CN109593454B - Polyurethane coating and preparation method and application thereof - Google Patents
Polyurethane coating and preparation method and application thereof Download PDFInfo
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- CN109593454B CN109593454B CN201811572619.4A CN201811572619A CN109593454B CN 109593454 B CN109593454 B CN 109593454B CN 201811572619 A CN201811572619 A CN 201811572619A CN 109593454 B CN109593454 B CN 109593454B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a polyurethane coating and a preparation method and application thereof, wherein the polyurethane coating comprises a component A and a component B, wherein the component A comprises the following components in percentage by weight: 10-30% of solvent, 2-8% of diformate, 45-75% of polyol, 0.5-4% of modified graphene oxide, 15-35% of titanium dioxide, 0.1-1% of polyamide wax, 0.1-1% of bentonite and 0.5-2% of auxiliary agent; the component B is an isocyanate curing agent. According to the invention, the modified graphene oxide is added into the component A and is matched with other components of the component A to be combined with the component B to prepare the polyurethane coating, so that the prepared coating has high adhesive force, excellent acid resistance, alkali resistance and salt mist resistance, is used for corrosion prevention of an outdoor steel structure, has excellent corrosion resistance, and is safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a polyurethane coating as well as a preparation method and application thereof.
Background
The metal is easy to corrode in various complex environments, and in order to prevent corrosion of a metal structure, the problem can be effectively solved by coating the anticorrosive coating on the surface of the metal, so that the anticorrosive coating has excellent performances in the aspects of adhesive force, weather resistance, acid and alkali resistance and the like, and the coating is safe and environment-friendly.
CN 108384429A discloses a polyurethane coating, which comprises the following raw materials in parts by weight: 0.25g of dibenzyl azodicarboxylate, 72g of polytetrahydrofuran ether glycol, 18g of hexamethylene diisocyanate, 0.68g of hexahydro-sym-triazoborane, 8.8g of methyl ethyl ketone, 1g of modified manganese hypophosphite, 3.2g of 4-carboxyphenylboronic acid, 3.5g of N-hydroxy-thiosuccinimide, 7.8g of triethylamine and 70g of water.
Therefore, in the art, it is desired to develop a polyurethane coating material having high adhesion and excellent acid resistance, alkali resistance and salt spray resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane coating, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a polyurethane coating comprising a component a and a component B;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent.
In the invention, the modified graphene oxide is added into the component A and is matched with other components of the component A to be combined with the component B to prepare the polyurethane coating, so that the prepared coating has high adhesive force and excellent acid resistance, alkali resistance and salt spray resistance.
In the present invention, in the component a, the solvent is preferably a mixed solvent of butyl ester and xylene.
Preferably, in the component A, the solvent is a mixed solution of butyl ester and xylene with a mass ratio of 2:1-5:1 (such as 2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.3:1, 3.5:1, 3.8:1, 4:1, 4.3:1, 4.5:1, 4.8:1 or 5:1), and the mass ratio of the butyl ester and the xylene is preferably 3: 1.
In the present invention, the solvent may be used in an amount of 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28% or 30% in the a component.
In the present invention, the diformate may be used in an amount of 2%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.5%, 4.8%, 5%, 5.5%, 5.8%, 6%, 6.3%, 6.5%, 6.8%, 7%, 7.3%, 7.5%, 7.8%, or 8%.
In the present invention, the polyol is an acrylic-modified polyol resin.
In the present invention, the polyol may be used in an amount of 45%, 48%, 50%, 53%, 55%, 58%, 60%, 63%, 65%, 68%, 70%, 73% or 75%.
In the invention, the modified graphene oxide is graphene oxide modified by a silane coupling agent.
Preferably, the silane coupling agent is a silane coupling agent with an active amino group, preferably gamma-aminopropyltriethoxysilane or silane coupling agent Z-6011.
Preferably, the modified graphene oxide is prepared by the following method: and dispersing graphene oxide into an organic solvent, adding a silane coupling agent into the obtained graphene oxide dispersion liquid, and reacting to obtain the modified graphene oxide.
Preferably, the organic solvent is a mixed solution of xylene and N-butanol or N, N-dimethylformamide.
Preferably, the mode of dispersion is ultrasonic dispersion.
Preferably, the time of ultrasonic dispersion is 10-40min, such as 10min, 13min, 15min, 18min, 20min, 25min, 28min, 30min, 35min, 38min or 40 min.
In the present invention, the amount of the organic solvent used in the graphene oxide dispersion is 10 to 100mL, for example, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL, 55mL, 60mL, 65mL, 70mL, 75mL, 80mL, 85mL, 90mL, 95mL, or 100mL, relative to 1g of graphene oxide.
Preferably, the temperature of the reaction is 70-90 ℃, such as 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃, 85 ℃, 88 ℃ or 90 ℃.
Preferably, the reaction is carried out with stirring.
Preferably, the time of the reaction is 5 to 24 hours, such as 5 hours, 7 hours, 9 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.
In the present invention, the amount of the modified graphene oxide is 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, or 4%.
In the invention, the amount of the titanium dioxide can be 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33% or 35%.
In the present invention, the polyamide wax may be used in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
In the present invention, the bentonite may be used in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
In the present invention, the amount of the auxiliary agent may be 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, or 2%.
Preferably, the auxiliary agent includes a leveling agent, a dispersing agent, and an antifoaming agent.
Preferably, the isocyanate curing agent is any one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or isophorone diisocyanate (IPDI) or a combination of at least two thereof.
Preferably, the mass ratio of the a-component to the B-component is 3:1 to 9:1, such as 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.3:1, 8.5:1, 8.8:1 or 9:1, preferably 4: 1.
In the invention, the preparation method of the polyurethane coating is to mix the components of the component A, then mix the component A and the component B, cure at normal temperature, and cure at 25 ℃ for more than 7 days (such as 7 days, 8 days, 9 days, 10 days and the like) to obtain the polyurethane coating.
In another aspect, the invention provides the use of a polyurethane coating as described above for the corrosion protection of outdoor steel structures.
Preferably, the polyurethane coating is used as a finish paint for outdoor steel structure corrosion prevention.
The polyurethane coating disclosed by the invention can be used for corrosion prevention of an outdoor steel structure, and has the advantages of good acid resistance, alkali resistance, salt mist resistance, high adhesive force and good corrosion resistance. It can be applied with graphene modified anticorrosion primer to enhance the anticorrosion performance.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the modified graphene oxide is added into the component A and is matched with other components of the component A to be combined with the component B to prepare the polyurethane coating, so that the prepared coating has high adhesive force, excellent acid resistance, alkali resistance and salt mist resistance, the adhesive force can reach more than 13MPa, the acid resistance and alkali resistance can reach more than 2000h, the humidity and heat resistance can reach more than 2200h, the water resistance can reach more than 5000h, and the modified graphene oxide coating has qualified temperature change resistance and ultraviolet resistance, is used for outdoor steel structure anticorrosion, has excellent anticorrosion performance, and is safe and environment-friendly.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this example, a polyurethane coating is provided, which includes a component a and a component B in a mass ratio of 4: 1;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent namely toluene diisocyanate.
The modified graphene oxide is modified by a silane coupling agent, and the preparation method comprises the following steps:
dispersing 6g of dried graphene oxide in 500mL of DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion for 30min to prepare graphene oxide dispersion liquid, then adding 100g of KH550 (gamma-aminopropyltriethoxysilane), heating to 80 ℃, stirring for 12 hours, after the reaction is finished, washing for 3 times by using deionized water, performing centrifugal separation, and performing vacuum drying treatment on the product to obtain the modified graphene oxide.
The preparation method of the polyurethane coating comprises the following steps: and mixing the components forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing at 25 ℃ for 7 days to obtain the polyurethane coating.
Example 2
In this example, a polyurethane coating is provided, which includes a component a and a component B in a mass ratio of 4: 1;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent namely toluene diisocyanate.
The modified graphene oxide is modified by a silane coupling agent, and the preparation method comprises the following steps:
dispersing 6g of dried graphene oxide in 180mL of DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion for 25min to prepare graphene oxide dispersion liquid, then adding 100g of KH550 (gamma-aminopropyltriethoxysilane), heating to 70 ℃, stirring for 20 hours, after the reaction is finished, washing for 3 times by using deionized water, performing centrifugal separation, and performing vacuum drying treatment on the product to obtain the modified graphene oxide.
The preparation method of the polyurethane coating comprises the following steps: and mixing the components forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing at 25 ℃ for 7 days to obtain the polyurethane coating.
Example 3
In this example, a polyurethane coating is provided, which includes a component a and a component B in a mass ratio of 9: 1;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent namely toluene diisocyanate.
The modified graphene oxide is modified by a silane coupling agent, and the preparation method comprises the following steps:
dispersing 6g of dried graphene oxide in 300mL of DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion for 40min to prepare graphene oxide dispersion liquid, then adding 100g of KH550 (gamma-aminopropyltriethoxysilane), heating to 900 ℃, stirring for 5 hours, after the reaction is finished, washing for 3 times by using deionized water, performing centrifugal separation, and performing vacuum drying treatment on the product to obtain the modified graphene oxide.
The preparation method of the polyurethane coating comprises the following steps: and mixing the components forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing at 25 ℃ for 9 days to obtain the polyurethane coating.
Example 4
In this example, a polyurethane coating is provided, which includes a component a and a component B in a mass ratio of 5: 1;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent, namely isophorone diisocyanate.
The modified graphene oxide is modified by a silane coupling agent, and the preparation method comprises the following steps:
dispersing 6g of dried graphene oxide in 600mL of DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion for 10min to prepare graphene oxide dispersion liquid, then adding 100g of KH550 (gamma-aminopropyltriethoxysilane), heating to 85 ℃, stirring for 18 hours, after the reaction is finished, washing for 3 times by using deionized water, performing centrifugal separation, and performing vacuum drying treatment on the product to obtain the modified graphene oxide.
The preparation method of the polyurethane coating comprises the following steps: and mixing the components forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing at 25 ℃ for 7 days to obtain the polyurethane coating.
Example 5
In this example, a polyurethane coating is provided, which includes a component a and a component B in a mass ratio of 6: 1;
the component A comprises the following components in percentage by weight:
the component B is an isocyanate curing agent, namely diphenylmethane diisocyanate.
The modified graphene oxide is modified by a silane coupling agent, and the preparation method comprises the following steps:
dispersing 6g of dried graphene oxide in 400mL of DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion for 20min to prepare graphene oxide dispersion liquid, then adding 100g of KH550 (gamma-aminopropyltriethoxysilane), heating to 75 ℃, stirring for 24 hours, after the reaction is finished, washing for 3 times by using deionized water, performing centrifugal separation, and performing vacuum drying treatment on the product to obtain the modified graphene oxide.
The preparation method of the polyurethane coating comprises the following steps: and mixing the components forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing for 8 days at 25 ℃ to obtain the polyurethane coating.
Comparative example 1
The only difference from example 1 is that the mass ratio of the A component and the B component is 2: 1.
Comparative example 2
The only difference from example 1 is that the mass ratio of the A component and the B component is 10: 1.
Comparative example 3
The difference from the embodiment 1 is that the component A does not contain modified graphene oxide, and the amount of the titanium dioxide is 23%.
The polyurethane coatings prepared in the examples and the comparative examples are used as finish paint to be coated on the surface of a steel structure for corrosion prevention, and the salt spray resistance, the acid and alkali resistance, the salt water resistance, the water resistance and the adhesive force performance of the polyurethane coatings are measured, and the test standards and index requirements are shown in table 1.
TABLE 1
The actual performance test data for the coatings of examples 1-5 and comparative examples 1-3 is shown in Table 2.
TABLE 2
The applicant states that the invention is illustrated by the above examples of the polyurethane coating of the invention and the preparation and application thereof, but the invention is not limited to the above examples, i.e. it is not meant that the invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. The polyurethane coating is characterized by comprising a component A and a component B;
the component A comprises the following components in percentage by weight:
10 to 30 percent of solvent
2 to 8 percent of diformate
45 to 75 percent of polyol
0.5 to 4 percent of modified graphene oxide
15 to 35 percent of titanium dioxide
Polyamide wax 0.1-1%
0.1 to 1 percent of bentonite
0.5-2% of an auxiliary agent;
the sum of the weight percentage of the components is 100 percent;
the component B is an isocyanate curing agent;
the mass ratio of the component A to the component B is 3:1-9: 1;
in the component A, a solvent is a mixed solution of butyl ester and xylene in a mass ratio of 2:1-5:1, and the polyol is acrylic acid modified polyol resin;
the modified graphene oxide is prepared by the following method: dispersing graphene oxide into an organic solvent, adding a silane coupling agent into the obtained graphene oxide dispersion liquid, and reacting to obtain the modified graphene oxide; the silane coupling agent is gamma-aminopropyl triethoxysilane;
the auxiliary agent is a flatting agent, a dispersing agent and a defoaming agent.
2. The polyurethane coating of claim 1, wherein the mass ratio of butyl ester to xylene is 3: 1.
3. The polyurethane coating according to claim 1, wherein the silane coupling agent is silane coupling agent Z-6011.
4. The polyurethane paint as claimed in claim 1, wherein the organic solvent is a mixed solution of xylene and n-butanol orN,N-dimethylformamide.
5. The polyurethane coating of claim 1, wherein, for the preparation of the modified graphene oxide, the dispersion is ultrasonic dispersion.
6. The polyurethane coating of claim 5, wherein the ultrasonic dispersion time is 10-40min for the preparation of the modified graphene oxide.
7. The polyurethane paint according to claim 1, wherein the amount of the organic solvent used in the graphene oxide dispersion is 10 to 100mL per 1g of graphene oxide.
8. The polyurethane coating of claim 1, wherein the reaction temperature is 70-90 ℃ for the preparation of the modified graphene oxide.
9. The polyurethane coating of claim 1, wherein for the preparation of the modified graphene oxide, the reaction is performed under agitation.
10. The polyurethane coating of claim 1, wherein the reaction time is 5-24 hours for the preparation of the modified graphene oxide.
11. The polyurethane coating of claim 1, wherein the isocyanate curing agent is any one of toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate or a combination of at least two thereof.
12. A method for preparing a polyurethane coating according to any one of claims 1-11, characterized in that the method is: and mixing the components for forming the component A, then mixing the component A with the component B, curing at normal temperature, and curing at 25 ℃ for more than 7 days to obtain the polyurethane coating.
13. Use of a polyurethane coating according to any one of claims 1-11 for corrosion protection of outdoor steel structures.
14. The use according to claim 13, characterized in that the polyurethane coating is used as a top coat for outdoor steel structure corrosion protection.
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| CN110804328A (en) * | 2019-11-05 | 2020-02-18 | 徐州汉通电子科技有限公司 | Polyurethane coating for electronic element |
| CN113087679A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Polyisocyanate curing agent with low free monomer, preparation method, coating composition and application |
| CN114163916A (en) * | 2021-12-23 | 2022-03-11 | 重庆品涂新材料科技有限公司 | Waterproof paint and production method thereof |
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| JPS5876464A (en) * | 1981-10-30 | 1983-05-09 | Mitui Toatsu Chem Inc | Pressurized one-package polyurethane coating and coating method using the same |
| JP5348986B2 (en) * | 2008-09-25 | 2013-11-20 | 富士フイルム株式会社 | Conductive material and manufacturing method thereof |
| CN104356860A (en) * | 2014-10-29 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Epoxy resin-oxidized graphene composite coating and application method thereof |
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