A hydrophobic and oleophobic film layer and a preparation method thereof

Abstract

The specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer and a preparation method thereof, the hydrophobic and oleophobic film layer is prepared by plasma chemical vapor deposition on a substrate surface under pulsed discharge at a frequency of 1-5000 kHz by using a perfluoropolyether monomer containing an acrylate group, the hydrophobic and oleophobic film layer has good hydrophobic and oleophobic properties, and hydrophobic stability and double-85 stability, is environment-friendly, and application of the film layer does not cause biological pollution.

Description

Technical Field

[0001] This disclosure relates to the field of surface modification, and in particular to a hydrophobic and oleophobic film layer and its preparation method. Background Technology

[0002] Hydrophobic and oleophobic coatings can be applied to substrates to achieve self-cleaning, antifouling, and anti-corrosion properties. Preparing oleophobic surfaces is more challenging than preparing hydrophobic surfaces because the surface tension of water (72 mN / m) is much higher than that of oil (25-40 mN / m). Oil can diffuse onto almost any fluorine-free substrate. Substrates or coatings only exhibit varying degrees of oleophobicity when their surface energy is lower than that of the oil. Therefore, the fabrication of oleophobic surfaces requires the use of fluorocarbon groups (-CF2 and -CF3), as they are more effective than hydrocarbons in reducing the surface tension of materials.

[0003] Long-chain perfluoroalkyl compounds (C n F 2n+1 -R, n≥7, LCPFAs are widely used in the preparation of hydrophobic and oleophobic surfaces. However, due to the bioaccumulation and toxicity of LCPFAs to the environment, humans and wildlife, and their difficulty in degradation in nature, their production and application have been phased out. The EU POPs regulation requires a ban on the use of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and their derivatives.

[0004] Perfluoropolyethers (PFPEs) can be used as an alternative to long-chain perfluoroalkyl substances. The perfluorocarbon chain in their main chain is separated by oxygen atoms, and they do not contain long-chain alkyl groups. They have no bioaccumulation toxicity, and their surface energy can be as low as 10-14 mN / m. They can be modified based on perfluoropolyether segments to prepare films with hydrophobic and oleophobic effects.

[0005] However, although the membrane prepared by perfluoropolyether modification has hydrophobic and oleophobic properties, due to the good flexibility of the perfluoropolyether chain segments, when in contact with polar molecules such as water molecules, the perfluoropolyether chains on the surface of the membrane are prone to rearrangement, exposing the polar ether bonds to the air surface, which leads to a decrease in the hydrophobic properties of the membrane, and thus it does not have stable hydrophobic properties in practical applications.

[0006] Therefore, it is necessary to prepare a film with good hydrophobic and oleophobic properties and hydrophobic and oleophobic stability. Summary of the Invention

[0007] A specific embodiment of this disclosure provides a hydrophobic and oleophobic film layer, wherein the hydrophobic and oleophobic film layer is a plasma-polymerized coating formed by plasma contacting a substrate with an organic monomer including monomer α, wherein the monomer α has the structure of formula (1).

[0008]

[0009] In formula (1), R1, R2 and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a linking group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1; the organic monomer is prepared by applying pulse discharge to the gaseous form of the organic monomer by plasma, and the pulse frequency of the pulse discharge is 1 to 5000 kHz.

[0010] Optionally, the pulse width of the pulse discharge is 0.2 to 5 μs, and the pulse voltage is 1 to 1000 V.

[0011] Optionally, the frequency of the pulse discharge is 50 to 500 kHz.

[0012] Optionally, the pulsed discharge is performed by placing a substrate in a plasma reaction chamber, the plasma reaction chamber being provided with two electrodes, and performing the pulsed discharge through the two electrodes; the two electrodes include: a central electrode located at the center of the plasma reaction chamber and a cavity wall electrode located on the inner wall of the plasma reaction chamber.

[0013] Optionally, the central electrode includes at least one cylindrical electrode, and the cavity wall electrode includes at least one electrode plate.

[0014] Optionally, the center electrode and the cavity wall electrode are electrically connected to the same power source.

[0015] Optionally, the organic monomer further includes monomer β, which has two or more carbon-carbon unsaturated bonds.

[0016] Optionally, the carbon-carbon unsaturated bond has the structure of formula (2).

[0017]

[0018] In formula (2), Z1, Z2 and Z3 are each independently selected from alkyl groups that are hydrogen atoms or C1-C4 atoms.

[0019] Optionally, the monomer β has the structure of formula (3).

[0020]

[0021] In equation (3), R5, R6, R7, R8, R9 and R 10 Each and every one is independently selected from alkyl groups consisting of hydrogen atoms or C1-C4 atoms; R 11 For C2-C 10The alkylene or substituted alkylene, where x is an integer from 1 to 10; the substituent of the substituted alkylene is a C1-C4 alkyl or a C1-C4 hydroxyalkyl.

[0022] Optionally, R5, R6, R7, R8, R9 and R 10 Each is independently selected from either a hydrogen atom or a methyl group.

[0023] Optionally, the monomer β has the structure of formula (4).

[0024]

[0025] In equation (4), R 12 For C1-C 10 Alkyl groups, or C groups with hydroxyl substitution 1- C 10 alkyl, R 13 R 14 and R 15 Each independently selected from C1-C 10 alkylene, R 16 R 17 and R 18 Each independently selected from C2-C 10 alkylene, R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27 Each of the following is independently selected from hydrogen atoms or C1-C4 alkyl groups, and y1, y2 and y3 are independently selected from integers from 0 to 10.

[0026] Optionally, in equation (4), the R 12 The R is a C1-C4 alkyl or C1-C4 hydroxyalkyl group. 13 R 14 and R 15 Each R is independently selected from alkylene groups of C1-C4. 16 R 17 and R 18 Each R is independently selected from alkylene groups of C2-C4. 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27Each of the atoms is independently selected from hydrogen atoms or methyl groups, and each of the atoms y1, y2 and y3 is independently selected from integers from 0 to 2.

[0027] Optionally, the monomer β is selected from: ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, 1,5-pentanediol diacrylate. The following are at least one of the following: ester, dipropylene glycol diacrylate, ditripropylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octtriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanediethanol divinyl ether.

[0028] Optionally, the monomer β is at least one of 1,6-hexanediol diacrylate and diethylene glycol diacrylate.

[0029] Optionally, the molar ratio of monomer α to monomer β is 0.5:9.5 to 9.5:0.5.

[0030] Optionally, in formula (1), R1, R2 and R3 are each independently selected from methyl or hydrogen atoms.

[0031] Optionally, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0032] Optionally, the weight-average molecular weight of the monomer α is 1000 or higher.

[0033] Optionally, in formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene groups.

[0034] Optionally, the substituent is one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

[0035] Optionally, in formula (1), L1 is a perfluorinated alkylene group.

[0036] Optionally, the monomer α has the structure shown in formula (5).

[0037]

[0038] In formula (5), a is an integer not less than 1; L2 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

[0039] Optionally, the monomer α has the structure shown in formula (6).

[0040]

[0041] In formula (6), b is an integer not less than 1, c is an integer not less than 1, and L3 is selected from C1-C3 alkylene groups that are linked by a bond or substituted or unsubstituted.

[0042] Optionally, the monomer of formula (1) has the structure shown in formula (7).

[0043]

[0044] In formula (7), d is an integer not less than 1, e is an integer not less than 1, and L4 is a C1-C3 alkylene group selected from the linking bond, or substituted or unsubstituted.

[0045] Optionally, the monomer α has the structure shown in formula (8).

[0046]

[0047] In formula (8), f is an integer not less than 1; L5 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

[0048] Optionally, the water contact angle of the hydrophobic and oleophobic film layer is above 115°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 70°.

[0049] Specific embodiments of this disclosure also provide a device having at least a portion of its surface having any of the hydrophobic and oleophobic film layers described above.

[0050] The specific embodiments of this disclosure also provide a method for preparing any of the above-described hydrophobic and oleophobic films, the method comprising: placing a substrate in a plasma reaction chamber; vaporizing an organic monomer including monomer α and introducing it into the plasma reaction chamber, activating plasma discharge, and chemically vapor-depositing the plasma of the organic monomer on the surface of the substrate to form the hydrophobic and oleophobic film.

[0051] Compared with the prior art, the technical solutions of the embodiments of this disclosure have the following beneficial effects:

[0052] The hydrophobic and oleophobic film layer provided in the specific embodiments of this disclosure is prepared by plasma chemical vapor deposition of an organic monomer including monomer α, wherein the frequency of the plasma discharge used is 1 to 5000 kHz. The water contact angle of the hydrophobic and oleophobic film layer is greater than 115°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is greater than 70°.

[0053] The hydrophobic and oleophobic film layer provided in the specific embodiments of this disclosure further includes an organic monomer β. The water contact angle of the prepared hydrophobic and oleophobic film layer decreases slowly under the conditions of temperature 85°C and humidity 85%RH, and has good hydrophobic and oleophobic stability.

[0054] The hydrophobic and oleophobic film layer provided in the specific embodiments of this disclosure further includes an organic monomer β, and the plasma discharge is implemented through the central electrode and the cavity wall electrode located in the plasma reaction chamber. The water contact angle of the prepared hydrophobic and oleophobic film layer decreases slowly under the conditions of temperature 85°C and humidity 85%RH, and has good hydrophobic and oleophobic stability. Attached Figure Description

[0055] Figure 1 The figures shown are examples of embodiments and comparative examples of the double 85 test results in the specific implementation of this disclosure. Detailed Implementation

[0056] The following describes specific embodiments of this disclosure in detail. This description is exemplary and is only used to explain this disclosure, and should not be construed as limiting this disclosure.

[0057] To achieve hydrophobic and oleophobic effects on the surfaces of substrates, devices, etc., and to possess hydrophobic and oleophobic stability without causing environmental problems, the specific embodiments of this disclosure provide a hydrophobic and oleophobic film layer. This hydrophobic and oleophobic film layer is a plasma-polymerized coating formed by plasma contacting an organic monomer, including monomer α, with the monomer α having the structure of formula (1).

[0058]

[0059] In formula (1), R1, R2, and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a linking group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1. The plasma of the organic monomer is prepared by applying a pulsed discharge to the gaseous form of the organic monomer, and the pulse frequency of the pulsed discharge is 1 to 5000 kHz.

[0060] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the pulse width of the pulsed discharge is 0.2–5 μs, and the pulse voltage is 1–1000 V. In some embodiments, the frequency of the pulsed discharge is 50–500 kHz.

[0061] The hydrophobic and oleophobic film layer of this disclosure, through research, has been found by the inventors to possess excellent hydrophobic and oleophobic effects and stability. This is achieved by using an organic monomer including monomer α and forming the film layer via plasma chemical vapor deposition under plasma discharge frequencies of 1–5000 kHz. The discharge frequency used in this disclosure is higher than that of conventionally used frequencies (less than 1 kHz), increasing the crosslinking density of the polymer. This limits the rearrangement of the perfluoropolyether chains contained in the film layer due to the influence of polar molecules such as polar water molecules, thus improving hydrophobic stability. For non-polar oils, the perfluoropolyether chains in the film layer are relatively stable and do not undergo rearrangement; furthermore, the oleophobic stability is strengthened with increased crosslinking density.

[0062] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the pulsed discharge is performed by placing a substrate in a plasma reaction chamber, the plasma reaction chamber being equipped with a dual electrode, and pulsed discharge being performed through the dual electrode; the dual electrode includes a central electrode located at the center of the plasma reaction chamber and a cavity wall electrode located on the inner wall of the plasma reaction chamber. Compared to single-electrode discharge, dual-electrode discharge is beneficial for forming a more uniform electric field, so that the excited plasma is more uniformly deposited on the substrate surface, forming a more uniform film layer, thereby improving the density of the film layer.

[0063] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the pulsed discharge is performed by placing the substrate in a plasma reaction chamber, wherein the plasma reaction chamber is provided with three or more electrodes, and pulsed discharge is performed through the three or more electrodes.

[0064] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the central electrode includes at least one cylindrical electrode, and the cavity wall electrode includes at least one electrode plate. In some embodiments, to create a more uniformly distributed electric field within the plasma reaction chamber, the cavity wall electrode includes multiple electrode plates uniformly distributed along the inner wall of the plasma chamber.

[0065] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the central electrode and the cavity wall electrode are electrically connected to the same power source to achieve synchronous discharge at the same frequency, thereby making the electric field formed in the plasma reaction chamber more uniform.

[0066] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the organic monomer further includes monomer β.

[0067] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the organic monomer is composed of monomer α and monomer β.

[0068] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β has two or more carbon-carbon unsaturated bonds.

[0069] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the carbon-carbon unsaturated bonds have a structure of formula (2).

[0070]

[0071] In formula (2), Z1, Z2 and Z3 are each independently selected from alkyl groups that are hydrogen atoms or C1-C4 atoms.

[0072] In some embodiments of the hydrophobic and oleophobic film layer of this disclosure, in formula (2), Z1 is selected as a hydrogen atom or a methyl group, and Z2 and Z3 are hydrogen atoms.

[0073] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β has the structure of formula (3).

[0074]

[0075] In equation (3), R5, R6, R7, R8, R9 and R 10 Each and every one is independently selected from alkyl groups consisting of hydrogen atoms or C1-C4 atoms; R 11 For C2-C 10 The alkylene group or substituted alkylene group; the substituent of the substituted alkylene group is a C1-C4 alkyl or a C1-C4 hydroxyalkyl. x is an integer from 1 to 10.

[0076] In some specific embodiments of the hydrophobic and oleophobic film layer of this disclosure, R5, R6, R7, R8, R9 and R... 10 Each is independently selected as a hydrogen atom or a methyl group; in some specific embodiments, R6 and R8 are independently selected as hydrogen atoms or methyl groups, and R5, R7, R9 and R... 10 It is a hydrogen atom.

[0077] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β has the structure of formula (4).

[0078]

[0079] In equation (4), R 12 For C1-C 10 Alkyl groups, or C groups with hydroxyl substitution 1- C 10 alkyl, R 13 R 14 and R 15 Each independently selected from C1-C 10 alkylene, R 16 R 17 and R 18 Each independently selected from C2-C 10 alkylene, R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27 Each of the following is independently selected from hydrogen atoms or C1-C4 alkyl groups, and y1, y2 and y3 are independently selected from integers from 0 to 10.

[0080] In some specific embodiments of the hydrophobic and oleophobic film layer of this disclosure, in formula (4), the R 12 It is a C1-C4 alkyl or C1-C4 hydroxyalkyl, R 13 R 14 and R 15 Each and every one is independently selected from alkylene groups of C1-C4, R 16 R 17 and R 18 Each and every one is independently selected from alkylene groups of C2-C4, R 19 R 20 R 21 R 22 R 23 R24 R 25 R 26 and R 27 Each of the following is independently selected from hydrogen atoms or methyl groups, and y1, y2 and y3 are independently selected from integers from 0 to 2.

[0081] In some specific embodiments of the hydrophobic and oleophobic film layer of this disclosure, in formula (4), the R 12 For ethyl, R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27 For hydrogen atoms, R 13 R 14 and R 15 The methyl group is 0, and y1, y2 and y3 are 0.

[0082] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β is selected from: ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol diacrylate. The following are included in the list of esters, 1,5-pentanediol diacrylate, dipropylene glycol diacrylate, ditripropylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octtriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanediethanol divinyl ether.

[0083] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β is at least one of 1,6-hexanediol diacrylate and diethylene glycol diacrylate.

[0084] In the specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the molar ratio of monomer α to monomer β is related to the hydrophobic, oleophobic, and hydrophobic / oleophobic stability of the film layer. Therefore, the molar ratio of monomer α to monomer β can be set according to the requirements of water contact angle and oil contact angle in actual applications. In some specific embodiments, the molar ratio of monomer α to monomer β is 0.5:9.5 to 9.5:0.5, specifically, for example: 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5, etc.

[0085] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer α has the structure of formula (1), in which R1, R2, and R3 are independently selected from methyl or hydrogen atoms. In some embodiments, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0086] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene groups.

[0087] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the substituent is one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen. In some embodiments, L1 is a straight-chain or branched perfluorinated alkylene group.

[0088] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the weight-average molecular weight of monomer α is 200 or higher. In other embodiments, to ensure better crosslinking density, the weight-average molecular weight of monomer α is 1000 or higher, specifically, for example, 1000, 2000, 3000, 4000, or 5000, etc.

[0089] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segments include a K-type structure, and the monomer α has the structure shown in formula (5).

[0090]

[0091] In formula (5), a is an integer not less than 1; L2 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene; the substituent is selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

[0092] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segments include a Y-type structure, and the monomer α has the structure shown in formula (6).

[0093]

[0094] In formula (6), b is an integer not less than 1, c is an integer not less than 1; L3 is selected from C1-C3 alkylene groups that are linked by a bond, substituted or unsubstituted; the substituents are selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

[0095] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segments include a Z-shaped structure, and the monomer α has the structure shown in formula (7).

[0096]

[0097] In formula (7), d is an integer not less than 1, e is an integer not less than 1; L4 is a C1-C3 alkylene group selected from the group that is linked by a bond or substituted or unsubstituted; the substituent is selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

[0098] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segments include a D-type structure, and the monomer α has the structure shown in formula (8).

[0099]

[0100] In formula (8), f is an integer not less than 1; L5 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene; the substituent is selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, urethane, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

[0101] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, R1 in formulas (5) to (8) is methyl.

[0102] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the water contact angle of the hydrophobic and oleophobic film layer is above 115°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 70°. The water contact angle of the hydrophobic and oleophobic film layer decreases slowly under conditions of 85°C and 85% RH, exhibiting good hydrophobic and oleophobic stability.

[0103] Specific embodiments of this disclosure also provide a device, wherein at least a portion of the surface of the device has any of the above-mentioned hydrophobic and oleophobic film layers. In some specific embodiments, the entire surface of the device has the hydrophobic and oleophobic film layer, for achieving a stable hydrophobic and oleophobic effect over a long period of time.

[0104] In some embodiments of the present disclosure, the device includes electrical components, optical instruments, electronic or electrical components, etc.

[0105] The specific embodiments of this disclosure also provide a method for preparing any of the above hydrophobic and oleophobic film layers. The preparation method includes: placing a substrate in a plasma reaction chamber; vaporizing an organic monomer including monomer α and introducing it into the plasma reaction chamber; turning on plasma discharge with a discharge frequency of 1 to 5000 kHz; and chemically vapor-depositing the plasma of the organic monomer on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0106] In some specific embodiments of the preparation method disclosed herein, the plasma discharge mode is pulsed discharge, and the pulse width of the pulsed discharge is 0.2 to 5 μs, specifically, for example, 0.2 μs, 0.5 μs, 0.8 μs, 1 μs, 2 μs, 3 μs, 4 μs, and 5 μs, etc.

[0107] In some specific embodiments of the preparation method disclosed herein, the plasma discharge mode is pulsed discharge, and the pulse frequency of the pulsed discharge is 1 to 5000 kHz, specifically, for example, 1 kHz, 50 kHz, 100 kHz, 200 kHz, 250 kHz, 300 kHz, 400 kHz, 500 kHz, 1000 kHz, 2000 kHz, 3000 kHz, 4000 kHz, and 5000 kHz, etc. In some specific embodiments, the pulse frequency of the pulsed discharge is 50 to 500 kHz, specifically, for example, 50 kHz, 100 kHz, 200 kHz, 250 kHz, 300 kHz, 400 kHz, or 500 kHz, etc.

[0108] In some specific embodiments of the preparation method disclosed herein, the plasma discharge mode is pulsed discharge, and the pulse voltage is 1 to 1000V, specifically, it can be 1V, 100V, 250V, 300V, 350V, 500V, 600V, 700V, 800V, 900V and 1000V, etc.

[0109] The preparation method of the specific embodiments disclosed herein uses a plasma discharge pulse frequency of 1 to 500 kHz, and no pretreatment step is required before coating.

[0110] In some specific embodiments of the preparation method disclosed herein, the discharge time of the plasma discharge is 60 to 36000 s, specifically for example: 60 s, 360 s, 1200 s, 2400 s, 3600 s, 7200 s, or 36000 s, etc.

[0111] In some specific embodiments of the preparation method disclosed herein, the organic monomer includes monomer α and monomer β; after vaporizing monomer α and monomer β, they are introduced into the plasma reaction chamber, specifically including: adding monomer α, a fluorinated solvent and a polymerization inhibitor to monomer tank one after they are mutually dissolved, and adding monomer β to monomer tank two; heating monomer tank one and monomer tank two to vaporize monomer α and monomer β and then introducing them into the plasma reaction chamber respectively.

[0112] The preparation method of this disclosure controls the molar amount of monomer α relative to monomer β entering the plasma reaction chamber during the coating time by controlling the flow rate ratio of monomer α and monomer β. The molar ratio of monomer α to monomer β is related to the hydrophobic and oleophobic properties, as well as the hydrophobic and oleophobic stability of the hydrophobic and oleophobic film. The flow rates of monomer α and monomer β can be set according to the actual application requirements of the film. In some specific embodiments, the ratio of the gas flow rate from monomer tank one to the gas flow rate from monomer tank two into the plasma reaction chamber is 0.5:9.5 to 9.5:0.5, specifically, for example, 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5, etc.

[0113] In some specific embodiments of the preparation method disclosed herein, the gas flow rate introduced into the plasma reaction chamber from the monomer tank is 10 to 2000 μL / min, specifically, for example: 10 μL / min, 15 μL / min, 30 μL / min, 90 μL / min, 100 μL / min, 120 μL / min, 150 μL / min, 180 μL / min, 210 μL / min, 270 μL / min, 285 μL / min, 300 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, or 2000 μL / min, etc. In some specific embodiments, the gas flow rate introduced into the plasma reaction chamber from the second monomer tank is 10 to 2000 μL / min, specifically, it can be: 10 μL / min, 15 μL / min, 30 μL / min, 90 μL / min, 100 μL / min, 120 μL / min, 150 μL / min, 180 μL / min, 210 μL / min, 270 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min or 2000 μL / min, etc.

[0114] The preparation method of this disclosure, due to the high molecular weight and viscosity of monomer α, involves adding a fluorinated solvent to ensure smooth passage of the monomer into the plasma reaction chamber. In some embodiments, the fluorinated solvent is a fluorocarbon solvent. In some embodiments, the fluorocarbon solvent includes one or more of the following: methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethyl propyl ether, perfluoropolyether oil, hexafluoropropylene oxide dimer, hexafluoropropylene oxide trimer, perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, 3M electronic fluorinated liquid 7100, 3M electronic fluorinated liquid 7200, 3M electronic fluorinated liquid 7300, 3M electronic fluorinated liquid 7500, and 3M electronic fluorinated liquid 7700.

[0115] In some specific embodiments of the preparation method disclosed herein, the weight ratio of monomer α to fluorinated solvent is 1:9 to 9:1, specifically, it can be 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 3:7, 1:2, 1:1, 2:1, 7:3, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9:1, etc.

[0116] The preparation method of this disclosure, in order to prevent monomer α from undergoing polymerization during heating and vaporization, involves adding a polymerization inhibitor to prevent it from polymerizing in the monomer tank. In some specific embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0117] In some specific embodiments of the preparation method disclosed herein, the amount of the polymerization inhibitor is 0.1% to 1% of the mass fraction of the monomer α, specifically for example: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, etc.

[0118] In some embodiments of the preparation method disclosed herein, to prevent polymerization of monomer β during heating and vaporization, a polymerization inhibitor is added to the monomer tank. The amount of the polymerization inhibitor is 0.1% to 1% by mass fraction of monomer β, specifically, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, etc. In some embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0119] In some specific embodiments of the preparation method disclosed herein, the monomer β molecular weight is not large and is not prone to polymerization reaction during heating and vaporization, so there is no need to add polymerization inhibitor.

[0120] In some specific embodiments of the preparation method disclosed herein, during the plasma polymerization process, the temperature of the reaction chamber is 30°C to 60°C, specifically, for example, 30°C, 40°C, 50°C, 55°C, or 60°C, etc.

[0121] The preparation method of this disclosure, in some specific embodiments, further includes post-processing, which includes: after the hydrophobic and oleophobic film layer is prepared on the surface of the substrate, introducing clean compressed air or inert gas until the plasma reaction chamber returns to atmospheric pressure, opening the plasma reaction chamber, and removing the substrate. In some specific embodiments, an inert gas is introduced, and the flow rate of the inert gas is 5–300 sccm.

[0122] The present invention will be further illustrated by specific embodiments below.

[0123] Example

[0124] Test Method Description

[0125] Thickness of the hydrophobic and oleophobic film: measured using a Filmetrics F20-UV film thickness meter (USA).

[0126] Water contact angle of the hydrophobic and oleophobic film: tested according to GB / T 30447-2013 standard.

[0127] Oil contact angle of the hydrophobic and oleophobic film: The contact angle between the film and n-hexadecane was tested using an SDC-100 standard contact angle meter.

[0128] Double 85 test: The substrate with the hydrophobic and oleophobic film layer formed on its surface is placed in an environment with a temperature of 85°C and a humidity of 85%RH. At different times, the water contact angle and oil contact angle of the hydrophobic and oleophobic film layer are tested to characterize the stability of the hydrophobic and oleophobic properties of the film layer.

[0129] Example 1

[0130] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced at a flow rate of 200 sccm, and the chamber temperature is 55°C.

[0131] Maintaining the chamber pressure at 120 mTorr and the helium flow rate at 200 sccm, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone at a weight ratio of 7:3:0.012 was added to monomer tank one. After the monomer in monomer tank one was vaporized at a vaporization temperature of 110℃, the gas from monomer tank one was introduced into the plasma chamber at a flow rate of 300 μL / min. Maintaining the chamber pressure at 120 mTorr and the helium flow rate at 200 sccm, plasma discharge was initiated. The plasma discharge was carried out through a cylindrical electrode located at the center of the plasma chamber. The energy output mode of the plasma discharge was pulsed, and plasma chemical vapor deposition was performed on the substrate surface. The pulse width was 1 μs, the pulse frequency was 250 kHz, the pulse voltage was 350 V, and the reaction time was 3600 s.

[0132] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0133] Comparative Example 1

[0134] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced at a flow rate of 200 sccm, and the chamber temperature is 55°C.

[0135] Maintain the chamber pressure at 120 mTorr and the helium flow rate at 200 sccm. Initiate plasma pulse discharge with a pulse duty cycle of 75% and a discharge power of 300 W. Continuously discharge for 300 s to pretreat the substrate.

[0136] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone were mixed in a weight ratio of 7:3:0.012 to form a homogeneous solution, which was then added to monomer tank one. After the monomer in monomer tank one was vaporized at a vaporization temperature of 110℃, the gas in monomer tank one was introduced into the plasma chamber at a flow rate of 300μL / min. The chamber pressure was maintained at 120 mTorr, the helium flow rate was maintained at 200 sccm, and the plasma discharge was started. The plasma discharge was carried out through a cylindrical electrode located at the center of the plasma chamber. The energy output mode of the plasma discharge was pulsed, and plasma chemical vapor deposition was performed on the substrate surface. The pulse duty cycle was 40%, the pulse frequency was 200Hz, the pulse discharge power was 250W, and the reaction time was 3600s.

[0137] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0138] Example 2

[0139] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced at a flow rate of 200 sccm, and the chamber temperature is 55°C.

[0140] Maintaining the chamber pressure at 120 mTorr and the helium flow rate at 200 sccm, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone at a weight ratio of 7:3:0.012 was added to monomer tank one. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were mixed at a weight ratio of 1:0.005 and added to monomer tank two. After vaporizing the monomers in monomer tanks one and two at a vaporization temperature of 110℃, the gas in monomer tank one... A flow rate of 270 μL / min is introduced into the plasma chamber, and the gas from the second individual tank is introduced into the plasma chamber at a flow rate of 30 μL / min, i.e., the flow rate ratio is 9:1; the chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 200 sccm, and the plasma discharge is initiated. The plasma discharge is carried out through a cylindrical electrode located at the center of the plasma chamber. The energy output mode of the plasma discharge is pulsed, and plasma chemical vapor deposition is performed on the substrate surface. The pulse width is 1 μs, the pulse frequency is 250 kHz, the pulse voltage is 350 V, and the reaction time is 3600 s.

[0141] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0142] Example 3

[0143] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced at a flow rate of 200 sccm, and the chamber temperature is 55°C.

[0144] Maintaining the chamber pressure at 120 mTorr and the helium flow rate at 200 sccm, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone at a weight ratio of 7:3:0.012 was added to monomer tank one. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were mixed at a weight ratio of 1:0.005 and added to monomer tank two. After vaporizing the monomers in monomer tanks one and two at a vaporization temperature of 110℃, the gas flow rate in monomer tank one was 270 μL / min. The gas from the second unit tank is introduced into the plasma chamber at a flow rate of 30 μL / min, i.e., the flow ratio is 9:1. The chamber pressure is maintained at 120 mTorr and the helium flow rate is maintained at 200 sccm. The plasma discharge is started. The cylindrical electrode at the center of the plasma chamber and the cavity wall electrode located on the inner wall of the plasma chamber are electrically connected through the same power supply to discharge. The energy output mode of the plasma discharge is pulsed. Plasma chemical vapor deposition is performed on the substrate surface. The pulse width is 1 μs, the pulse frequency is 250 kHz, the pulse voltage is 350 V, and the reaction time is 3600 s.

[0145] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0146] Example 4

[0147] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 100 mTorr, helium is introduced at a flow rate of 200 sccm, and the chamber temperature is 55°C.

[0148] Maintaining a chamber pressure of 100 mTorr and a helium flow rate of 200 sccm, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone in a weight ratio of 7:3:0.012 was added to monomer tank one. After the monomer in monomer tank one was vaporized at a vaporization temperature of 110℃, the gas from monomer tank one was introduced into the plasma chamber at a flow rate of 250 μL / min. Maintaining a chamber pressure of 100 mTorr and a helium flow rate of 200 sccm, plasma discharge was initiated. The cylindrical electrode at the center of the plasma chamber and the cavity wall electrode located on the inner wall of the plasma chamber were electrically connected through the same power source to discharge. The energy output mode of the plasma discharge was pulsed, and plasma chemical vapor deposition was performed on the substrate surface. The pulse width was 2 μs, the pulse frequency was 50 kHz, the pulse voltage was 250 V, and the reaction time was 3600 s.

[0149] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0150] Example 5

[0151] The Si wafer is placed on the substrate support of the plasma chamber, the chamber is evacuated to 90 mTorr, helium is introduced at a flow rate of 150 sccm, and the chamber temperature is 55°C.

[0152] Maintaining the chamber pressure at 90 mTorr and the helium flow rate at 150 sccm, a homogeneous solution of 3M-7500 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone at a weight ratio of 7:3:0.012 was added to monomer tank one. Diethylene glycol diacrylate (DEGDA) and 2,6-di-tert-butyl-p-cresol were added to monomer tank two after being miscibly dissolved at a weight ratio of 1:0.005. After vaporizing the monomers in monomer tanks one and two at a vaporization temperature of 110℃, the gas in monomer tank one was released at a flow rate of 270 μL / min. The flow rate of n is introduced into the plasma chamber, and the gas from the second unit tank is introduced into the plasma chamber at a flow rate of 30 μL / min, i.e., the flow rate ratio is 9:1; the chamber pressure is maintained at 90 mTorr, the helium flow rate is maintained at 150 sccm, the plasma discharge is started, and the cylindrical electrode at the center of the plasma chamber and the cavity wall electrode located on the inner wall of the plasma chamber are electrically connected through the same power supply to discharge. The energy output mode of the plasma discharge is pulsed, and plasma chemical vapor deposition is performed on the substrate surface, wherein the pulse width is 0.5 μs, the pulse frequency is 500 kHz, the pulse voltage is 300 V, and the reaction time is 3600 s;

[0153] After coating, compressed air was introduced to restore the chamber to normal pressure. The coated substrate was then removed, and the film thickness, water contact angle, and oil contact angle were tested. The test results are listed in Table 1 below. The substrate was then placed in a high-temperature and high-humidity environment for a double 85 test; the test results are shown below. Figure 1 .

[0154] Table 1. Test results of water contact angle and oil contact angle

[0155] Film thickness / nm Water contact angle / ° Oil (n-hexadecane) contact angle / ° Example 1 167 118 74 Comparative Example 1 153 117 72 Example 2 234 116 73 Example 3 260 117 71 Example 4 134 115 70 Example 5 245 118 73

[0156] Figure 1 The graphs showing the double 85 test results of Examples 1 to 5 and Comparative Example 1 are illustrated. Figure 1 It can be seen that, compared to Comparative Example 1, the films prepared using higher discharge frequencies in Examples 1 and 4 exhibit better stability of water contact angle in a double 85°C environment. Higher discharge frequencies result in greater plasma energy, making it easier to activate chemical bonds in monomers, leading to more readily formed cross-linked structures and better film density. Therefore, the water contact angle decreases more slowly in a double 85°C environment. The films prepared in Examples 1 to 5 show a slower decrease in water contact angle compared to the film prepared in Comparative Example 1 in an environment of 85°C and 85% RH.

[0157] Compared to Example 1, Example 2 uses a higher frequency plasma discharge and also uses the monomer β described in the specific embodiments of this disclosure to prepare a film with a higher crosslinking density. As a result, the film prepared in Example 2 has a slower rate of decrease in water contact angle over time in an environment with a temperature of 85°C and a humidity of 85%RH, and its hydrophobic stability is higher.

[0158] Compared to Example 2, Examples 3 and 5, in addition to implementing higher frequency plasma discharge through cylindrical electrodes, also use cavity wall electrodes for simultaneous discharge. The electric field distribution in the plasma chamber is more uniform, the number of monomers generated by the activated plasma increases, and a film layer with higher crosslinking density is obtained. The film layers prepared in Examples 3 and 5 have a slower decrease in water contact angle over time in an environment of 85°C and 85%RH, and their hydrophobic stability is higher.

[0159] The membrane prepared in Example 5 exhibits optimal hydrophobic stability under double 85 conditions.

[0160] As shown in Table 1, compared with Comparative Example 1, under the same coating time conditions, the film prepared in Example 1 has a greater thickness and a faster film formation speed, thus providing better protection for the substrate.

[0161] In Examples 2, 3, and 5, monomer β, as described in the specific embodiments of this disclosure, was added. Since monomer β has two or more double bonds, it increases the crosslinking density of the film layer, increases the film formation rate on the substrate surface, and the film layer prepared in the same time has a greater thickness.

[0162] The above description is merely an exemplary embodiment used to illustrate the principles of this disclosure and is not intended to limit the scope of protection of this disclosure. Various modifications and improvements can be made by those skilled in the art without departing from the spirit and substance of this disclosure, and these modifications and improvements are also within the scope of protection of this disclosure.

Claims

1. A hydrophobic and oleophobic film layer, characterized in that, The hydrophobic and oleophobic film layer is a plasma-polymerized coating formed by contacting a substrate with an organic monomer including monomer α and monomer β, wherein the monomer α has the structure of formula (1). ， （1） In formula (1), R1, R2 and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a linking group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1; The monomer β has two or more carbon-carbon unsaturated bonds; The plasma of the organic monomer is prepared by applying a pulsed discharge to the gaseous form of the organic monomer, wherein the frequency of the pulsed discharge is 1~5000kHz.

2. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The pulse width of the pulse discharge is 0.2~5μs, and the pulse voltage is 1~1000V.

3. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The frequency of the pulse discharge is 50~500kHz.

4. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The pulsed discharge is performed by placing a substrate in a plasma reaction chamber, the plasma reaction chamber being provided with two electrodes, and performing the pulsed discharge through the two electrodes; the two electrodes include: a central electrode located at the center of the plasma reaction chamber and a cavity wall electrode located on the inner wall of the plasma reaction chamber.

5. The hydrophobic and oleophobic film layer according to claim 4, characterized in that, The central electrode includes at least one cylindrical electrode, and the cavity wall electrode includes at least one electrode plate.

6. The hydrophobic and oleophobic film layer according to claim 5, characterized in that, The central electrode and the cavity wall electrode are electrically connected to the same power source.

7. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The carbon-carbon unsaturated bonds have the structure of formula (2). ， （2） In formula (2), Z1, Z2 and Z3 are each independently selected from alkyl groups that are hydrogen atoms or C1-C4 atoms.

8. The hydrophobic and oleophobic film layer according to claim 7, characterized in that, The monomer β has the structure of formula (3). ， （3） In equation (3), R5, R6, R7, R8, R9 and R 10 Each and every one is independently selected from alkyl groups consisting of hydrogen atoms or C1-C4 atoms; R 11 For C2-C 10 Alkylene or substituted alkylene, where x is an integer from 1 to 10; The substituents of the substituted alkylene group are C1-C4 alkyl or C1-C4 hydroxyalkyl.

9. The hydrophobic and oleophobic film layer according to claim 8, characterized in that, The R5, R6, R7, R8, R9 and R 10 Each is independently selected from either a hydrogen atom or a methyl group.

10. The hydrophobic and oleophobic film layer according to claim 7, characterized in that, The monomer β has the structure of formula (4). ， （4） In equation (4), R 12 For C1-C 10 Alkyl groups, or C groups with hydroxyl substitution 1- C 10 alkyl, R 13 R 14 and R 15 Each independently selected from C1-C 10 alkylene, R 16 R 17 and R 18 Each independently selected from C2-C 10 alkylene, R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27 Each of the following is independently selected from hydrogen atoms or C1-C4 alkyl groups, and y1, y2 and y3 are independently selected from integers from 0 to 10.

11. The hydrophobic and oleophobic film layer according to claim 10, characterized in that, In equation (4), R 12 The R is a C1-C4 alkyl or C1-C4 hydroxyalkyl group. 13 R 14 and R 15 Each R is independently selected from alkylene groups of C1-C4. 16 R 17 and R 18 Each R is independently selected from alkylene groups of C2-C4. 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 and R 27 Each of the atoms is independently selected from hydrogen atoms or methyl groups, and each of the atoms y1, y2 and y3 is independently selected from integers from 0 to 2.

12. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer β is selected from: ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, 1,5-pentanediol diacrylate. The following are at least one of the following: dipropylene glycol diacrylate, ditripropylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octtriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanediethanol divinyl ether.

13. The hydrophobic and oleophobic film layer according to claim 12, characterized in that, The monomer β is at least one of 1,6-hexanediol diacrylate and diethylene glycol diacrylate.

14. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The molar ratio of monomer α to monomer β is 0.5:9.5 ~ 9.5:0.

5.

15. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, In formula (1), R1, R2 and R3 are each independently selected from methyl or hydrogen atoms.

16. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, In formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

17. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The weight-average molecular weight of the monomer α is above 1000.

18. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, In formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene groups.

19. The hydrophobic and oleophobic film layer according to claim 18, characterized in that, The substituent is one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate ion, carboxylate ester, carbamate, alkoxy, ketone, aldehyde, amino, amide, hydroxyl, nitrile, nitrite, and halogen.

20. The hydrophobic and oleophobic film layer according to claim 19, characterized in that, In formula (1), L1 is a perfluorinated alkylene group.

21. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer α has the structure shown in formula (5). ， （5） In formula (5), a is an integer not less than 1; L2 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

22. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer α has the structure shown in formula (6). ， （6） In formula (6), b is an integer not less than 1, c is an integer not less than 1, and L3 is selected from C1-C3 alkylene groups that are linked by a bond or substituted or unsubstituted.

23. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer α has the structure shown in formula (7). ， （7） In formula (7), d is an integer not less than 1, e is an integer not less than 1, and L4 is a C1-C3 alkylene group selected from the linking bond, or substituted or unsubstituted.

24. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer α has the structure shown in formula (8). ， （8） In formula (8), f is an integer not less than 1; L5 is selected from the linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

25. The hydrophobic and oleophobic film layer according to any one of claims 1-24, characterized in that, The water contact angle of the hydrophobic and oleophobic film layer is 115°. o The hexadecane contact angle of the aforementioned hydrophobic and oleophobic film layer is 70°. o above.

26. A method for preparing a hydrophobic and oleophobic film layer as described in any one of claims 1-25, characterized in that, include: The substrate is placed inside the plasma reaction chamber; The organic monomers, including monomers α and β, are vaporized and introduced into the plasma reaction chamber. Plasma discharge is then initiated, and the plasma of the organic monomers is chemically vapor-deposited on the substrate surface to form the hydrophobic and oleophobic film layer.

27. A device, characterized in that, At least a portion of the surface of the device has a hydrophobic and oleophobic film layer as described in any one of claims 1-25.

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