Hydrophobic and oleophobic film layer and preparation method thereof

Abstract

The specific embodiment of the invention provides a hydrophobic and oleophobic film layer and a preparation method of the hydrophobic and oleophobic film layer. The coating is a plasma polymerization coating formed by plasmas of monofunctional perfluoropolyether (methyl) acrylate, a monomer with more than two carbon-carbon unsaturated bonds and a silane monomer with at least one silicon-oxygen bond and an unsaturated group, and the film layer is good and stable in hydrophobic and oleophobic performance and good in friction resistance.

Description

Technical Field

[0001] The present disclosure relates to the field of surface modification, and particularly to a hydrophobic and oleophobic film layer and a preparation method thereof. Background Art

[0002] The hydrophobic and oleophobic film layer can be applied to a substrate to achieve surface self-cleaning, anti-fouling, anti-corrosion, etc. The preparation of an oleophobic surface is more challenging than that of a hydrophobic surface 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. Only when the surface energy of the substrate or coating is lower than that of the oil, the substrate or coating shows different degrees of oleophobicity. Therefore, for the manufacture of oleophobic surfaces, fluorocarbon groups (-CF2 and -CF3) need to be used because they can reduce the surface tension of materials more effectively than hydrocarbons.

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

[0004] Perfluoropolyethers (PFPEs) can be used as substitutes for long-chain perfluoroalkyl substances. The perfluorocarbon chains in their main chains are interrupted by oxygen atoms, without long fluorocarbon chain alkyl groups, and have no bioaccumulative toxicity. Moreover, their surface energy can be as low as 10 - 14 mN / m, and a film layer with hydrophobic and oleophobic effects can be prepared by modifying based on perfluoropolyether segments.

[0005] However, although the film layer prepared by perfluoropolyether modification has hydrophobic and oleophobic properties, due to the good flexibility of the perfluoropolyether segments, when in contact with polar molecules such as water, the perfluoropolyether chains on the surface of the film layer are prone to rearrangement, exposing the polar ether bonds on the air surface, resulting in a decrease in the hydrophobic performance of the film layer; in addition, the film layer prepared by perfluoropolyether modification generally has poor friction resistance and is difficult to have stable hydrophobic performance in practical applications.

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

[0007] A specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer, which is a plasma polymerization coating formed by a substrate contacting the plasma of monomer α, monomer β, and monomer γ. Monomer α has the structure of formula (1),

[0008]

[0009] In formula (1), R1, R2, and R3 are each 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 m repeating units, n in each repeating unit is independently selected from integers not less than 1; the monomer β has two or more carbon-carbon unsaturated bonds, and the monomer γ has the structure of formula (2),

[0010]

[0011] In formula (2), L2 is a linking group; R5 is selected from substituted or unsubstituted C1-C4 hydrocarbon groups, substituted or unsubstituted C1-C4 acyl groups, or substituted or unsubstituted C1-C 10 alkylsilyl groups; R6 and R7 are each independently selected from substituted or unsubstituted C1-C4 hydrocarbon oxy groups, substituted or unsubstituted C1-C4 hydrocarbon groups, substituted or unsubstituted C1-C4 acyloxy groups, or substituted or unsubstituted C1-C 10 alkylsiloxanyl groups; R8 includes one or more of acryloxy groups, epoxy groups, cycloalkyl groups, alkenyl groups, or cyano groups.

[0012] In some embodiments, R8 is selected from substituted or unsubstituted C1-C4 alkenyl groups, substituted or unsubstituted C1-C4 alkynyl groups, cyano groups, substituted or unsubstituted epoxy groups, C2-C 10 epoxyalkoxy groups, or C3-C 10 epoxycycloalkyl groups.

[0013] In some embodiments, the L2 is selected from a linking bond, substituted or unsubstituted C1-C4 alkylene groups, the structure of formula (3), or the structure of formula (4).

[0014]

[0015] In some embodiments, the R5 is selected from alkoxy-substituted C1-C4 alkyl groups, C1-C4 alkyl groups, C1-C4 acyl groups, or C1-C6 trialkylsilyl groups; the R6 and R7 are each independently selected from alkoxy-substituted C1-C4 alkoxy groups, C1-C4 alkoxy groups, C1-C4 alkyl groups, C1-C4 acyloxy groups, or C1-C6 trialkylsiloxanyl groups.

[0016] In some embodiments, the L2 is selected from the structure of formula (3), the R8 is selected from substituted or unsubstituted C1-C4 alkenyl groups; the R5 is selected from C1-C4 alkyl groups or C1-C6 trialkylsilyl groups; the R6 and R7 are each independently selected from C1-C4 alkoxy groups, C1-C4 alkyl groups, or C1-C6 trialkylsiloxanyl groups.

[0017] In some embodiments, R8 is selected from vinyl or isopropenyl.

[0018] In some embodiments, R8 is selected from glycidyloxy or epoxycyclohexyl, L2 is selected from substituted or unsubstituted C1-C4 alkylene, R5 is selected from C1-C4 alkyl, and R6 and R7 are each independently selected from C1-C4 alkoxy or C1-C4 alkyl.

[0019] In some embodiments, R8 is selected from vinyl, propenyl, isopropenyl or cyano, L2 is selected from a linking bond, or substituted or unsubstituted C1-C4 alkylene, R5 is selected from alkoxy-substituted C1-C4 alkyl, C1-C4 alkyl, C1-C4 acyl; R6 and R7 are each independently selected from alkoxy-substituted C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkyl, or C1-C4 acyloxy.

[0020] In some embodiments, the monomer γ is selected from at least one of: 3-(methacryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris(trimethylsiloxy)silane, 3-methacryloyloxypropyltriethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)methyldimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, γ-glycidylethoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)-silane, vinyltriisopropoxysilane, methylvinyldimethoxysilane, vinyltriacetoxysilane, cyanoethyltriethoxysilane, cyanoethyltrimethoxysilane, cyanoethylmethyldiethoxysilane, cyanoethylmethyldimethoxysilane, cyanoethyltriacetoxysilane.

[0021] In some embodiments, the monomer γ is selected from at least one of: γ-methacryloyloxypropyltris(trimethylsiloxy)silane, 3-(methacryloyloxy)propyltrimethoxysilane, or 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0022] In some embodiments, the carbon-carbon unsaturated bond of the monomer β has the structure of formula (5).

[0023]

[0024] In formula (5), Z1, Z2 and Z3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0025] In some embodiments, the monomer β has the structure of formula (6),

[0026]

[0027] In formula (6), R9, R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 15 is an alkylene or substituted alkylene group having 2 to 10 carbon atoms, x is an integer from 1 to 10; the substituent of the substituted alkylene group is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms.

[0028] In some embodiments, the R9, R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from a hydrogen atom or a methyl group.

[0029] In some embodiments, the monomer β is selected from at least one of: 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, 1,3 - butanediol diacrylate, 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, dipropylene glycol diacrylate or dipropylene glycol triacrylate.

[0030] In some embodiments, the monomer β has the structure of formula (7),

[0031]

[0032] In formula (7), R 16 is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1- C 10 carbon atoms substituted with a hydroxyl group, R17 , R 18 and R 19 are each independently selected from C1-C 10 alkylene, R 20 , R 21 and R 22 are each independently selected from C2-C 10 alkylene, R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from a hydrogen atom, or an alkyl group of C1-C4. y1, y2, and y3 are each independently selected from integers from 0 to 10.

[0033] In some embodiments, in formula (7), the R 16 is an alkyl group of C1-C4 or a hydroxyalkyl group of C1-C4, the R 17 , R 18 and R 19 are each independently selected from C1-C4 alkylene, the R 20 , R 21 and R 22 are each independently selected from C2-C4 alkylene, the R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from a hydrogen atom or a methyl group, and the y1, y2, and y3 are each independently selected from integers from 0 to 2.

[0034] In some embodiments, the monomer β is selected from at least one of: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0035] In some embodiments, the monomer β is selected from at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol 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-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether, etc.

[0036] In some embodiments, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane trimethacrylate, and 1,6-hexanediol dimethacrylate.

[0037] In some embodiments, the ratio of the mass of the monomer α to the sum of the masses of the monomer β and the monomer γ is 0.5:9.5 to 9.5:0.5.

[0038] In some embodiments, the ratio of the mass of the monomer α to the sum of the masses of the monomer β and the monomer γ is 3:7 to 9:1.

[0039] In some embodiments, the mass of the monomer γ accounts for 5% to 95% of the sum of the masses of the monomer β and the monomer γ.

[0040] In some embodiments, in formula (1), R1, R2, and R3 are each independently selected from a methyl group or a hydrogen atom.

[0041] In some embodiments, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0042] In some embodiments, the weight-average molecular weight of the monomer α is 200 to 5000.

[0043] In some embodiments, in formula (1), L1 is selected from substituted or unsubstituted C1-C4 alkylene groups.

[0044] In some embodiments, the substituents of the substitution are one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl, carboxylate ion, carboxylic ester group, carbamate group, alkoxy group, ketone group, aldehyde group, amine group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

[0045] In some embodiments, in formula (1), L1 is a perfluorinated alkylene group.

[0046] In some embodiments, the monomer α has the structure shown in formula (8).

[0047]

[0048] In formula (8), a is an integer not less than 1; L3 is selected from a linking bond, a substituted methylene or ethylene group, or an unsubstituted methylene or ethylene group.

[0049] In some embodiments, the monomer α has the structure shown in formula (9),

[0050]

[0051] In formula (9), b is an integer not less than 1, and c is an integer not less than 1; L4 is selected from a linking bond, or a substituted or unsubstituted C1-C3 alkylene group.

[0052] In some embodiments, the monomer α has the structure shown in formula (10),

[0053]

[0054] In formula (10), d is an integer not less than 1, and e is an integer not less than 1; L5 is selected from a linking bond, or a substituted or unsubstituted C1-C3 alkylene group.

[0055] In some embodiments, the monomer α has the structure shown in formula (11),

[0056]

[0057] In formula (11), f is an integer not less than 1; L6 is selected from a linking bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

[0058] In some embodiments, the water contact angle of the hydrophobic and oleophobic film layer is above 105°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 60°.

[0059] In some embodiments, when the hydrophobic and oleophobic film layer uses a dust-free cloth as a friction material, a friction resistance test is carried out under the conditions of a pressure of 1 N and a rotation speed of 50 r / min. After 1000 times of friction, the water contact angle of the hydrophobic and oleophobic film layer is above 100°.

[0060] The specific embodiments of the present disclosure further provide a device, at least part of the surface of which has the above-mentioned hydrophobic and oleophobic film layer.

[0061] The specific embodiments of the present disclosure further provide a preparation method of the above-mentioned hydrophobic and oleophobic film layer. The preparation method includes: placing a substrate in a plasma reaction chamber; vaporizing the monomer α, monomer β, and monomer γ and introducing them into the plasma reaction chamber, and turning on plasma discharge. The plasma of the monomer α, monomer β, and monomer γ undergoes chemical vapor deposition on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0062] In some embodiments, introducing the vaporized monomer α, monomer β, and monomer γ into the plasma reaction chamber includes: mixing monomer α, a solvent, and an inhibitor to form mixture 1, and mixing monomer β and monomer γ to form mixture 2; heating to vaporize mixture 1 and mixture 2 and then introducing them into the plasma reaction chamber separately.

[0063] In some embodiments, the flow rate of mixture 1 introduced into the plasma reaction chamber is 10 - 2000 μL / min, and the flow rate of mixture 2 introduced into the plasma reaction chamber is 10 - 2000 μL / min.

[0064] In some embodiments, the mass of the inhibitor is 0.1% - 1% of the mass of monomer α.

[0065] In some embodiments, an inhibitor is also added to mixture 2, and the mass of the inhibitor is 0.1% - 1% of the total mass of monomer β and monomer γ.

[0066] In some embodiments, the weight ratio of monomer α to the solvent is 1:9 - 9:1.

[0067] In some embodiments, the solvent includes one or both of a fluorinated acrylate and an organic solvent; the fluorinated acrylate includes one or more of trifluoroethyl methacrylate, trifluoroethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, heptafluorobutyl methacrylate, heptafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H-perfluoropropyl methacrylate, perfluoroalkyl ethyl methacrylate, (2H-perfluoropropyl)-2-acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate; the organic solvent includes one or more of ethyl acetate, butyl acetate, and acetone.

[0068] In some embodiments, the solvent includes one or more of a fluorinated acrylate and butyl acetate.

[0069] In some embodiments, the plasma discharge is continuous discharge, the discharge power is 10 - 300 W, and the discharge time is 60 - 36000 s.

[0070] In some embodiments, the plasma discharge is a pulsed discharge, with a discharge power of 10 - 400 W, a pulse duty cycle of 0.1% - 90%, a pulse frequency of 10 - 500 Hz, and a discharge time of 200 - 36000 s.

[0071] In some embodiments, the method for preparing the hydrophobic and oleophobic film layer further includes: before the chemical vapor deposition, evacuating to 10 - 200 mTorr, introducing a mixed gas of one or more of the gases He, Ar, and O2, and turning on the plasma discharge to pre-treat the substrate.

[0072] Compared with the prior art, the technical solutions of the embodiments of the present disclosure have the following beneficial effects:

[0073] The hydrophobic and oleophobic film layer provided by the embodiments of the present disclosure is a plasma polymerization coating formed by plasma of a monofunctional perfluoropolyether (meth)acrylate, a monomer having two or more carbon-carbon unsaturated bonds, and a silane monomer having at least one siloxane bond and an unsaturated group, and has good hydrophobic and oleophobic properties. The water contact angle of the hydrophobic and oleophobic film layer is above 105°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 60°. Further, the water contact angle of the hydrophobic and oleophobic film layer is above 110°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 65°.

[0074] The hydrophobic and oleophobic film layer provided by the specific embodiments of the present disclosure has good friction resistance. When using a non-woven cloth as the friction material and performing a friction resistance test under the conditions of a pressure of 1 N and a rotation speed of 50 r / min, the water contact angle of the hydrophobic and oleophobic film layer is above 100° after 1000 frictions, and the water contact angle of the hydrophobic and oleophobic film layer is above 95° after 2000 frictions. Description of the Drawings

[0075] Figure 1 It is a schematic diagram of the friction resistance performance test results of the film layers in Embodiments 1 - 4 and Comparative Examples 1 - 4 of the present disclosure. Detailed Description of the Embodiments

[0076] The following details the specific embodiments of the present disclosure. The description is exemplary and is only used to explain the present disclosure, and should not be construed as a limitation to the present disclosure.

[0077] The inventors found through research that a hydrophobic and oleophobic film layer formed by plasma chemical vapor deposition of a monofunctional perfluoropolyether (meth)acrylate, a monomer β having two or more carbon-carbon unsaturated bonds, and a silane monomer γ having at least one siloxane bond and an unsaturated group has good hydrophobic and oleophobic properties and friction resistance, and thus has high hydrophobic and oleophobic stability. The monomer β, the monomer γ and the monomer α undergo plasma polymerization, which increases the crosslinking density of the polymer, restricts the rearrangement of the perfluoropolyether chains, and improves the friction resistance and hydrophobic and oleophobic stability.

[0078] To achieve the hydrophobic and oleophobic effects on the surfaces of substrates, devices, etc., and have good friction resistance and hydrophobic and oleophobic stability, while not causing environmental problems, the specific embodiments of the present disclosure provide a hydrophobic and oleophobic film layer, and the hydrophobic and oleophobic film layer is a plasma polymerization coating formed by the plasma of a substrate contacting the monomer α, the monomer β and the monomer γ.

[0079] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, the monomer α has the structure of formula (1),

[0080]

[0081] In formula (1), R1, R2 and R3 are each independently selected from a C1-C4 hydrocarbon group or a hydrogen atom; R4 is selected from a C1-C4 perfluoro-substituted alkyl group or a fluorine atom; L1 is a linking group; m is an integer not less than 1; in m repeating units, n of each repeating unit is independently selected from an integer not less than 1.

[0082] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, the monomer α has the structure of formula (1), and in formula (1), R1, R2 and R3 are each independently selected from a methyl group or a hydrogen atom. In some specific embodiments, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0083] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, in order to ensure better crosslinking density, the weight-average molecular weight of the monomer α is 200 to 5000, and specifically, for example, it can be 200, 500, 800, 1000, 2000, 3000, 4000 or 5000, etc.

[0084] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, in formula (1), L1 is selected from: a substituted or unsubstituted C1-C4 alkylene group.

[0085] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure. In some specific embodiments, the substituents of the substitution are one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl group, carboxylate ion, carboxylate ester group, carbamate group, alkoxy group, keto group, aldehyde group, amine group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen. In some specific embodiments, L1 is a straight-chain or branched perfluoro-substituted alkylene group. In some specific embodiments, L1 is a perfluoro-substituted alkylene group.

[0086] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure. In some specific embodiments, the perfluoropolyether chain segment includes a K-type structure, and the monomer α has the structure shown in formula (8).

[0087]

[0088] In formula (8), a is an integer not less than 1; L3 is selected from a linking bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group; the substituents of the substitution are selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl group, carboxylate ion, carboxylate ester group, carbamate group, alkoxy group, keto group, aldehyde group, amine group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

[0089] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure. In some specific embodiments, the perfluoropolyether chain segment includes a Y-type structure, and the monomer α has the structure shown in formula (9).

[0090]

[0091] In formula (9), b is an integer not less than 1, and c is an integer not less than 1; L4 is selected from a linking bond, a substituted or unsubstituted C1-C3 alkylene group; the substituents of the substitution are selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl group, carboxylate ion, carboxylate ester group, carbamate group, alkoxy group, keto group, aldehyde group, amine group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

[0092] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure. In some specific embodiments, the perfluoropolyether chain segment includes a Z-type structure, and the monomer α has the structure shown in formula (10).

[0093]

[0094] In formula (10), d is an integer not less than 1, and e is an integer not less than 1; L5 is selected from a linking bond or a substituted or unsubstituted C1-C3 alkylene group; the substituents of the substitution are selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl group, carboxylate ion, carboxylic acid ester group, carbamate group, alkoxy group, keto group, aldehyde group, amino group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

[0095] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the perfluoropolyether chain segment includes a D-type structure, and the monomer α has the structure shown in formula (11).

[0096]

[0097] In formula (11), f is an integer not less than 1; L6 is selected from a linking bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group; the substituents of the substitution are selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl group, carboxylate ion, carboxylic acid ester group, carbamate group, alkoxy group, keto group, aldehyde group, amino group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

[0098] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formulas (8) to (11), R1 is a methyl group.

[0099] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, the monomer γ has the structure of formula (2).

[0100]

[0101] In formula (2), L2 is a linking group; R5 is selected from a substituted or unsubstituted C1-C4 hydrocarbon group, a substituted or unsubstituted C1-C4 acyl group, or a substituted or unsubstituted C1-C 10 alkylsilyl group; wherein, C1-C4 and C1-C 10 do not include the number of carbon atoms in the substituents. The substituents of the substitution include: C1-C3 alkyl group, C1-C3 alkoxy group, halogen atom, etc.

[0102] In some specific embodiments, R5 is selected from the substituted or unsubstituted C1-C4 hydrocarbon group or C1-C4 acyl group, and may be a straight-chain structure or a branched-chain structure. In some specific embodiments, R5 is selected from the substituted or unsubstituted C1-C 10 alkylsilyl group, wherein the alkyl groups connected to the silicon atom can be 1 to 3, and the alkyl groups connected to the silicon atom can be the same or different alkyl groups.

[0103] In some specific embodiments, R5 is selected from alkoxy-substituted C1-C4 alkyl, C1-C4 alkyl, C1-C4 acyl, or C1-C6 trialkylsilyl; in the alkoxy-substituted C1-C4 alkyl, specifically, it can be methoxyethyl, methoxymethyl, ethoxymethyl, ethoxyethyl, etc.; for the C1-C6 trialkylsilyl, specifically, it can be trimethylsilyl, triethylsilyl, dimethylethylsilyl, diethylmethylsilyl, etc.

[0104] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in formula (2), R6 and R7 are each independently selected from substituted or unsubstituted C1-C4 hydrocarbyloxy, substituted or unsubstituted C1-C4 hydrocarbyl, substituted or unsubstituted C1-C4 acyloxy, or substituted or unsubstituted C1-C 10 alkylsiloxanyl; wherein, C1-C4 and C1-C 10 do not include the number of carbon atoms in the substituent. The substituents of the substitution include: C1-C3 alkyl, C1-C3 alkoxy, halogen atoms, etc.

[0105] In some specific embodiments, R6 and R7 are each independently selected from the substituted or unsubstituted C1-C4 hydrocarbyl, C1-C4 hydrocarbyloxy, C1-C4 acyloxy, and can be in a straight-chain structure or a branched-chain structure. In some specific embodiments, R6 and R7 are each independently selected from substituted or unsubstituted C1-C 10 alkylsiloxanyl, wherein the alkyl groups connected to the silicon atom can be 1 to 3, and the alkyl groups connected to the silicon atom can be the same or different alkyl groups.

[0106] In some specific embodiments, R6 and R7 are each independently selected from alkoxy-substituted C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 acyloxy, or C1-C6 trialkylsiloxanyl; for the alkoxy-substituted C1-C4 alkoxy, specifically, it can be methoxyethoxy, methoxymethoxy, ethoxymethoxy, ethoxyethoxy, etc.; for the C1-C6 trialkylsiloxanyl, specifically, it can be trimethylsiloxanyl, triethylsiloxanyl, dimethylethylsiloxanyl, diethylmethylsiloxanyl, etc.

[0107] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in formula (2), R8 includes one or more of acryloyloxy, epoxy, cycloalkyl, alkenyl, or cyano.

[0108] In some specific embodiments, R8 is selected from substituted or unsubstituted C1-C4 alkenyl, substituted or unsubstituted C1-C4 alkynyl, cyano, substituted or unsubstituted epoxy, C2-C 10 epoxyalkyloxy, or C3-C 10Epoxy cycloalkyl group. For a substituted C1-C4 alkenyl group or a substituted C1-C4 alkynyl group, where C1-C4 does not include the number of carbon atoms in the substituent. For a substituted C1-C4 alkenyl group, a substituted C1-C4 alkynyl group, and a substituted epoxy group, the substituents of the substitution include: a C1-C3 alkyl group, a C1-C3 alkoxy group, a halogen atom, etc.

[0109] In some specific embodiments of the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, L2 is selected from a linking bond, a substituted or unsubstituted C1-C4 alkylene group, the structure of formula (3), or the structure of formula (4).

[0110]

[0111] In some specific embodiments of the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, L2 is selected from the structure of formula (3), R8 is selected from a substituted or unsubstituted C1-C4 alkenyl group; R5 is selected from a C1-C4 alkyl group or a trialkylsilyl group with C1-C6; R6 and R7 are each independently selected from a C1-C4 alkoxy group, a C1-C4 alkyl group, or a trialkylsiloxanyl group with C1-C6.

[0112] In some specific embodiments, R8 is selected from vinyl, propenyl, isopropenyl, etc.

[0113] In some specific embodiments, the monomer γ is selected from one or more of: 3-(methacryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris(trimethylsiloxy)silane, 3-methacryloyloxypropyltriethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)methyldimethoxysilane.

[0114] In some specific embodiments of the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, R8 is selected from epoxypropoxy or epoxycyclohexyl; L2 is selected from a substituted or unsubstituted C1-C4 alkylene group, R5 is selected from a C1-C4 alkyl group, and R6 and R7 are each independently selected from a C1-C4 alkoxy group or a C1-C4 alkyl group.

[0115] In some specific embodiments, the monomer γ is selected from: 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, or one or more of them.

[0116] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, R8 is selected from vinyl, propenyl, isopropenyl or cyano, L2 is selected from a linking bond, or a substituted or unsubstituted C1-C4 alkylene group, and R5 is selected from an alkoxy-substituted C1-C4 alkyl group, a C1-C4 alkyl group, or a C1-C4 acyl group; R6 and R7 are each independently selected from an alkoxy-substituted C1-C4 alkoxy group, a C1-C4 alkoxy group, a C1-C4 alkyl group, or a C1-C4 acyloxy group.

[0117] In some specific embodiments, R8 is vinyl or isopropenyl; L2 is a linking bond.

[0118] In some specific embodiments, R8 is cyano and L2 is a C1-C4 alkylene group.

[0119] In some specific embodiments, the monomer γ is selected from at least one of: vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriisopropoxysilane, methylvinyldimethoxysilane, vinyltriacetoxysilane, cyanoethyltriethoxysilane, cyanoethyltrimethoxysilane, cyanoethylmethyldiethoxysilane, cyanoethylmethyldimethoxysilane, cyanoethyltriacetoxysilane.

[0120] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, the monomer γ is selected from at least one of: γ-methacryloxypropyltris(trimethylsiloxy)silane, 3-(methacryloxy)propyltrimethoxysilane, or 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0121] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, the monomer β has two or more carbon-carbon unsaturated bonds.

[0122] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, the carbon-carbon unsaturated bond of the monomer β has the structure of formula (5).

[0123]

[0124] In formula (5), Z1, Z2, and Z3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0125] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, in some specific embodiments, in formula (5), Z1 is selected from a hydrogen atom or a methyl group, and Z2 and Z3 are hydrogen atoms.

[0126] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, in some specific embodiments, the monomer β has the structure of formula (6),

[0127]

[0128] In formula (6), R9, R 10 , R 11 , R 12 , R 13 , and R 14 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 15 is an alkylene group or a substituted alkylene group having 2 to 10 carbon atoms; the substituent of the substituted alkylene group is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. x is an integer from 1 to 10.

[0129] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, in some specific embodiments, in formula (6), R9, R 10 , R 11 , R 12 , R 13 , and R 14 are each independently selected from a hydrogen atom or a methyl group; in some specific embodiments, R 10 and R 12 are each independently selected from a hydrogen atom or a methyl group, and R9, R 11 , R 13 , and R 14 are hydrogen atoms.

[0130] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, in some specific embodiments, in formula (6), R9, R 10 , R 11 , R 12 , R 13 , and R 14 are hydrogen atoms, R 15 is an ethylene group, and x is 2.

[0131] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, in some specific embodiments, in formula (6), R9, R 10 , R 11 , R 12 , R 13 and R14 is a hydrogen atom, and R 15 is a hexamethylene group, and x is 1.

[0132] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the monomer β is selected from at least one of 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, 1,3-butanediol diacrylate, 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, dipropylene glycol diacrylate or dipropylene glycol triacrylate.

[0133] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the monomer β has the structure of formula (7),

[0134]

[0135] In formula (7), R 16 is an alkyl group of C1-C 10 or an alkyl group of C 1- C 10 substituted with a hydroxyl group, and R 17 , R 18 and R 19 are each independently selected from an alkylene group of C1-C 10 , and R 20 , R 21 and R 22 are each independently selected from an alkylene group of C2-C 10 , and R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from a hydrogen atom or an alkyl group of C1-C4, and y1, y2 and y3 are each independently selected from an integer from 0 to 10.

[0136] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formula (7), the R 16is an alkyl group of C1-C4 or a hydroxyalkyl group of C1-C4, R 17 , R 18 and R 19 are each independently selected from an alkylene group of C1-C4, R 20 , R 21 and R 22 are each independently selected from an alkylene group of C2-C4, R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from a hydrogen atom or a methyl group, and y1, y2 and y3 are each independently selected from an integer of 0 to 2.

[0137] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formula (7), the R 16 is ethyl, and R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are hydrogen atoms, R 17 , R 18 and R 19 are methyl groups, and y1, y2 and y3 are 0.

[0138] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the monomer β is selected from at least one of: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0139] For the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the monomer β is selected from at least one of: pentaerythritol tetraacrylate, polydi(ethylene glycol) pentaacrylate, polydi(ethylene glycol) 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-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether, etc.

[0140] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure. In some specific embodiments, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane trimethacrylate, and 1,6 - hexanediol dimethacrylate.

[0141] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, the mass ratio of the monomer α, the monomer β, and the monomer γ is related to the hydrophobic property, oleophobic property, and friction resistance of the hydrophobic and oleophobic film layer. Therefore, the mass ratio of the monomer α, the monomer β, and the monomer γ can be set according to the requirements of the water contact angle and oil contact angle in actual applications. In some specific embodiments, the ratio of the mass of the monomer α to the sum of the masses of the monomer β and the monomer γ is 0.5:9.5 to 9.5:0.5. Specifically, for example, it can be 0.5:9.5, 3:7, 1:9, 5:5, 6:4, 7:3, 8:2, 9:1, or 9.5:0.5, etc.

[0142] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, the mass ratio of the monomer α to the monomer β is 3:7 to 9:1.

[0143] For the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, by setting the dosage between the monomer β and the monomer γ, the hydrophobic and oleophobic properties and friction resistance of the film layer are enhanced. In some specific embodiments, the mass of the monomer γ accounts for 5% - 95% of the sum of the masses of the monomer β and the monomer γ; further, the mass of the monomer γ accounts for 20% - 80% of the sum of the masses of the monomer β and the monomer γ.

[0144] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure has good hydrophobic and oleophobic properties. In some specific embodiments, the water contact angle of the hydrophobic and oleophobic film layer is above 105°, and the n - hexadecane contact angle of the hydrophobic and oleophobic film layer is above 60°; in some specific embodiments, the water contact angle of the hydrophobic and oleophobic film layer is above 110°, and the n - hexadecane contact angle of the hydrophobic and oleophobic film layer is above 65°.

[0145] The hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure has good friction resistance. In some specific embodiments, when the hydrophobic and oleophobic film layer uses a non - woven cloth as the friction material, under the conditions of a pressure of 1 N and a speed of 50 r / min, through a friction resistance tester for friction resistance testing, after 1000 times of friction, the water contact angle of the hydrophobic and oleophobic film layer is above 100°; in some specific embodiments, after 2000 times of friction, the water contact angle of the hydrophobic and oleophobic film layer is above 95°.

[0146] The specific embodiments of the present disclosure further provide a device, at least part of the surface of which has any of the above hydrophobic and oleophobic film layers. In some specific embodiments, all surfaces of the device have the hydrophobic and oleophobic film layers, so that the surface of the device has good hydrophobic and oleophobic properties and friction resistance, and can stably achieve the hydrophobic and oleophobic effects for a long time.

[0147] In some specific embodiments, the device of the specific embodiments of the present disclosure includes electrical components, optical instruments, electronic or electrical components, etc.

[0148] The specific embodiments of the present disclosure further provide a method for preparing a hydrophobic and oleophobic film layer for preparing any of the above hydrophobic and oleophobic film layers. The preparation method includes: placing a substrate in a plasma reaction chamber; vaporizing monomer α, monomer β, and monomer γ and introducing them into the plasma reaction chamber, and turning on plasma discharge. The plasma of monomer α, monomer β, and monomer γ undergoes chemical vapor deposition on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0149] In some specific embodiments of the preparation method of the specific embodiments of the present disclosure, vaporizing monomer α, monomer β, and monomer γ and introducing them into the plasma reaction chamber includes: mixing monomer α, a solvent, and an inhibitor to form mixture 1, and mixing monomer β and monomer γ to form mixture 2; heating to vaporize mixture 1 and mixture 2 and introducing them into the plasma reaction chamber respectively.

[0150] In the preparation method of the specific embodiments of the present disclosure, by controlling the flow rates of monomer α, monomer β, and monomer γ, the ratio of the mass of monomer α entering the plasma reaction chamber during the coating time to the sum of the masses of monomer β and monomer γ is controlled. The ratio of the mass of monomer α to the sum of the masses of monomer β and monomer γ is related to the hydrophobic property, oleophobic property, and friction resistance of the hydrophobic and oleophobic film layer. The flow rates of monomer α, monomer β, and monomer γ can be set according to the actual application requirements of the film layer. In some specific embodiments, the ratio of the flow rate of mixture 1 introduced into the plasma reaction chamber to the flow rate of mixture 2 introduced into the plasma reaction chamber is 0.5:9.5 to 9.5:0.5, specifically, for example, it can be 0.5:9.5, 3:7, 1:9, 5:5, 6:4, 7:3, 8:2, 9:1, or 9.5:0.5, etc.

[0151] In some specific embodiments of the preparation method of the specific embodiments of the present disclosure, the ratio of the flow rate of mixture 1 introduced into the plasma reaction chamber to the flow rate of mixture 2 introduced into the plasma reaction chamber is 3:7 to 9:1, and in some specific embodiments, it is 5:5 to 8:2.

[0152] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the gas flow rate of mixture 1 introduced into the plasma reaction chamber is 10 - 2000 μL / min. Specifically, for example, 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, 240 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 of mixture 2 introduced into the plasma reaction chamber is 10 - 2000 μL / min. Specifically, for example, it can be: 10 μL / min, 15 μL / min, 30 μL / min, 60 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.

[0153] The preparation method of the specific embodiments of the present disclosure. Since the molecular weight of monomer α is relatively high and it has a certain viscosity, in order to ensure that monomer α can be smoothly introduced into the vaporization device for vaporization and then introduced into the plasma reaction chamber, a solvent is added to increase its fluidity. For most solvents, they will also vaporize when monomer α vaporizes and enter the plasma reaction chamber together. Therefore, the influence of the solvent on the hydrophobic and oleophobic properties and the friction resistance of the prepared film layer needs to be considered. In some specific embodiments, the solvent includes one or two of fluorinated acrylate and organic solvent.

[0154] In some specific embodiments, the fluorinated acrylate includes one or more of: trifluoroethyl methacrylate, trifluoroethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, heptafluorobutyl methacrylate, heptafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H-perfluoropropyl methacrylate, perfluoroalkyl ethyl methacrylate, (2H-perfluoropropyl)-2-acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate.

[0155] In some specific embodiments, the fluorinated acrylate is trifluoroethyl methacrylate.

[0156] In some specific embodiments, the organic solvent includes one or more of: ethyl acetate, butyl acetate, acetone. In some specific embodiments, the organic solvent is ethyl acetate or butyl acetate.

[0157] In the preparation method of the specific embodiments of the present disclosure, in some specific embodiments, the weight ratio of the monomer α to the solvent is 1:9 to 9:1, specifically, for example, 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.

[0158] In the preparation method of the specific embodiments of the present disclosure, in some specific embodiments, to prevent the monomer α from undergoing a polymerization reaction during the heating and gasification process, a polymerization inhibitor is added to prevent it from polymerizing to form a polymer before being introduced into the reaction chamber. In some specific embodiments, the polymerization inhibitor includes one or more of: hydroquinone, p-benzoquinone, methylhydroquinone, p-methoxyphenol, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0159] In some specific embodiments, the polymerization inhibitor is p-methoxyphenol or hydroquinone.

[0160] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the dosage of the polymerization inhibitor is 0.1% to 1% by mass of the dosage of monomer α. Specifically, for example, it can be: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc.

[0161] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, to prevent the polymerization reaction of monomer β and monomer γ during the heating and gasification process, a polymerization inhibitor is further added to the mixture 2. In some specific embodiments, the polymerization inhibitor includes: one or several of hydroquinone, p-benzoquinone, methylhydroquinone, p-methoxyphenol, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0162] In some specific embodiments, the polymerization inhibitor is p-methoxyphenol or hydroquinone.

[0163] In some specific embodiments, the dosage of the polymerization inhibitor is 0.1% to 1% by mass of the total dosage of monomer β and monomer γ. Specifically, for example, it can be: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc.

[0164] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the molecular weights of monomer β and monomer γ are not large, and it is not easy to undergo a polymerization reaction during the heating and gasification process, so there is no need to add a polymerization inhibitor.

[0165] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, during the plasma polymerization process, the temperature of the reaction chamber is 30°C to 60°C. Specifically, for example, it can be 30°C, 40°C, 50°C, 55°C or 60°C, etc.

[0166] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the plasma discharge is continuous discharge, and the discharge power is 10 to 300 W. Specifically, for example, it can be: 10 W, 50 W, 100 W, 200 W or 300 W, etc. The discharge time is 60 to 36000 s. Specifically, for example, it can be: 60 s, 360 s, 1200 s, 2400 s, 3600 s, 7200 s or 36000 s, etc.

[0167] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the plasma discharge is a pulsed discharge, and the discharge power is 10 - 400 W. Specifically, for example, it can be: 10 W, 50 W, 100 W, 180 W, 200 W, 240 W, 250 W, 300 W or 400 W, etc. The pulse duty cycle is 0.1% - 90%. Specifically, for example, it can be: 0.1%, 1%, 10%, 25%, 30%, 35%, 50%, 60%, 70%, 80% or 90%, etc. The pulse frequency is 10 - 500 Hz. Specifically, for example, it can be: 10 Hz, 100 Hz, 200 Hz, 250 Hz, 300 Hz or 500 Hz, etc. The discharge time is 200 - 36000 s. Specifically, for example, it can be: 200 s, 360 s, 1200 s, 2400 s, 3600 s, 7200 s or 36000 s, etc.

[0168] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, before the chemical vapor deposition, evacuate to 10 - 200 mTorr and introduce a mixed gas of one or more of the gases He, Ar, and O2, and turn on the plasma discharge to pre-treat the substrate.

[0169] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, in the pre-treatment, the plasma discharge is a continuous discharge, and the discharge power is 50 - 600 W. Specifically, for example, it can be: 50 W, 100 W, 120 W, 200 W, 250 W, 300 W, 400 W or 600 W, etc. The discharge time is 60 - 2400 s. Specifically, for example, it can be: 60 s, 360 s, 600 s, 1200 s, 1800 s or 2400 s, etc.

[0170] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, in the pre-treatment, the plasma discharge is a pulsed discharge, and the discharge power is 10 - 500 W. Specifically, for example, it can be: 10 W, 50 W, 100 W, 180 W, 200 W, 300 W or 500 W, etc. The pulse duty cycle is 0.1% - 90%. Specifically, for example, it can be: 0.1%, 1%, 10%, 25%, 35%, 50%, 60%, 70%, 80% or 90%, etc. The pulse frequency is 10 - 500 Hz. Specifically, for example, it can be: 10 Hz, 100 Hz, 200 Hz, 250 Hz, 300 Hz or 500 Hz, etc. The discharge time is 60 - 2400 s. Specifically, for example, it can be: 60 s, 360 s, 600 s, 1200 s, 1800 s or 2400 s, etc.

[0171] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, in the pretreatment, the plasma discharge modes include: electrodeless discharge, single-electrode discharge, double-electrode discharge or multi-electrode discharge. In some specific embodiments, the electrodeless discharge includes: radio frequency inductively coupled discharge, microwave discharge, etc. In some specific embodiments, the single-electrode discharge includes: corona discharge, plasma jet formed by monopolar discharge, etc. In some specific embodiments, the double-electrode discharge includes: dielectric barrier discharge, bare electrode radio frequency glow discharge, etc. In some specific embodiments, the multi-electrode discharge includes: discharge using a floating electrode as the third electrode, etc.

[0172] The preparation method of the specific embodiments of the present disclosure. In some specific embodiments, the preparation method further includes post-treatment. The post-treatment includes: after the preparation of the hydrophobic and oleophobic film layer on the surface of the substrate, introducing clean compressed air or inert gas until the plasma reaction chamber returns to normal pressure, opening the plasma reaction chamber, and taking out the substrate. In some specific embodiments, an inert gas is introduced, and the flow rate of the inert gas is 5-300 sccm.

[0173] The following further illustrates the present invention through specific examples.

[0174] Example

[0175] Description of the test method

[0176] Thickness of the hydrophobic and oleophobic film layer: Measured using the American Filmetrics F20-UV - thin film thickness measuring instrument;

[0177] Water contact angle of the hydrophobic and oleophobic film layer: Tested according to the GB / T 30447-2013 standard.

[0178] Oil contact angle of the hydrophobic and oleophobic film layer: Tested using an SDC-100 standard contact angle measuring instrument to measure the contact angle between the film layer and n-hexadecane.

[0179] Friction resistance performance test: Conducted on a wear-resistant testing machine, the friction material is lint-free cloth, and the water contact angles are tested under the conditions of a pressure of 1 N and a rotational speed of 50 r / min for 0, 100, 500, 1000, and 2000 friction cycles respectively.

[0180] Example 1

[0181] Place the Si wafer and the glass slide as the coating substrates on the substrate placement bracket in the plasma chamber, evacuate the chamber to 80 mTorr, introduce helium gas with a flow rate of 80 sccm, and the chamber temperature is 50 °C;

[0182] Maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 80 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0183] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈500) (Suzhou Cangmu New Materials Co., Ltd.) and ethyl acetate (weight ratio 2:8), and p-methoxyphenol (added amount is 0.2 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a uniform solution as Mixture 1; γ-methacryloxypropyltris(trimethylsiloxy)silane and diethylene glycol diacrylate (weight ratio 7:3), and p-methoxyphenol [added amount is 0.2 wt% of the total mass of γ-methacryloxypropyltris(trimethylsiloxy)silane and diethylene glycol diacrylate] are formulated into a uniform solution as Mixture 2; according to the flow rate of Mixture 1: the flow rate of Mixture 2 = 6:4 (the flow rate of Mixture 1 is 180 μL / min, and the flow rate of Mixture 2 is 120 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 80 sccm, turn on radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 300 Hz, the pulse discharge power is 250 W, and the reaction time is 3600 s;

[0184] After film coating is completed, compressed air is filled to restore the chamber to normal pressure, the coated substrate is taken out, and the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured. The measurement results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0185] Example 2

[0186] Place the Si wafer and the glass slide as coated substrates on the substrate placement bracket in the plasma chamber, evacuate the chamber to 100 mTorr, introduce helium with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0187] Maintain the chamber pressure at 100 mTorr, maintain the helium flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 250 W, and continuously discharge for 600 s to pre-treat the substrate;

[0188] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.) and ethyl acetate (weight ratio 5:5), hydroquinone (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a uniform solution as Mixture 1; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and trimethylolpropane tri(meth)acrylate (weight ratio 6:4), hydroquinone [added amount is 0.2 wt% of the total mass of 3-(2,3-epoxypropoxy)propyltrimethoxysilane and trimethylolpropane tri(meth)acrylate] are formulated into a uniform solution as Mixture 2; According to the flow rate of Mixture 1: the flow rate of Mixture 2 = 7:3 (the flow rate of Mixture 1 is 210 μL / min, and the flow rate of Mixture 2 is 90 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; keep the chamber pressure at 100 mTorr, keep the helium flow rate at 100 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 25%, the pulse frequency is 200 Hz, the pulse discharge power is 300 W, and the reaction time is 3600 s;

[0189] After the coating is completed, compressed air is filled into the chamber to restore the normal pressure, the coated substrate is taken out, the film thickness, water contact angle and oil contact angle of the film layer on the Si wafer are tested, and the test results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0190] Example 3

[0191] Place the Si wafer and the glass slide as the coating substrates on the substrate placement bracket in the plasma chamber, evacuate the chamber to 120 mTorr, introduce helium, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0192] Keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the continuous plasma discharge, the discharge power is 300 W, and the continuous discharge is 600 s to pre-treat the substrate;

[0193] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) and butyl acetate (weight ratio 3:7), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a uniform solution as Mixture 1; 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate (weight ratio 5:5), and p-methoxyphenol [added amount is 0.3 wt% of the total mass of 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate] are formulated into a uniform solution as Mixture 2; according to the flow rate of Mixture 1: the flow rate of Mixture 2 = 8:2 (the flow rate of Mixture 1 is 240 μL / min, and the flow rate of Mixture 2 is 60 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0194] After the coating is completed, compressed air is filled into the chamber to restore the normal pressure, the coated substrate is taken out, and the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are tested. The test results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0195] Example 4

[0196] The Si wafer and the glass slide are placed on the substrate placement bracket in the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0197] Keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the continuous plasma discharge, the discharge power is 300 W, and the continuous discharge is 600 s to pre-treat the substrate;

[0198] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) and trifluoroethyl methacrylate (weight ratio 5:5), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a homogeneous solution as Mixture 1; 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate (weight ratio 5:5), and p-methoxyphenol [added amount is 0.3 wt% of the total mass of 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate] are formulated into a homogeneous solution as Mixture 2; According to the flow rate of Mixture 1: the flow rate of Mixture 2 = 5:5 (the flow rate of Mixture 1 is 150 μL / min, and the flow rate of Mixture 2 is 150 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0199] After the coating is completed, compressed air is filled to restore the chamber to normal pressure, the coated substrate is taken out, and the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured. The measurement results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0200] Comparative Example 1

[0201] The Si wafer and the glass slide are placed on the substrate placement bracket in the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0202] Keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the continuous plasma discharge, the discharge power is 300 W, and the continuous discharge is 600 s to pre-treat the substrate;

[0203] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000), trifluoroethyl methacrylate (weight ratio 5:5), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a homogeneous solution as Mixture 1; 1,6-hexanediol di(meth)acrylate and p-methoxyphenol [added amount is 0.3 wt% of the mass of 1,6-hexanediol di(meth)acrylate] are formulated into a homogeneous solution as Mixture 2; according to the flow rate of Mixture 1: flow rate of Mixture 2 = 5:5 (the flow rate of Mixture 1 is 150 μL / min, and the flow rate of Mixture 2 is 150 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; the chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 150 sccm, radio frequency plasma discharge is turned on, the energy output mode of the radio frequency is pulsed, plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0204] After the coating is completed, compressed air is introduced to restore the chamber to normal pressure, the coated substrate is taken out, the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured, and the measurement results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0205] Comparative Example 2

[0206] The Si wafer and the glass slide are placed on the substrate placement bracket in the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0207] The chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 150 sccm, continuous plasma discharge is turned on, the discharge power is 300 W, and the continuous discharge lasts for 600 s to pre-treat the substrate;

[0208] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) and trifluoroethyl methacrylate (weight ratio 5:5), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a homogeneous solution as Mixture 1; 3-(methacryloyloxy)propyltrimethoxysilane and p-methoxyphenol [added amount is 0.3 wt% of the mass of 3-(methacryloyloxy)propyltrimethoxysilane] are formulated into a homogeneous solution as Mixture 2; According to the flow rate of Mixture 1: the flow rate of Mixture 2 = 5:5 (the flow rate of Mixture 1 is 150 μL / min, and the flow rate of Mixture 2 is 150 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; The chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 150 sccm, radio frequency plasma discharge is turned on, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0209] After film coating is completed, compressed air is introduced to restore the chamber to normal pressure, the coated substrate is taken out, the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured, and the measurement results are listed in Table 1 below; The coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0210] Comparative Example 3

[0211] The Si wafer and the glass slide are placed on the substrate placement bracket in the plasma chamber, the chamber is evacuated to 120 mTorr, helium is introduced, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0212] The chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 150 sccm, continuous plasma discharge is turned on, the discharge power is 300 W, and continuous discharge is carried out for 600 s to pre-treat the substrate;

[0213] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) and perfluorotripropylamine (weight ratio 5:5), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a homogeneous solution as Mixture 1; 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate (weight ratio 5:5), and p-methoxyphenol [added amount is 0.3 wt% of the total mass of 3-(methacryloyloxy)propyltrimethoxysilane and 1,6-hexanediol di(meth)acrylate] are formulated into a homogeneous solution as Mixture 2; According to the flow rate of Mixture 1: the flow rate of Mixture 2 = 5:5 (the flow rate of Mixture 1 is 150 μL / min, and the flow rate of Mixture 2 is 150 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0214] After the coating is completed, compressed air is filled to restore the chamber to normal pressure, the coated substrate is taken out, and the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured. The measurement results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0215] Comparative Example 4

[0216] Place the Si wafer and the glass slide as the coating substrates on the substrate placement bracket in the plasma chamber, evacuate the chamber to 120 mTorr, introduce helium, and the flow rate is 150 sccm, and the chamber temperature is 50 °C;

[0217] Keep the chamber pressure at 120 mTorr, keep the helium flow rate at 150 sccm, turn on the continuous plasma discharge, the discharge power is 300 W, and the continuous discharge is 600 s to pre-treat the substrate;

[0218] Then, a monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) and trifluoroethyl methacrylate (weight ratio 5:5), and p-methoxyphenol (added amount is 0.3 wt% of the mass of the monofunctional perfluoropolyether (meth)acrylate) are formulated into a homogeneous solution as Mixture 1; methyltriethoxysilane and 1,6-hexanediol di(meth)acrylate (weight ratio 5:5), and p-methoxyphenol [added amount is 0.3 wt% of the total mass of methyltriethoxysilane and 1,6-hexanediol di(meth)acrylate] are formulated into a homogeneous solution as Mixture 2; according to the flow rate of Mixture 1: the flow rate of Mixture 2 = 5:5 (the flow rate of Mixture 1 is 150 μL / min, and the flow rate of Mixture 2 is 150 μL / min), after vaporization at a vaporization temperature of 110 °C, it is introduced into the plasma chamber; the chamber pressure is maintained at 120 mTorr, the helium flow rate is maintained at 150 sccm, radio frequency plasma discharge is initiated, the energy output mode of the radio frequency is pulsed, plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 30%, the pulse frequency is 250 Hz, the pulse discharge power is 240 W, and the reaction time is 3600 s;

[0219] After film coating is completed, compressed air is filled to restore the chamber to normal pressure, the coated substrate is taken out, the film thickness, water contact angle, and oil contact angle of the film layer on the Si wafer are measured, and the measurement results are listed in Table 1 below; the coated glass slide is subjected to a friction resistance test, and the test results are listed in Table 2 below.

[0220] Table 1 Test results of water contact angle and oil contact angle

[0221] Film thickness / nm Water contact angle / ° Oil (n - hexadecane) contact angle / ° Example 1 105 107 62 Example 2 89 113 68 Example 3 95 117 72 Example 4 117 116 69 Comparative Example 1 110 118 71 Comparative Example 2 85 116 70 Comparative Example 3 98 117 71 Comparative Example 4 102 116 69

[0222] According to the test results in Table 1, in Example 1, Example 2, and Example 3, the flow rate ratios of Mixture 1: Mixture 2 are 6:4, 7:3, and 8:2 respectively. The hydrophobic and oleophobic properties of the film layer are mainly provided by the monofunctional perfluoropolyether (meth)acrylate in Mixture 1. Within a certain flow rate ratio range, the greater the flow rate of Mixture 1 relative to Mixture 2, the better the hydrophobic and oleophobic properties.

[0223] Table 2 Test results of friction resistance

[0224]

[0225] According to the test results in Table 2, in Examples 1 to 4, monomers with two or more carbon-carbon unsaturated bonds (monomer β) and silane monomers with at least one silicon-oxygen bond and an unsaturated group (monomer γ) were used. The obtained film layers had good friction resistance. The water contact angle was above 100° after 1000 rubs. After 2000 rubs, the water contact angle of Example 1 was 96°, and the water contact angles of Examples 2 to 4 were above 100°. In Comparative Example 1, only monomer β was used, and in Comparative Example 2, only monomer γ was used. The friction resistance of the obtained film layers was inferior to those of Examples 1 to 4. Especially when the number of rubs reached 1000 and 2000, the water contact angles of Comparative Example 1 and Comparative Example 2 decreased significantly.

[0226] In Comparative Example 3, the solvent used was perfluorotripropylamine, a fluorocarbon. In Examples 3 and 4, butyl acetate and trifluoroethyl methacrylate were used as solvents respectively. The film layers of Examples 3 and 4 had more excellent friction resistance. Especially, the water contact angles after 1000 and 2000 rubs were above 110°, indicating that the type of solvent had a certain influence on the friction resistance of the film layer. Compared with fluorocarbon solvents, fluorinated acrylate solvents and butyl acetate were more conducive to improving the friction resistance of the film layer.

[0227] In Comparative Example 4, the silane monomer used was methyltriethoxysilane, and its molecular structure had no crosslinking groups such as (meth)acryloyloxy, epoxy, cycloalkyl, alkenyl or cyano groups. Compared with Comparative Example 4, the silane monomers used in Example 4 were different. Under the same other conditions, the film layer in Example 4 had better friction resistance than the film layer in Comparative Example 4.

[0228] Figure 1 is a graph showing the relationship between the water contact angle and the number of rubs drawn based on the test results in Table 2. It can be Figure 1 seen that when the number of rubs reached 1000, the water contact angles of the film layers of Examples 1 to 4 were greater than those of Comparative Examples 1 to 4, and the hydrophobicity was better. When the number of rubs was 2000, the difference between the water contact angles of the film layers of Examples 1 to 4 and those of Comparative Examples 1 to 4 further increased, indicating that compared with Comparative Examples 1 to 4, the film layers of Examples 1 to 4 had better friction resistance.

[0229] The above is only an exemplary embodiment adopted to illustrate the principle of the present disclosure and is not used to limit the protection scope of the present disclosure. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present disclosure, and these modifications and improvements are also within the protection scope of the present disclosure.

Claims

1. A hydrophobic and oleophobic film layer, characterized in that, The hydrophobic and oleophobic film layer is a plasma polymerization coating formed by the plasma of substrate-contact monomers α, β, and γ. Monomer α has the structure of formula (1). In formula (1), R1, R2, and R3 are each independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluoro-substituted alkyl groups or fluorine atoms; L1 is a linking group; m is an integer not less than 1; in m repeating units, n of each repeating unit is independently selected from integers not less than 1; Monomer β has two or more carbon-carbon unsaturated bonds; Monomer γ has the structure of formula (2). In formula (2), L2 is a linking group; R5 is selected from substituted or unsubstituted C1-C4 hydrocarbon groups, substituted or unsubstituted C1-C4 acyl groups, or substituted or unsubstituted C1-C 10 alkylsilyls; R6 and R7 are each independently selected from substituted or unsubstituted C1-C4 hydrocarbon oxy groups, substituted or unsubstituted C1-C4 hydrocarbon groups, substituted or unsubstituted C1-C4 acyloxy groups, or substituted or unsubstituted C1-C 10 alkylsiloxanyl groups; R8 includes one or more of acryloxy, epoxy, cycloalkyl, alkenyl, or cyano groups.

2. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, R8 is selected from substituted or unsubstituted C1-C4 alkenyl, substituted or unsubstituted C1-C4 alkynyl, cyano, substituted or unsubstituted epoxy group, C2-C 10 epoxyalkyloxy, or C3-C 10 epoxycycloalkyl.

3. The hydrophobic and oleophobic film layer according to claim 2, characterized in that, L2 is selected from a linking bond, a substituted or unsubstituted C1-C4 alkylene group, the structure of formula (3), or the structure of formula (4).

4. The hydrophobic and oleophobic film layer according to claim 3, characterized in that, R5 is selected from alkoxy-substituted C1-C4 alkyl groups, C1-C4 alkyl groups, C1-C4 acyl groups, or C1-C6 trialkylsilyl groups; R6 and R7 are each independently selected from alkoxy-substituted C1-C4 alkoxy groups, C1-C4 alkoxy groups, C1-C4 alkyl groups, C1-C4 acyloxy groups, or C1-C6 trialkylsiloxy groups.

5. The hydrophobic and oleophobic film layer according to claim 3, characterized in that, L2 is selected from the structure of formula (3), R8 is selected from substituted or unsubstituted C1-C4 alkenyl groups; R5 is selected from C1-C4 alkyl groups or C1-C6 trialkylsilyl groups; R6 and R7 are each independently selected from C1-C4 alkoxy groups, C1-C4 alkyl groups, or C1-C6 trialkylsiloxy groups.

6. The hydrophobic and oleophobic film layer according to claim 5, characterized in that, R8 is selected from vinyl or isopropenyl.

7. The hydrophobic and oleophobic film layer according to claim 3, characterized in that, R8 is selected from glycidyloxy or epoxycyclohexyl, L2 is selected from substituted or unsubstituted C1-C4 alkylene groups, R5 is selected from C1-C4 alkyl groups, and R6 and R7 are each independently selected from C1-C4 alkoxy groups or C1-C4 alkyl groups.

8. The hydrophobic and oleophobic film layer according to claim 3, characterized in that, R8 is selected from vinyl, propenyl, isopropenyl, or cyano groups, L2 is selected from a linking bond or a substituted or unsubstituted C1-C4 alkylene group, R5 is selected from alkoxy-substituted C1-C4 alkyl groups, C1-C4 alkyl groups, C1-C4 acyl groups; R6 and R7 are each independently selected from alkoxy-substituted C1-C4 alkoxy groups, C1-C4 alkoxy groups, C1-C4 alkyl groups, or C1-C4 acyloxy groups.

9. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer γ is selected from at least one of: 3-(methacryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris(trimethylsiloxy)silane, 3-methacryloyloxypropyltriethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)methyldimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)-silane, vinyltriisopropoxysilane, methylvinyldimethoxysilane, vinyltriacetoxysilane, cyanoethyltriethoxysilane, cyanoethyltrimethoxysilane, cyanoethylmethyldiethoxysilane, cyanoethylmethyldimethoxysilane, cyanoethyltriacetoxysilane.

10. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The monomer γ is selected from at least one of: γ-methacryloyloxypropyltris(trimethylsiloxy)silane, 3-(methacryloyloxy)propyltrimethoxysilane, or 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

11. The hydrophobic and oleophobic film layer according to claim 1, characterized in that, The carbon-carbon unsaturated bond of the monomer β has the structure of formula (5), In formula (5), Z1, Z2 and Z3 are each independently selected from a hydrogen atom or an alkyl group of C1-C4.

12. The hydrophobic and oleophobic film layer according to claim 11, characterized in that, The monomer β has the structure of formula (6), In formula (6), R9, R 10 , R 11 , R 12 , R 13 , and R 14 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 15 is an alkylene or substituted alkylene group having 2 to 10 carbon atoms, and x is an integer from 1 to 10; The substituent of the substituted alkylene group is an alkyl group of C1-C4 or a hydroxyalkyl group of C1-C4.

13. The hydrophobic and oleophobic film layer according to claim 12, characterized in that,The R9, R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from a hydrogen atom or a methyl group.

14. The hydrophobic and oleophobic film layer according to claim 12, wherein The monomer β is selected from at least one of: 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, 1,3-butanediol diacrylate, 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, dipropylene glycol diacrylate or dipropylene glycol triacrylate.

15. The hydrophobic and oleophobic film layer according to claim 11, wherein The monomer β has the structure of formula (7), In formula (7), R 16 is an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 1- carbon atoms substituted with a hydroxyl group, R 10 , R 17 , and R 18 are each independently selected from alkylene groups having 1 to 19 carbon atoms, R 10 , R 20 , and R 21 are each independently selected from alkylene groups having 2 to 22 carbon atoms, R 10 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , and R 31 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and y1, y2, and y3 are each independently selected from integers from 0 to 10.

16. The hydrophobic and oleophobic film layer according to claim 15, wherein In formula (7), the R 16 is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and the R 17 , R 18 and R 19 are each independently selected from alkylene groups having 1 to 4 carbon atoms, and the R 20 , R 21 and R 22 are each independently selected from alkylene groups having 2 to 4 carbon atoms, and the R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from a hydrogen atom or a methyl group, and y1, y2 and y3 are each independently selected from integers from 0 to 2.

17. The hydrophobic and oleophobic film layer according to claim 15, wherein The monomer β is selected from at least one of: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

18. The hydrophobic and oleophobic film layer according to claim 1, wherein The monomer β is selected from at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol 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-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether, etc.

19. The hydrophobic and oleophobic film layer according to claim 1, wherein The monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane trimethacrylate, and 1,6-hexanediol dimethacrylate.

20. The hydrophobic and oleophobic film layer according to claim 1, wherein The ratio of the mass of the monomer α to the sum of the masses of the monomer β and the monomer γ is 0.5:9.5 to 9.5:0.

5.

21. The hydrophobic and oleophobic film layer according to claim 20, wherein The ratio of the mass of the monomer α to the sum of the masses of the monomer β and the monomer γ is 3:7 to 9:

1.

22. The hydrophobic and oleophobic film layer according to claim 1, wherein The mass of the monomer γ accounts for 5% to 95% of the sum of the masses of the monomer β and the monomer γ.

23. The hydrophobic and oleophobic film layer according to claim 1, wherein In formula (1), the R1, R2, and R3 are each independently selected from a methyl group or a hydrogen atom.

24. The hydrophobic and oleophobic film layer according to claim 1, wherein In formula (1), the R1 is a methyl group, and the R2 and R3 are hydrogen atoms.

25. The hydrophobic and oleophobic film layer according to claim 1, wherein The weight-average molecular weight of the monomer α is 200 to 5000.

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

27. The hydrophobic and oleophobic film layer according to claim 26, wherein The substituents of the substitution are one or more of the following groups: alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, heterocyclic group, carboxyl group, carboxylate ion, carboxylic acid ester group, carbamate group, alkoxy group, ketone group, aldehyde group, amine group, amide group, hydroxyl group, nitrile group, nitroso group, and halogen.

28. The hydrophobic and oleophobic film layer according to claim 27, wherein In formula (1), L1 is a perfluoro-substituted alkylene group.

29. The hydrophobic and oleophobic film layer according to claim 1, wherein The monomer α has the structure shown in formula (8). In formula (8), a is an integer not less than 1; L3 is selected from a linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

30. The hydrophobic and oleophobic film layer according to claim 1, whereinThe monomer α has the structure shown in formula (9). In formula (9), b is an integer not less than 1, and c is an integer not less than 1; L4 is selected from a linking bond, or substituted or unsubstituted C1-C3 alkylene groups.

31. The hydrophobic and oleophobic film layer according to claim 1, wherein, The monomer α has the structure shown in formula (10). In formula (10), d is an integer not less than 1, and e is an integer not less than 1; L5 is selected from a linking bond, or substituted or unsubstituted C1-C3 alkylene groups.

32. The hydrophobic and oleophobic film layer according to claim 1, wherein, The monomer α has the structure shown in formula (11). In formula (11), f is an integer not less than 1; L6 is selected from a linking bond, substituted or unsubstituted methylene, or substituted or unsubstituted ethylene.

33. The hydrophobic and oleophobic film layer according to any one of claims 1-32, wherein, The water contact angle of the hydrophobic and oleophobic film layer is above 105°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is above 60°.

34. The hydrophobic and oleophobic film layer according to any one of claims 1-32, wherein, The hydrophobic and oleophobic film layer is subjected to a friction resistance test using a dust-free cloth as a friction material under the conditions of a pressure of 1 N and a rotational speed of 50 r / min. After 1000 times of friction, the water contact angle of the hydrophobic and oleophobic film layer is above 100°.

35. A method for preparing a hydrophobic and oleophobic film layer according to any one of claims 1-34, wherein, Including: Placing the substrate in a plasma reaction chamber; After gasifying monomer α, monomer β, and monomer γ, they are introduced into the plasma reaction chamber, and plasma discharge is initiated. The plasmas of monomer α, monomer β, and monomer γ chemically vapor deposit on the surface of the substrate to form the hydrophobic and oleophobic film layer.

36. The method for preparing a hydrophobic and oleophobic film layer according to claim 35, wherein, Gasifying monomer α, monomer β, and monomer γ and introducing them into the plasma reaction chamber includes: Mixing monomer α, a solvent, and an inhibitor to form mixture 1, and mixing monomer β and monomer γ to form mixture 2; Heating to gasify mixture 1 and mixture 2 and then introducing them into the plasma reaction chamber separately.

37. The method for preparing a hydrophobic and oleophobic film layer according to claim 36, wherein, The flow rate of mixture 1 introduced into the plasma reaction chamber is 10 - 2000 μL / min, and the flow rate of mixture 2 introduced into the plasma reaction chamber is 10 - 2000 μL / min.

38. The method for preparing a hydrophobic and oleophobic film layer according to claim 36, wherein, The mass of the inhibitor is 0.1% - 1% of the mass of monomer α.

39. The method for preparing a hydrophobic and oleophobic film layer according to claim 36, wherein, An inhibitor is also added to mixture 2, and the mass of the inhibitor is 0.1% - 1% of the total mass of monomer β and monomer γ.

40. The method for preparing a hydrophobic and oleophobic film layer according to claim 36, wherein, The weight ratio of monomer α to the solvent is 1:9 - 9:

1.

41. The method for preparing a hydrophobic and oleophobic film layer according to claim 36, wherein, The solvent includes one or both of fluorinated acrylate and organic solvent; The fluorinated acrylate includes one or several of trifluoroethyl methacrylate, trifluoroethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, heptafluorobutyl methacrylate, heptafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H-perfluoropropyl methacrylate, perfluoroalkyl ethyl methacrylate, (2H-perfluoropropyl)-2-acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate; The organic solvent includes one or several of ethyl acetate, butyl acetate, and acetone.

42. The preparation method of the hydrophobic and oleophobic film layer according to claim 41, wherein, The solvent includes one or several of perfluoroacrylate and butyl acetate.

43. The preparation method of the hydrophobic and oleophobic film layer according to any one of claims 36 - 42, wherein, The plasma discharge is continuous discharge, the discharge power is 10 - 300 W, and the discharge time is 60 - 36000 s.

44. The preparation method of the hydrophobic and oleophobic film layer according to any one of claims 36 - 42, wherein, The plasma discharge is pulsed discharge, the discharge power is 10 - 400 W, the pulse duty cycle is 0.1% - 90%, the pulse frequency is 10 - 500 Hz, and the discharge time is 200 - 36000 s.

45. The preparation method of the hydrophobic and oleophobic film layer according to any one of claims 36 - 42, wherein, It also includes: Before the chemical vapor deposition, evacuate to 10 - 200 mTorr, and introduce a mixed gas of one or several of gases He, Ar, and O2, and initiate plasma discharge to pre-treat the substrate.

46. A device, wherein, At least part of the surface of the device has the hydrophobic and oleophobic film layer as described in any one of claims 1 - 34.

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