CN109232964B - Flexible lubricating coating and preparation method and application thereof - Google Patents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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Abstract
The invention provides a preparation method of a flexible lubricating coating, which is characterized in that flexible molecules containing fluorine/organic silicon are uniformly coated on the porous surface of a polymer by brush coating to obtain the lubricating coating. The coating prepared by the preparation method is provided, the coating has a super-hydrophobic super-oleophylic lubricating coating with a porous structure, the preparation method is simple to operate, the technical requirement is low, large-scale preparation is easy, and the coating has good anti-icing characteristic after adsorbing lubricating oil. Also provided is the use of the coating in a flexible lubricious coating in an anti-icing coating.
Description
Technical Field
The invention relates to a flexible lubricating coating and a preparation method and application thereof, belonging to the field of coating preparation and application.
Background
The icing phenomenon under the low temperature condition brings inconvenience to human society in the fields of traffic, spaceflight, electric power, telecommunication and the like, and even causes serious safety accidents. At present, the preparation methods of the super-hydrophobic surface, such as a sol-gel method, a chemical corrosion method, chemical vapor deposition, a photoetching method, a template method and the like, which are researched more frequently have the problems of complex method, high technical requirement, difficulty in large-scale preparation and the like, and the problem can be well solved by preparing the super-hydrophobic surface by a coagulation bath method, but the microstructure of the super-hydrophobic surface is easily damaged, so that the durability of the anti-icing performance is influenced; moreover, studies have shown that the anti-icing properties of superhydrophobic surfaces under high humidity conditions are not ideal. In recent years, the flexible lubricating surface prepared by adsorbing flexible molecular compounds or oligomers to replace air in a super-hydrophobic surface becomes a hot spot of current research, and has wide application potential in the anti-icing field. .
Disclosure of Invention
In order to solve the problems, the invention provides a flexible lubricating coating, a preparation method and application thereof.
The invention is realized by the following technical scheme:
a flexible lubricating coating is composed of a fluorine-containing polymer porous surface and fluorine-containing/organic silicon flexible molecules.
According to the preparation method of the flexible lubricating coating, the fluorine/organic silicon containing flexible molecules are uniformly coated on the porous surface of the polymer by brush coating, so that the lubricating coating is obtained.
Preferably, the flexible molecule is the fluorine-containing or organosilicon flexible molecule is perfluoropolyether (30/35/40 mm)2Per second), perfluorotripentylamine, perfluorotributylamine and silicone oil (10/20/50/100 mPa/s) in an amount of 0.2-1.0L/m2。
Preferably, the preparation method of the polymer porous surface comprises the following steps: firstly, dissolving a polymer in a solvent to prepare a solution with the mass fraction of 10-40%, preparing a polymer membrane by a spraying or blade coating method, then soaking the polymer membrane in a coagulating bath at 10-40 ℃ for 12-96 hours, and drying at room temperature for 12-24 hours to obtain the polymer porous membrane with the thickness of 250-1000 mu m.
Preferably, the polymer is obtained by olefin metathesis polymerization of norbornene or cyclooctene fluorine-containing ester; the catalyst for metathesis polymerization is a Gela cloth second-generation catalyst, the reaction temperature is 25-35 ℃, and the reaction time is 12-24 hours.
More preferably, the norbornene has the structure shown below:
R1Comprises the following steps:
preferably, the molecular weight of the polymer is 20000-120000, the water contact angle of the flat surface of the polymer is more than 95 degrees, and the structure of the polymer is shown as formula II:
R2comprises the following steps:
the reaction process is as follows:
preferably, the solvent is one or a mixture of two of dichloromethane, trifluorotoluene, N-dimethylformamide, tetrahydrofuran, toluene and pentafluorodichloropropane; the coagulating bath is n-hexane, n-heptane, anhydrous ethanol and water.
The tensile strength of the polymer porous membrane is 1-10MPa, and the elongation at break is 100-850%.
The lubricating coating prepared by the preparation method has a water contact angle of more than 102 degrees and a contact angle hysteresis of less than 20 degrees.
Use of a flexible lubricious coating as described above in an anti-icing coating.
Advantageous effects
The lubricating coating is formed by compounding a homopolymer porous surface and lubricating oil through adsorption. The polymer film has high tensile strength (1-10 MPa), good flexibility and elongation at break up to 850%, the water contact angle of the prepared lubricating coating is larger than 102 degrees, the contact angle hysteresis is lower than 20 degrees, the ice adhesion strength of the lubricating surface is lower than 50Kpa, lubricating oil is stored in a surface porous structure and is not easy to lose, and the polymer film still has low ice adhesion strength after 20 times of icing and deicing cycles, and the anti-icing performance is durable and stable.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the norbornene carboxylic acid tetrafluoropropyl ester comprises the following steps: first, 4.62g of tetrafluoropropanol, 5.53g of 5-norbornene-2-carboxylic acid, 7.45g of trimethylacetic anhydride and 42.76mg of 4-methylaminopyridine were dissolved in 50ml of tetrahydrofuran, reacted at 50 ℃ for 24 hours, and then subjected to saturated NaHCO3Washing the solution with saturated NaCl solution and water, adding proper anhydrous MgSO4Drying and rotary evaporation to obtain a light yellow viscous liquid.
Preparing a norbornene carboxylic acid tetrafluoropropyl ester polymer by the following preparation method: first, 3.03g of tetrafluoropropyl norbornene carboxylate was dissolved in 50ml of methylene chloride in an ice bath, and then oxygen was removed by introducing nitrogen gas, and then Gribbs 2 was used as a second generation catalystnd) 50.94mg of the polymer was dissolved in methylene chloride and injected into a reaction flask via a syringe, nitrogen was continuously introduced for 30 minutes, the ice bath was removed, the reaction was carried out at 35 ℃ for 12 hours, then two drops of 2-perfluorooctylethylene were added dropwise to terminate the reaction, and the polymer was obtained by rotary evaporation.
Preparation of a polymeric porous surface: 1g (molecular weight: 20000) of the prepared norbornene carboxylic acid tetrafluoropropyl homopolymer was dissolved in 1.5g of methylene chloride to prepare a 40% solution by mass fraction. The solution was then drawn down on a glass plate, then soaked in n-hexane at 40 ℃ for 12 hours, the solvent dichloromethane was removed to form a porous structure, and after drying at room temperature for 12 hours, a porous surface of the polymer was obtained with a thickness of 250 μm.
Preparing a lubricating coating: perfluoropolyether (40 mm)2S, the brush coating amount is 0.2L/m2) UniformityThe lubricating coating is obtained by coating the surface of the polymer porous surface.
Example 2
The preparation method of the norbornene carboxylic acid octafluoropentyl ester comprises the following steps: first 8.12g of octafluoropentyl ester, 5.53g of 5-norbornene-2-carboxylic acid, 7.45g of trimethylacetic anhydride and 42.76mg of 4-methylaminopyridine were dissolved in 50ml of tetrahydrofuran, reacted at 60 ℃ for 18 hours, and then saturated NaHCO was added thereto3Washing the solution with saturated NaCl solution and water, adding proper anhydrous MgSO4Drying and rotary evaporation to obtain a light yellow viscous liquid.
The preparation method of the norbornene carboxylic acid octafluoropentyl ester polymer comprises the following steps: firstly, 3.15g of norbornene carboxylic acid octafluoropentyl ester is dissolved in 50ml of dichloromethane under ice bath, nitrogen is introduced to remove oxygen, and then the Grubbs 2 catalyst is removednd) 37.99mg of the polymer is dissolved in dichloromethane and injected into a reaction bottle through a syringe, nitrogen is continuously introduced for 30 minutes, the ice bath is removed, the reaction is carried out for 18 hours at the temperature of 30 ℃, then two drops of 2-perfluorooctylethylene are added dropwise to stop the reaction, and the polymer is obtained by rotary evaporation.
Preparation of a polymeric porous surface: 1g (molecular weight: 75000) of the prepared norbornene carboxylic acid octafluoropentyl ester homopolymer was dissolved in 2.3g of tetrahydrofuran to prepare a solution having a mass fraction of 30%. The solution was then drawn down on a glass plate, then soaked in distilled water at 25 ℃ for 48 hours, the solvent tetrahydrofuran was removed to form a porous structure, and after drying at room temperature for 18 hours, a porous surface of the polymer was obtained with a thickness of 500 μm.
Preparing a lubricating coating: perfluorotripentylamine (brushing amount 0.7L/m)2) And uniformly brushing the mixture on the porous surface of the polymer to obtain the lubricating coating.
Example 3
Preparation of perfluorooctylethyl cyclooctene: firstly, 6.50g of 2-perfluorooctylethyl alcohol, 3.20g of cyclooctene-4-mercapto-acetic acid, 2.98g of trimethylacetic anhydride and 23mg of 4-methylaminopyridine are dissolved in 30ml of tetrahydrofuran, reacted for 12 hours at 70 ℃, and subjected to saturated NaHCO3Washing the solution with saturated NaCl solution and water, adding proper anhydrous MgSO4Drying, and rotary steaming to obtain yellowish viscous liquidAnd (3) a body.
The preparation method of the cyclooctene perfluorooctyl ethyl ester polymer comprises the following steps: perfluorooctylethyl cyclooctene 5.58g was first dissolved in 50ml of dichloromethane in an ice bath, deoxygenated by purging with nitrogen, and then the catalyst Grubbs 2nd) 36.71mg of the polymer was dissolved in dichloromethane and injected into a reaction flask via a syringe for 30 minutes under nitrogen, the ice bath was removed, the reaction was carried out at 25 ℃ for 24 hours, and then two drops of 2-perfluorooctylethylene were added dropwise to terminate the reaction, and the polymer was obtained by rotary evaporation.
Preparation of a polymeric porous surface: 1.86g (molecular weight: 120000) of the produced cyclooctene perfluorooctyl ethyl ester homopolymer was dissolved in 16.74g of trifluorotoluene to prepare a solution having a mass fraction of 10%. Spraying the solution on a 300-mesh steel wire mesh, soaking the steel wire mesh in absolute ethyl alcohol at 10 ℃ for 96 hours, removing the solvent benzotrifluoride to form a porous structure, and drying the porous structure for 24 hours at room temperature to obtain a polymer porous surface with the thickness of 1000 mu m and the pore diameter of 20-30 mu m.
Preparing a lubricating coating: the silicone oil (10 mPa/s, brush coating amount is 1.0L/m)2) And uniformly brushing the mixture on the porous surface of the polymer to obtain the lubricating coating.
The mechanical properties and anti-icing properties of the flexible lubricating coatings prepared in examples 1-3 are shown in table 1:
TABLE 1 mechanical and anti-icing Properties of Flexible lubricating coatings
Compared with the smooth metal aluminum surface, the ice adhesion strength of the flexible lubricating coating prepared by the invention on the anti-icing coating surface is reduced by 96%, and the ice coating amount is reduced by 75% at-20 ℃; the water icing delay time of the surface of the flexible lubricating coating is more than 60s, and the elongation at break is up to 845%.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (3)
1. A preparation method of a flexible lubricating coating is characterized in that flexible molecules containing fluorine or organic silicon are uniformly coated on a porous surface of a polymer by brush coating to obtain the lubricating coating; the water contact angle of the lubricating coating is larger than 102 degrees, and the contact angle hysteresis is lower than 20 degrees;
wherein the fluorine-containing or organic silicon flexible molecule is perfluoropolyether, perfluorotripentylamine, perfluorotributylamine and silicone oil, and the brush coating amount is 0.2-1.0L/m2；
The preparation method of the polymer porous surface comprises the following steps: firstly, dissolving a polymer in a solvent to prepare a solution with the mass fraction of 10-40%, preparing a polymer membrane with the thickness of 250-1000 mu m by a spraying or blade coating method, then soaking the polymer membrane in a coagulating bath at 10-40 ℃ for 12-96 hours, and drying at room temperature for 12-24 hours to obtain the polymer porous membrane; the tensile strength of the polymer porous membrane is 1-10MPa, and the elongation at break is 100-850%;
the molecular weight of the polymer is 20000-120000, the water contact angle of the flat surface of the polymer is more than 95 degrees, and the structure of the polymer is shown as formula II:
formula II
R2Comprises the following steps:
the polymer is obtained by olefin metathesis polymerization of norbornene or cyclooctene fluorine-containing ester; the catalyst for metathesis polymerization is a Gela cloth second-generation catalyst, the reaction temperature is 25-35 ℃, and the reaction time is 12-24 hours;
the structure of the norbornene or cyclooctene fluorine-containing ester is shown as follows:
R1comprises the following steps:
the solvent is one or a mixture of two of dichloromethane, trifluorotoluene, N-dimethylformamide, tetrahydrofuran, toluene and pentafluorodichloropropane; the coagulating bath is n-hexane, n-heptane, anhydrous ethanol and water.
2. A flexible lubricating coating produced by the production method according to claim 1.
3. Use of a flexible lubricating coating according to claim 2 in an anti-icing coating.
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| CN114656594B (en) * | 2021-12-14 | 2023-08-15 | 济南大学 | Preparation method and application of high-strength anti-icing organogel |
| CN114213632B (en) * | 2021-12-14 | 2023-08-22 | 济南大学 | Preparation method and application of amphiphilic fluorine-containing copolymer membrane with protein adsorption resistance |
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| CN105713476A (en) * | 2016-02-02 | 2016-06-29 | 浙江大学 | Super-smooth anti-icing coating with heat energy deicing performance |
| CN107502127A (en) * | 2017-09-06 | 2017-12-22 | 济南大学 | A kind of fluorine-containing lubricant coating and its preparation method and application |
| CN107501484A (en) * | 2017-09-06 | 2017-12-22 | 济南大学 | A kind of fluorine-containing polyolefin copolymer of combed and preparation method and application |
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| WO2015153021A2 (en) * | 2014-03-31 | 2015-10-08 | Exxonmobil Research And Engineering Company | Low viscosity, low volatility lubricating basestocks |
| CN105713476A (en) * | 2016-02-02 | 2016-06-29 | 浙江大学 | Super-smooth anti-icing coating with heat energy deicing performance |
| CN107502127A (en) * | 2017-09-06 | 2017-12-22 | 济南大学 | A kind of fluorine-containing lubricant coating and its preparation method and application |
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