CN110615998A - Wear-resistant super-hydrophobic coating composition - Google Patents
Wear-resistant super-hydrophobic coating composition Download PDFInfo
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- CN110615998A CN110615998A CN201910843532.4A CN201910843532A CN110615998A CN 110615998 A CN110615998 A CN 110615998A CN 201910843532 A CN201910843532 A CN 201910843532A CN 110615998 A CN110615998 A CN 110615998A
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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
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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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Abstract
The invention relates to a wear-resistant super-hydrophobic coating composition based on diatomite, which at least comprises the following components: a superhydrophobic diatomaceous earth dispersion having an active group, (ii) a resin, and (iii) a curing agent capable of bonding the superhydrophobic diatomaceous earth and the resin by covalent bonding. Wherein the active group of the super-hydrophobic diatomite is preferably a hydroxyl group, an amino group or an epoxy group. The coating composition can be coated on the surface of a base material such as glass, metal, plastic, ceramic, wood, paper and the like by using a method of dip coating, spin coating, roll coating, spray coating or curtain coating to form a wear-resistant super-hydrophobic coating. Wherein the coating formed on the glass has excellent hydrophobicity and abrasion resistance: the contact angle to water is 161 degrees, and the rolling angle is 1 degree; grinding with 240-mesh sand paper under the pressure of 500g weight, wherein the contact angle is still larger than 155 degrees after 265 times of grinding for 10cm each time; the pencil hardness of the coating on the base materials such as glass, metal and the like is 4-5H, and the adhesive force is 0-1 grade.
Description
Technical Field
The invention relates to an abrasion-resistant super-hydrophobic coating composition. And more particularly, to a superhydrophobic coating composition prepared from diatomaceous earth having excellent superhydrophobic properties and good mechanical properties.
Background
In recent years, the super-hydrophobic surface has attracted people's attention because of its wide application prospect in the industrial and biological fields. The super-hydrophobic surface is a surface with a contact angle to water of more than 150 degrees and a rolling angle of less than 10 degrees. The surface has obvious application value in the aspects of self-cleaning, drag reduction, corrosion prevention, ice coating prevention, oil-water separation, marine antifouling and the like.
There are many reports on superhydrophobic coatings so far, but in practical application, the micro-nano structure of the superhydrophobic surface is fragile, and the surface structure or chemical composition of the superhydrophobic surface may be damaged when being worn by external force or chemically corroded so as to lose hydrophobic property, which limits the large-scale practical application of the superhydrophobic surface. Therefore, the improvement of the wear resistance and durability of the superhydrophobic surface is of great significance to the application thereof in various fields.
According to literature reports, self-healing components, adhesives and the like are introduced into the coating, so that the surface wear resistance and durability of the super-hydrophobic material can be remarkably improved. Wu Gang et al prepared self-healing super-hydrophobic coatings, and after the coating structure was destroyed by external force, the active substances in the microcapsules were released to repair the micro-nano structure. The self-healing performance of the super-hydrophobic microcapsule can prolong the service life of the super-hydrophobic surface to a certain extent, but the problem of poor wear resistance cannot be fundamentally solved. LuYao et al use an adhesive to adhere superhydrophobic materials to various substrates, resulting in superhydrophobic surfaces with excellent abrasion resistance. However, the method has high construction requirements and brings inconvenience in practical application. Therefore, the construction of the single-layer coating with both the surface and the body having the super-hydrophobicity is the most ideal strategy for improving the wear resistance and the durability of the super-hydrophobic coating, and meanwhile, the preparation process of the body super-hydrophobic coating is simple, and the coating can be applied in a large area, so that the method has a practical prospect.
The diatomite is a natural mineral compound formed by diatomite fossil, mainly consists of amorphous silicon dioxide, has a micro-nano structure and low price, and is an ideal material for preparing the body super-hydrophobic coating. According to the invention, the diatomite is subjected to graft modification and hydrophobic modification, so that chemical crosslinking can be formed between modified diatomite particles and polyurethane resin, and the overall compactness of the coating is improved, thus the mechanical property and adhesive force of the super-hydrophobic coating are improved, and the super-hydrophobic coating with excellent mechanical property is prepared.
Disclosure of Invention
The invention mainly aims at the problems and provides a method for preparing a simple wear-resistant super-hydrophobic coating composition, and a coating prepared from the super-hydrophobic coating composition has excellent super-hydrophobic property and mechanical property.
To achieve the object of the present invention, the present invention includes the following items:
the composition at least comprises a component A, a component B and a component C, wherein the component A is a super-hydrophobic diatomite dispersion liquid with active groups, the component B is resin, and the component C is a curing agent.
The abrasion resistant superhydrophobic coating composition according to claim 1, wherein said a component is a diatomaceous earth dispersion modified with a reactive group coupling agent and a hydrophobic agent.
The abrasion-resistant superhydrophobic coating composition according to claim 1 or 2, wherein the superhydrophobic diatomite dispersion liquid having active groups of component a is prepared by: dissolving a silane coupling agent containing active groups in a solvent, adding a proper amount of water, and adding acid to adjust the pH value to be acidic, so as to obtain a prehydrolysis solution of the silane coupling agent. And adding a silane coupling agent prehydrolysis solution into the calcined diatomite, adding a certain amount of solvent, adding acid to adjust the pH value to acidity, heating and reacting at a certain temperature for a period of time, then performing suction filtration, washing for 3 times by using the solvent, and drying to obtain the diatomite with active groups. And then mixing the hydrophobing agent, the diatomite with active groups and a proper amount of solvent, performing suction filtration after reacting for a period of time at room temperature, washing for 3 times by using the solvent, and drying to obtain the super-hydrophobic diatomite. And dispersing the super-hydrophobic diatomite in a solvent to prepare the super-hydrophobic diatomite dispersion liquid. Wherein the mass ratio of the diatomite to the silane coupling agent to the hydrophobic agent is 1: 0.01-0.1: 0.08-0.5, the modification reaction temperature range of the silane coupling agent is 20-100 ℃, and the pH range is 2-6.
The abrasion-resistant superhydrophobic coating composition according to claims 1-3, wherein the diatomaceous earth of component A is disc-shaped, elliptical, columnar and amorphous diatomaceous earth, preferably columnar diatomaceous earth with a size of 1-100 μm.
The abrasion-resistant superhydrophobic coating composition according to claim 1-3, wherein the superhydrophobic diatomite dispersion of component A, the solvent is preferably tetrahydrofuran, acetone, ethyl acetate and combination thereof, and the solid content is 10-50%, preferably 15-30%.
An abrasion resistant superhydrophobic coating composition according to claim 1 or 2, wherein said a-component has reactive groups, preferably hydroxyl, amino or epoxy groups and any combination thereof.
The abrasion resistant superhydrophobic coating composition according to claim 1 or 2, wherein the hydrophobic agent is heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrichlorosilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrichlorosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltrichlorosilane, and combinations thereof.
The wear-resistant super-hydrophobic coating composition as claimed in claim 1-3, wherein the solvent used for modifying the component A silane coupling agent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol and pentanol, and the solvent used for modifying the hydrophobic agent is one or more of n-pentane, n-hexane, n-heptane and petroleum ether.
The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the resin of the B-component is a polyurethane resin containing polyhydroxy or polyamino groups or a fluorine-modified polyurethane resin.
The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the curing agent of component C is an aliphatic or aromatic di-or poly-isocyanate.
The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the mass ratio of the a component, the B component and the C component is: 0.72-7: 1: 0.8-1.8.
The abrasion-resistant superhydrophobic coating composition according to any one of claims 1-9, wherein the base material is one of glass, metal, plastic, ceramic, wood, paper.
In the invention, the super-hydrophobic diatomite with active groups endows the surface with super-hydrophobic performance through the micro-nano rough structure of the diatomite and the low surface energy of a hydrophobic agent. The polyurethane resin generally has no super-hydrophobicity, but can remarkably improve the mechanical strength of the super-hydrophobic coating after being combined with super-hydrophobic diatomite.
The wear-resistant super-hydrophobic coating composition can be coated by adopting a conventional coating method, such as dip coating, spin coating, roll coating, spray coating or curtain coating, and the coating composition is uniformly stirred before construction. The base material can be glass, metal, plastic, ceramic, wood, paper and the like, and the application range is wide.
In the present invention, a suitable curing agent is selected according to the kind of the selected resin and the kind of the super hydrophobic diatomaceous earth active group, and the curing agent is usually aliphatic or aromatic di-or poly-isocyanate.
In the coating composition of the present invention, it is also possible to add additives such as accelerators, defoamers, anti-settling agents, leveling agents and the like for improving the coating composition.
Compared with the existing super-hydrophobic coating, the invention has the beneficial effects that:
(1) the wear-resistant super-hydrophobic coating composition has good wear resistance, is ground on 240-mesh abrasive paper under the pressure of a 500g weight, is 10cm each time, and has a contact angle of more than 155 degrees after being ground for 265 times.
(2) The coating formed by the wear-resistant super-hydrophobic coating composition has high hardness and good adhesion. For example, the pencil hardness on glass and aluminum alloy plates is as high as 4-5H, and the adhesion is 0 grade.
(3) The wear-resistant super-hydrophobic coating composition is convenient to construct and can be coated by various methods such as dip coating, spin coating, roller coating, spray coating or curtain coating.
(4) The wear-resistant super-hydrophobic coating composition disclosed by the invention is wide in application and can be coated on various substrates such as glass, metal, plastic, ceramic, wood, paper and the like.
(6) The wear-resistant super-hydrophobic coating composition has the advantages of low price of raw materials, simple preparation process and mild conditions, so the method has higher practical value.
Drawings
FIG. 1 is a state diagram of a contact angle of the super-hydrophobic coating obtained in example 1 to water before being abraded;
FIG. 2 is a graph showing the state of contact angle of the superhydrophobic coating obtained in example 1 with water after being abraded for 100 times;
FIG. 3 is a graph showing the state of contact angle with water after 200 times of polishing of the superhydrophobic coating obtained in example 1;
FIG. 4 is a state diagram of the contact angle of the super-hydrophobic coating obtained in example 2 to water before being abraded;
FIG. 5 is a state diagram of the contact angle of the super-hydrophobic coating obtained in example 3 to water before being abraded;
FIG. 6 is a state diagram of the contact angle of the super-hydrophobic coating obtained in example 3 with water after polishing;
FIG. 7 is a state diagram of the contact angle of the super-hydrophobic coating obtained in example 4 with water before being abraded;
FIG. 8 is a graph showing the state of the contact angle of the superhydrophobic coating obtained in example 5 with water before abrasion.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following examples, which are intended to give a better understanding of the invention, but do not limit the scope of the invention.
Example 1
First, a three-component coating composition having the following formulation was prepared: 90g of a monoamino silane coupling agent-modified superhydrophobic diatomaceous earth dispersion in tetrahydrofuran as a solvent and having a solids content of 15%, (ii) 17g of a polyurethane resin, and (iii) 15g of a curing agent. 17g of polyurethane resin was added to 67.5g of the monoamino silane coupling agent-modified superhydrophobic diatomaceous earth dispersion, stirred for 30min, then 15g of the curing agent was added, and stirring was continued for 1 h. Finally, the coating was applied by roller coating onto a 7cm x 2.5cm glass slide and cured at 180 ℃ for 20 min.
The cured super-hydrophobic coating has good wear resistance and hydrophobicity. The superhydrophobic coating of this example had a contact angle for water of 158.3 deg. as measured using a contact angle measuring instrument (fig. 1) and a roll angle of 2 deg.. The coating was abraded with a 500g weight of 10cm over 240 mesh sandpaper 100 times to obtain a contact angle of 157.6 ° with water (FIG. 2), and after 200 grindings to obtain a contact angle of 156.0 ° with water (FIG. 3). The super-hydrophobic coating of the present example had a pencil hardness of 4H and an adhesion rating of 0.
Example 2
First, a three-component coating composition having the following formulation was prepared: 45g of a polyaminosilane coupling agent-modified superhydrophobic diatomaceous earth dispersion in tetrahydrofuran as solvent and having a solids content of 30%, (ii) 17g of a polyurethane resin, and (iii) 15g of a curing agent. 17g of polyurethane resin was added to 67.5g of the monoamino silane coupling agent-modified superhydrophobic diatomaceous earth dispersion, stirred for 30min, then 15g of the curing agent was added, and stirring was continued for 1 h. Finally, the coating was applied by roller coating onto a 7cm x 2.5cm glass slide and cured at 180 ℃ for 20 min.
The cured super-hydrophobic coating has good wear resistance and hydrophobicity. The superhydrophobic coating of this example had a contact angle of 159.7 ° measured using a contact angle measuring instrument (fig. 4) and a sliding angle of 2 °. The coating remained superhydrophobic after 210 grindings with 10cm each, on 240 mesh sandpaper under a 500g weight. The super-hydrophobic coating of the present example had a pencil hardness of 4H and an adhesion rating of 0.
Example 3
First, a three-component coating composition having the following formulation was prepared: 67.5g of a polyaminosilane coupling agent-modified superhydrophobic diatomaceous earth dispersion in tetrahydrofuran as the solvent and having a solids content of 20%, (ii) 14g of a polyurethane resin, and (iii) 18g of a curing agent. 14g of polyurethane resin is added into 90g of the super-hydrophobic diatomite dispersion modified by the monoamino silane coupling agent, stirred for 30min, then 18g of the curing agent is added, and stirring is continued for 1 h. Finally, the coating is applied by spraying onto a 7cm x 2.5cm glass slide and cured at 180 ℃ for 20 min.
The cured super-hydrophobic coating has good wear resistance and hydrophobicity. The superhydrophobic coating of this example had a contact angle of 158.0 ° measured with a contact angle measuring instrument (fig. 5) and a sliding angle of 2 °. The contact angle was 157.2 ℃ after 240 grindings with 10cm each on 240-mesh sandpaper under a pressure of 500g weight (FIG. 6). The super-hydrophobic coating of the present example had a pencil hardness of 5H and an adhesion rating of 0.
Example 4
First, a three-component coating composition having the following formulation was prepared: 67.5g of a polyaminosilane coupling agent-modified superhydrophobic diatomaceous earth dispersion in acetone as the solvent and having a solids content of 20%, (ii) 14g of a polyurethane resin, and (iii) 18g of a curing agent. 14g of polyurethane resin was added to 67.5g of the monoamino silane coupling agent-modified superhydrophobic diatomaceous earth dispersion, stirred for 30min, 18g of the curing agent was added, and stirring was continued for 1 h. Finally, the coating was applied to a 7cm x 2.5cm slide and cured at 180 ℃ for 20 min.
The cured super-hydrophobic coating has good wear resistance and hydrophobicity. The superhydrophobic coating of this example had a contact angle of 157.1 ° measured with a contact angle measuring instrument (fig. 7) and a rolling angle of 2 °. The coating remained superhydrophobic after 160 passes of grinding 10cm on 240 mesh sandpaper under a 500g weight. The super-hydrophobic coating of the example has pencil hardness of 5H and adhesion of grade 0.
Example 5
Firstly, preparing a mixture of 3 volume ratio of acetone to ethyl acetate: 1. Next, a three-component coating composition having the following formulation was prepared: 67.5g of polyamino silane coupling agent modified super-hydrophobic diatomite dispersion with a solid content of 20% and a solvent of acetone and ethyl acetate, and (ii) 14g of polyurethane resin and (iii) 18g of curing agent. 14g of polyurethane resin was added to 67.5g of the monoamino silane coupling agent-modified superhydrophobic diatomaceous earth dispersion, stirred for 30min, 18g of the curing agent was added, and stirring was continued for 1 h. Finally, the coating was applied to a 7cm x 2.5cm slide and cured at 180 ℃ for 20 min.
The cured super-hydrophobic coating has good wear resistance, self-cleaning performance and underwater hydrophobicity. The hydrophobic coating of this example had a contact angle of 161.0 deg. (FIG. 8) and a sliding angle of 1 deg. as measured with a contact angle measuring instrument. The coating remained superhydrophobic after 265 grindings with 10cm each on 240 mesh sandpaper under a 500g weight. And (3) spreading fine dust on the surface of the glass slide coated with the super-hydrophobic coating to enable the inclination angle of the glass slide to be 10 degrees, then dripping water drops on the polluted surface, and immediately adsorbing the pollutants on the surface of the water drops and then quickly rolling off, thereby showing that the prepared super-hydrophobic coating has good self-cleaning performance. When the super-hydrophobic coating is soaked under water, a silver mirror phenomenon can be generated at a water-air interface. The glass slide coated with the super-hydrophobic coating is soaked in water with the depth of 20cm, and the silver mirror phenomenon can be maintained for 223 hours, which shows that the prepared coating has good underwater hydrophobicity.
Claims (10)
1. The composition at least comprises a component A, a component B and a component C, wherein the component A is a super-hydrophobic diatomite dispersion liquid with active groups, the component B is resin, and the component C is a curing agent.
2. The abrasion resistant superhydrophobic coating composition according to claim 1, wherein said a component is a diatomaceous earth dispersion modified with a reactive group coupling agent and a hydrophobic agent.
3. The abrasion-resistant superhydrophobic coating composition according to claim 1 or 2, wherein the superhydrophobic diatomite dispersion liquid having active groups of component a is prepared by: dissolving a silane coupling agent containing an active group in a solvent, adding a proper amount of water, adding acid to adjust the pH to acidity to obtain a prehydrolysis solution of the silane coupling agent, then adding the prehydrolysis solution of the silane coupling agent into calcined diatomite, adding a certain amount of solvent, adding acid to adjust the pH to acidity, heating and reacting at a certain temperature for a period of time, performing suction filtration, washing with the solvent for 3 times, drying to obtain diatomite with the active group, then mixing a hydrophobic agent, the diatomite with the active group and the proper amount of solvent, performing suction filtration after reacting at room temperature for a period of time, washing with the solvent for 3 times, drying to obtain super-hydrophobic diatomite, dispersing the super-hydrophobic diatomite in the solvent to obtain a super-hydrophobic diatomite dispersion liquid, wherein the mass ratio of the dosages of the diatomite to the silane coupling agent to the hydrophobic agent is 1: 0.01-0.1: 0.08-0.5, the modification reaction temperature range of the silane coupling agent is 20-100 ℃, the pH range is 2-6.
4. The abrasion-resistant superhydrophobic coating composition according to claims 1-3, wherein the diatomaceous earth of component A is disc-shaped, elliptical, columnar and amorphous diatomaceous earth, preferably columnar diatomaceous earth with a size of 1-100 μm.
5. The abrasion-resistant superhydrophobic coating composition according to claim 1-3, wherein the superhydrophobic diatomite dispersion of component A, the solvent is preferably tetrahydrofuran, acetone, ethyl acetate and combination thereof, and the solid content is 10-50%, preferably 15-30%.
6. An abrasion resistant superhydrophobic coating composition according to claim 1 or 2, wherein said a-component has reactive groups, preferably hydroxyl, amino or epoxy groups and any combination thereof.
7. The abrasion resistant superhydrophobic coating composition according to claim 1 or 2, wherein the hydrophobic agent is heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrichlorosilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrichlorosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltrichlorosilane, and combinations thereof.
8. The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the resin of the B-component is a polyurethane resin containing polyhydroxy or polyamino groups or a fluorine-modified polyurethane resin.
9. The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the curing agent of component C is an aliphatic or aromatic di-or poly-isocyanate.
10. The abrasion-resistant superhydrophobic coating composition according to claim 1, wherein the mass ratio of the a component, the B component and the C component is: 0.72-7: 1: 0.8-1.8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425508A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Metal material with super-hydrophobic surface, preparation method and application thereof, and oil-water separation method |
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| CN109777260A (en) * | 2019-01-28 | 2019-05-21 | 中国科学院兰州化学物理研究所 | A method of traditional coating is changed into super hydrophobic coating |
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Application publication date: 20191227 |