CN111171648A - Preparation method of wear-resistant super-hydrophobic coating - Google Patents
Preparation method of wear-resistant super-hydrophobic coating Download PDFInfo
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- CN111171648A CN111171648A CN202010168772.1A CN202010168772A CN111171648A CN 111171648 A CN111171648 A CN 111171648A CN 202010168772 A CN202010168772 A CN 202010168772A CN 111171648 A CN111171648 A CN 111171648A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2301/00—Inorganic additives or organic salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2320/00—Organic additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
Abstract
The invention relates to a preparation method of a wear-resistant super-hydrophobic coating, which comprises the following steps of mixing 8.4-23.2% of silicate ester, 4.8-9.5% of long-chain siloxane coupling agent, 3.1-9.4% of deionized water, 59.7-75.6% of alcohol solvent and 0.15-0.22% of alkaline catalyst for reaction to obtain super-hydrophobic silicon dioxide; stirring 4.5-11.2% of acrylate A, 3.9-25.4% of acrylate B, 15.4-42.2% of other components, 1.4-6.3% of thermal initiator and 45-70% of solvent to react to obtain an acrylate copolymer; uniformly mixing the super-hydrophobic silicon dioxide, the acrylate copolymer and the alcohol solvent according to the proportion of 1-5: 8:70, spraying the mixture onto a base material, and curing to obtain the wear-resistant super-hydrophobic coating. The method has the advantages of simple and easily-controlled process, good adaptability of the coating base material, friction resistance, strong adhesive force, long service life and environmental friendliness.
Description
Technical Field
The invention relates to a preparation method of a wear-resistant super-hydrophobic coating, and particularly belongs to the technical field of paint preparation.
Background
Super-hydrophobic materials have been known for a number of years because of their extensive use in the fields of self-cleaning, oil-water separation, ice-over prevention, etc. Two key factors for constructing the super-hydrophobic material are the micro-nano structure and the low surface energy. For metal materials, the traditional method is to obtain a micro-nano structure by etching materials, and the premise of protecting the materials is that the materials are damaged to a certain extent unreasonably. Other methods such as electrospinning are highly equipment demanding and are not suitable for large scale production. In addition, the super-hydrophobic material has low wear resistance and durability, which limits the use of the super-hydrophobic material in many fields. In order to enhance the wear resistance and prolong the service life of the material, one possible method is to endow the material with self-repairing performance, when the material is rubbed off one layer on the outermost surface, substances with low surface energy spontaneously migrate to the surface of the material under the stimulation of environment to complete the super-hydrophobic self-repairing, but actually proves that even if the self-repairing super-hydrophobic material of the type is developed, the application requirements of the material in reality are difficult to meet.
At present, the wear-resistant super-hydrophobic coating can only be used on the same base material, or the wear-resistant condition is met but the super-hydrophobic function of the surface is uneven, and the fluorine coupling agent which is difficult to degrade is more likely to be used as a hydrophobic modifier to cause harm to the environment. The invention has low cost and substrate adaptability, meets the wear resistance of the coating and is environment-friendly.
Disclosure of Invention
The invention aims to provide a preparation method of a wear-resistant super-hydrophobic coating, which is simple, convenient and nontoxic, can be used for large-scale preparation and production, and can solve the problems that the existing super-hydrophobic material is difficult to produce on a large scale and has poor durability.
The invention is realized in such a way that the preparation method of the wear-resistant super-hydrophobic coating comprises the following three steps:
step 1: preparation of super-hydrophobic silica
According to the mass percentage, 8.4 to 23.2 percent of silicate ester, 4.8 to 9.5 percent of long-chain siloxane coupling agent, 3.1 to 9.4 percent of deionized water, 59.7 to 75.6 percent of alcohol solvent and 0.15 to 0.22 percent of alkaline catalyst are controlled;
adding silicate ester and a long-chain siloxane coupling agent into a mixed solvent of an alcohol solvent and deionized water according to the raw material proportion, then adding an alkaline catalyst, and stirring and mixing at 60-70 ℃ for 6-16 h to obtain the long-chain siloxane coupling agent modified super-hydrophobic silicon dioxide; wherein the concentration of the silicate ester and the long-chain siloxane coupling agent in the mixed solvent is not more than 0.45 mol/L;
step 2: preparation of acrylate copolymer:
according to the mass percentage, 4.5 to 11.2 percent of the acrylate A component, 3.9 to 25.4 percent of the acrylate B component, 15.4 to 42.2 percent of other components, 1.4 to 6.3 percent of thermal initiator and 45 to 70 percent of solvent are controlled;
stirring and mixing the materials at 65-70 ℃ for 7-14 h to obtain an acrylate copolymer;
and step 3: preparation of the coating
Controlling the proportion of the super-hydrophobic silicon dioxide, the acrylate copolymer and the alcohol solvent to be 1-5: 8:70 in percentage by mass, uniformly mixing, spraying the mixture onto a base material, controlling the spraying pressure to be 0.8 Mpa and spraying a layer of coating for 2s, wherein the distance between a spray gun and a substrate of the base material is 30cm, and the caliber of the spray gun is 1.0 mm; after spraying, curing the coating with the thickness of 200-300 mu m for 5-60 min at room temperature to form a film, and obtaining the wear-resistant super-hydrophobic coating.
The alcohol solvent is one or a combination of methanol, ethanol or isopropanol.
The silicate is one or the combination of three of tetrabutyl orthosilicate, propyl orthosilicate, ethyl silicate or methyl orthosilicate;
the long-chain siloxane coupling agent is one or a combination of more of dodecyl trimethoxy silane coupling agent, hexadecyl trimethoxy silane coupling agent, octadecyl trimethoxy silane coupling agent, dodecyl triethoxy silane coupling agent, hexadecyl triethoxy silane coupling agent and octadecyl triethoxy silane coupling agent.
The alkaline catalyst is one or the combination of two of ammonia water, sodium hydroxide or potassium hydroxide.
The thermal initiator is one or the combination of two of benzoyl peroxide and azodiisobutyronitrile.
The solvent is one or a combination of more of tetrahydrofuran, toluene and isopropanol.
The acrylate A, the acrylate B and other components are respectively different one of methyl acrylate, methyl methacrylate, butyl acrylate, isobutyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, ethyl methacrylate, lauryl methacrylate or lauryl acrylate.
The invention has the beneficial effects that: the preparation process is simple and easy to control, the scale production is easy, the super-hydrophobic coating base material has good adaptability, the coating is durable, the friction resistance is high, the adhesive force is strong, the service life is long, and the environment-friendly effect is realized.
Drawings
FIG. 1 is a graph of the hydrophobic effect of the superhydrophobic coating of the invention.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
This example illustrates the formulation of an abrasion resistant superhydrophobic coating provided by the present invention.
The first step is as follows: preparation of super-hydrophobic silica: propyl orthosilicate, ethanol, deionized water and octadecyltrimethoxysilane coupling agent are mixed in a three-neck flask according to the mass ratio of 12.4: 72.8: 5.9: 7.9, and stirred for 8 hours at 64 ℃ in an oil bath kettle.
The second step is that: preparation of acrylate copolymer: mixing hydroxyethyl methacrylate, butyl methacrylate, acrylic acid, azobisisobutyronitrile, toluene in a ratio of 10: 10: 40: 0.4: 60 parts by weight of the components are mixed in a four-neck flask and stirred for 7 hours in an oil bath kettle at 70 ℃.
The third step: uniformly mixing the super-hydrophobic silicon dioxide of the first step, the acrylate copolymer of the second step and ethanol in a mass ratio of 4: 8:70, spraying the mixture onto a substrate, and curing for 1 hour at room temperature.
Example 2
This example illustrates the formulation of an abrasion resistant superhydrophobic coating provided by the present invention.
The first step is as follows: super-hydrophobic silica: ethyl orthosilicate, ethanol, deionized water and dodecyl trimethoxy silane are mixed in a ratio of 13.4: 73.2: 9.9: 6.5 in mass ratio, and stirred in an oil bath kettle at 68 ℃ for 8 hours.
The second step is that: preparation of acrylate copolymer: mixing methyl methacrylate, butyl methacrylate, acrylic acid, azobisisobutyronitrile, toluene in a ratio of 10: 11: 40: 0.35: 40 in a four-necked flask and stirred in an oil bath pan at 64 ℃ for 12 hours.
The third step: uniformly mixing the super-hydrophobic silicon dioxide of the first step, the acrylate copolymer of the second step and ethanol according to the mass ratio of 8:8:70, spraying the mixture on a substrate, and curing for 25 hours at room temperature.
Example 3
This example illustrates the formulation of an abrasion resistant superhydrophobic coating provided by the present invention.
The first step is as follows: super-hydrophobic silica: ethyl orthosilicate, ethanol, deionized water, hexadecyl trimethoxy silane, and a reaction product of 18.4: 63.2: 14.9: 3.5, stirring the mixture in a three-neck flask for 8 hours.
The second step is that: preparation of acrylate copolymer: mixing isooctyl acrylate, butyl methacrylate, acrylic acid, azobisisobutyronitrile, tetrahydrofuran and water in a weight ratio of 8: 10: 42: 0.4: 60 parts by weight were stirred in a four-necked flask for 7 hours.
The third step: and (3) uniformly mixing the super-hydrophobic silicon dioxide of the first step, the acrylate copolymer of the second step and ethanol in a ratio of 6:9:90, spraying the mixture on a substrate, and curing the mixture at room temperature for 30 min.
Claims (8)
1. A preparation method of a wear-resistant super-hydrophobic coating is characterized by comprising the following steps: the preparation method comprises the following three steps:
step 1: preparation of super-hydrophobic silica
According to the mass percentage, 8.4 to 23.2 percent of silicate ester, 4.8 to 9.5 percent of long-chain siloxane coupling agent, 3.1 to 9.4 percent of deionized water, 59.7 to 75.6 percent of alcohol solvent and 0.15 to 0.22 percent of alkaline catalyst are controlled;
adding silicate ester and a long-chain siloxane coupling agent into a mixed solvent of an alcohol solvent and deionized water according to the raw material proportion, then adding an alkaline catalyst, and stirring and mixing at 60-70 ℃ for 6-16 h to obtain the long-chain siloxane coupling agent modified super-hydrophobic silicon dioxide; wherein the concentration of the silicate ester and the long-chain siloxane coupling agent in the mixed solvent is not more than 0.45 mol/L;
step 2: preparation of acrylate copolymer:
according to the mass percentage, 4.5 to 11.2 percent of the acrylate A component, 3.9 to 25.4 percent of the acrylate B component, 15.4 to 42.2 percent of other components, 1.4 to 6.3 percent of thermal initiator and 45 to 70 percent of solvent are controlled;
stirring and mixing the materials at 65-70 ℃ for 7-14 h to obtain an acrylate copolymer;
and step 3: preparation of the coating
Controlling the proportion of the super-hydrophobic silicon dioxide, the acrylate copolymer and the alcohol solvent to be 1-5: 8:70 in percentage by mass, uniformly mixing, spraying the mixture onto a base material, controlling the spraying pressure to be 0.8 Mpa and spraying a layer of coating for 2s, wherein the distance between a spray gun and a substrate of the base material is 30cm, and the caliber of the spray gun is 1.0 mm; after spraying, curing the coating with the thickness of 200-300 mu m for 5-60 min at room temperature to form a film, and obtaining the wear-resistant super-hydrophobic coating.
2. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the alcohol solvent is one or a combination of methanol, ethanol or isopropanol.
3. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the silicate is one or the combination of three of tetrabutyl orthosilicate, propyl orthosilicate, ethyl silicate or methyl orthosilicate.
4. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the long-chain siloxane coupling agent is one or a combination of more of dodecyl trimethoxy silane coupling agent, hexadecyl trimethoxy silane coupling agent, octadecyl trimethoxy silane coupling agent, dodecyl triethoxy silane coupling agent, hexadecyl triethoxy silane coupling agent and octadecyl triethoxy silane coupling agent.
5. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the alkaline catalyst is one or the combination of two of ammonia water, sodium hydroxide or potassium hydroxide.
6. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the thermal initiator is one or the combination of two of benzoyl peroxide and azodiisobutyronitrile.
7. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the solvent is one or a combination of more of tetrahydrofuran, toluene and isopropanol.
8. The method for preparing an abrasion-resistant superhydrophobic coating of claim 1, wherein: the acrylate A, the acrylate B and other components are respectively different one of methyl acrylate, methyl methacrylate, butyl acrylate, isobutyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, ethyl methacrylate, lauryl methacrylate or lauryl acrylate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647306A (en) * | 2020-07-14 | 2020-09-11 | 南通贝得彩色印刷有限公司 | In situ generation of organized SiO2Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof |
| CN112981973A (en) * | 2021-03-19 | 2021-06-18 | 南昌航空大学 | Preparation method of pH response super-hydrophobic material |
| CN116376406A (en) * | 2023-06-05 | 2023-07-04 | 西南石油大学 | TiO (titanium dioxide) 2 /H-SiO 2 EP superhydrophobic composite coating, preparation method and application thereof |
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| WO2005021843A1 (en) * | 2003-09-02 | 2005-03-10 | Sabanci Universitesi | Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them |
| CN103865372A (en) * | 2014-04-08 | 2014-06-18 | 中山职业技术学院 | Preparation method of fluorine-containing acrylic acid super-hydrophobic coating |
| CN107892270A (en) * | 2017-12-18 | 2018-04-10 | 广州中科检测技术服务有限公司 | A kind of super-hydrophobic nano particle and preparation method and application |
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2020
- 2020-03-12 CN CN202010168772.1A patent/CN111171648A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021843A1 (en) * | 2003-09-02 | 2005-03-10 | Sabanci Universitesi | Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them |
| CN103865372A (en) * | 2014-04-08 | 2014-06-18 | 中山职业技术学院 | Preparation method of fluorine-containing acrylic acid super-hydrophobic coating |
| CN107892270A (en) * | 2017-12-18 | 2018-04-10 | 广州中科检测技术服务有限公司 | A kind of super-hydrophobic nano particle and preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647306A (en) * | 2020-07-14 | 2020-09-11 | 南通贝得彩色印刷有限公司 | In situ generation of organized SiO2Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof |
| CN112981973A (en) * | 2021-03-19 | 2021-06-18 | 南昌航空大学 | Preparation method of pH response super-hydrophobic material |
| CN116376406A (en) * | 2023-06-05 | 2023-07-04 | 西南石油大学 | TiO (titanium dioxide) 2 /H-SiO 2 EP superhydrophobic composite coating, preparation method and application thereof |
| CN116376406B (en) * | 2023-06-05 | 2024-02-09 | 西南石油大学 | TiO (titanium dioxide) 2 /H-SiO 2 EP superhydrophobic composite coating, preparation method and application thereof |
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Application publication date: 20200519 |