurethane resin.
3. The self-cleaning wear-resistant waterborne polyurethane exterior wall coating of claim 1, wherein: the filler is mainly prepared from porous nano titanium dioxide and tetramethyl disiloxane.
4. The self-cleaning wear-resistant waterborne polyurethane exterior wall coating of claim 2, wherein:
the eugenol modified polyurethane resin is mainly prepared by the reaction of polyether polyol, diisocyanate, eugenol and a catalyst;
the fluorosilane modified polyurethane resin is mainly prepared by the reaction of polyether polyol, diisocyanate, hydroxyl-terminated fluorine-containing siloxane, ethylenediamine and a catalyst.
5. The self-cleaning wear-resistant waterborne polyurethane exterior wall coating of claim 2, wherein: the mass ratio of the eugenol modified polyurethane resin to the fluorosilane modified polyurethane resin is 20-70: 20 to 70 parts by weight.
6. The self-cleaning wear-resistant waterborne polyurethane exterior wall coating of claim 4, wherein: the catalyst is azodiisobutyronitrile or dibutyltin dilaurate.
7. A preparation method of self-cleaning wear-resistant waterborne polyurethane exterior wall coating is characterized by comprising the following steps: comprises the following steps;
(1) preparing a filler: dispersing the porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting at 50-70 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; reacting under the protection of nitrogen; cooling, adding eugenol, and reacting under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating for reaction under the protection of nitrogen; adding hydroxyl-terminated fluorine-containing siloxane, stirring for reaction, cooling, adding ethylenediamine, and reacting under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and a 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution for reaction, carrying out heat preservation and aging, carrying out reduced pressure distillation to remove a solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 3-5 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (2); reducing stirring speed, adding thickener, defoamer and film forming agent, stirring for 10-15min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
8. The preparation method of the self-cleaning wear-resistant waterborne polyurethane exterior wall coating according to claim 7, wherein the self-cleaning wear-resistant waterborne polyurethane exterior wall coating is characterized in that: comprises the following steps;
(1) preparing a filler: dispersing porous nano titanium dioxide in a tetramethyldisiloxane solution, reacting for 10-12h at 50-70 ℃, washing with deionized water, and drying to obtain modified porous nano titanium dioxide;
(2) preparing a composite polyurethane resin:
s1, preparing eugenol modified polyurethane resin: mixing polyether polyol, diisocyanate and dimethylformamide, stirring, and adding a catalyst; heating to 70-80 ℃ under the protection of nitrogen, and reacting for 3-5 h; cooling to 55-60 ℃, adding eugenol, and reacting for 2-3h under the protection of nitrogen to obtain eugenol modified polyurethane resin;
s2, preparing fluorosilane modified polyurethane resin: mixing polyether polyol, diisocyanate and tetrahydrofuran, stirring and adding a catalyst; heating to 70-80 ℃ under the protection of nitrogen, and reacting for 3-5 h; adding hydroxyl-terminated fluorine-containing siloxane, stirring and reacting for 1-2h, cooling to 40-45 ℃, adding ethylenediamine, and reacting for 1-2h under the protection of nitrogen to obtain fluorosilane modified polyurethane resin;
s3, preparing composite polyurethane resin: melting the eugenol modified polyurethane resin prepared in the step S1, adding the modified porous nano titanium dioxide prepared in the step (1) and the 1, 4-dioxane solution, mixing, stirring uniformly, carrying out nitrogen protection, dropwise adding a chloroplatinic acid solution at the temperature of 60-70 ℃, reacting for 1.5-2h, keeping the temperature at 60-70 ℃, aging for 20-24h, carrying out reduced pressure distillation to remove the solvent, and drying; adding the fluorosilane modified polyurethane resin prepared by the step S2, and blending to obtain a composite polyurethane resin;
(3) preparing an exterior wall coating:
s1, sequentially adding light calcium, kaolin, titanium dioxide, pH adjusting agent, wetting agent and bactericide into water, and stirring for 3-5 min; increasing the stirring speed, and adding the composite polyurethane resin prepared in the step (2); reducing stirring speed, adding thickener, defoamer and film forming agent, stirring for 10-15min to obtain component A;
and S2, mixing the component A and the component B, and uniformly stirring to obtain a finished product of the exterior wall coating.
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| CN116063653B (en) * | 2023-03-06 | 2023-06-06 | 开贝科技(苏州)有限公司 | Modified polyurethane and preparation method and application thereof |
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