CN108517161A - Super-hydrophobic oleophobic coating and preparation method thereof, super-hydrophobic oleophobic film - Google Patents

Super-hydrophobic oleophobic coating and preparation method thereof, super-hydrophobic oleophobic film Download PDF

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CN108517161A
CN108517161A CN201810307253.1A CN201810307253A CN108517161A CN 108517161 A CN108517161 A CN 108517161A CN 201810307253 A CN201810307253 A CN 201810307253A CN 108517161 A CN108517161 A CN 108517161A
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super
emulsion
hydrophobic oleophobic
monomer
coating
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CN108517161B (en
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郝红
赵夏
杜鲜萍
王君
刘建连
段延萍
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Northwest University
Northwestern University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Abstract

A kind of super-hydrophobic oleophobic coating of present invention offer and preparation method thereof, including step：1) mixture of water, inorganic weak bases, glycols homologue, alkyl phenol polyoxyethylene ether class emulsifier, sulfonate and/or sulfate type anion emulsifier, cross-linking monomer and cross-linked evocating agent is stirred into obtain milky white colour-stable pre-emulsion；2) milky white colour-stable pre-emulsion reacts 1 8h at 40~90 DEG C, adjusts pH value to 7~8 by ammonium hydroxide after cooling, obtains silicone acrylic emulsion；3) silicone acrylic emulsion, alcohols solvent, ethyl orthosilicate and ammonium hydroxide are stirred evenly, is heated to 40 80 DEG C of 1 10h of reaction, obtain cohydrolysis condensation suspension；4) it is condensed in suspension to cohydrolysis and perfluoroalkyl triethoxysilane and/or perfluoroalkyl trimethoxy silane is added, 0.5 8h is reacted at 50 70 DEG C, obtains super-hydrophobic oleophobic coating.The super-hydrophobic oleophobic coating preparation is simple, has good super-hydrophobic fuel shedding quality.The invention also discloses the super-hydrophobic oleophobic films based on coating.

Description

Super-hydrophobic oleophobic coating and preparation method thereof, super-hydrophobic oleophobic film
Technical field
The invention belongs to special technology for coating field, it is related to a kind of super-hydrophobic oleophobic coating and preparation method thereof and super-hydrophobic Oleophobic film.
Background technology
Since the 1990s, quickly grown based on the super hydrophobic surface that " lotus leaf effect " is constructed, under water environment Automatically cleaning, anti-freeze etc. be widely used.Because the surface of solids can not only touch water, it is also possible to touch other surfaces The relatively small liquid of tension, such as n-hexane, soybean oil, diiodomethane, these oil-based liquids are easy to sprawl in hydrophobic surface It opens, limits automatic cleaning action of the super hydrophobic surface under oil pollution environment.Therefore double thin, super-double-hydrophobic surfaces come into being.Double thin tables Face refers to having hydrophobic, oleophobic property a kind of surface simultaneously, and 90 ° are both greater than with the contact angle of water, oil；Super-double-hydrophobic surface refer to The contact angle of water and oil is both greater than 150 ° of surface.In contrast, double-hydrophobic surface is than hydrophobic, oleophobic surface is more complicated, in reality Also there is great potential in, so its exploitation is even more to be concerned with development.It is by the respective spy of hydrophobic, oleophobic surface Property rolls into one, and in addition to the basic functions such as anti-pollution, automatically cleaning, in the anti-corrosion of petroleum pipeline inner wall, antenna is anti-icing, anti-biological attached It, lubricating oil is anti-to creep, and leather and fur products oil resistant, mechanical resistant scratch etc. also have outstanding performance, make it in numerous industrial circles And it has a wide range of applications in daily life.
Studies have shown that double thin property of the surface of solids are codetermined by the chemical composition and micro-geometry on surface, The compound diadactic structure of micro-nano is built i.e. in low-surface energy substance or has coarse micro-nano compound using low-surface energy substance modification The surface of structure.In past 20 years, many methods have successfully been worked out to prepare double thin, super-amphiphobic coatings, such as chemical etching Method, spin coating dip coating, sol-gel method, chemical deposition and plasma technology etc..
Although having had much about double thin, super-double-hydrophobic surface reports, but still asked there is also much urgently to be resolved hurrily Topic.From technical method, the method that is much used to prepare amphiphobic material still has that equipment raw material are expensive, step is complicated, again Renaturation is poor, is only suitable for laboratory research is but not used to prepare large area double-hydrophobic surface etc.；In terms of stability, mesh Preceding most of double-hydrophobic surface poor chemical stability prepared and very sensitive to mechanicals efforts, be mainly manifested in rugged environment and Certain mechanicals efforts are easy that double thin performances is made to lose, these all greatly hinder practical application and the industry of double-hydrophobic surface Production.Therefore, select economic suitable material, exploitation is easy to operate, rapidly and efficiently, it is reproducible, there is excellent stability, can The target of researchers' effort is increasingly becomed with double thin, super-double-hydrophobic surfaces of large area commercial Application.
Invention content
The object of the present invention is to provide a kind of super-hydrophobic oleophobic coating and preparation method thereof, the super-hydrophobic oleophobic coating preparations Simply, there is good super-hydrophobic fuel shedding quality.
The present invention also aims to provide super-hydrophobic oleophobic coating to do the super-hydrophobic oleophobic film prepared.
The present invention is to be achieved through the following technical solutions：
A kind of preparation method of super-hydrophobic oleophobic coating, including step：
1) by water, inorganic weak bases, glycols homologue, alkyl phenol polyoxyethylene ether class emulsifier, sulfonate and/or sulfuric acid The mixture of salt form anion emulsifier, cross-linking monomer and cross-linked evocating agent stirs to obtain milky white colour-stable pre-emulsion；
Wherein, the cross-linking monomer includes acrylic ester monomer, hydroxyalkyl acrylates class monomer, acrylic compounds list Body and vinyl trialkyl oxysilane, according to quality meter, acrylic ester monomer：Hydroxyalkyl acrylates class monomer：Propylene Acrylic monomer：Vinyl trialkyl oxysilane=(30~99)：(0~20)：(0~30)：(1~20)；The quality of inorganic weak bases It is the 0.05%~5% of cross-linking monomer quality, the quality of glycols homologue is the 0.01%-5% of cross-linking monomer quality, emulsification The gross mass of agent is the 0.1%-5% of cross-linking monomer quality；
2) milky white colour-stable pre-emulsion reacts 1-8h at 40~90 DEG C, and pH value is adjusted to 7~8 by ammonium hydroxide after cooling, Obtain silicone acrylic emulsion；
3) silicone acrylic emulsion, alcohols solvent, ethyl orthosilicate and ammonium hydroxide are stirred evenly, is heated to 40-80 DEG C of reaction 1- 10h obtains cohydrolysis condensation suspension；According to weight meter, silicone acrylic emulsion：Alcohols solvent：Ethyl orthosilicate=(1-30)：(40- 98)：(1-30)；Ammonium hydroxide accounts for the 0.5%-10% of cohydrolysis condensation suspension gross mass；
4) it is condensed in suspension to cohydrolysis and perfluoroalkyl triethoxysilane and/or perfluoroalkyl trimethoxy silicon is added Alkane reacts 0.5-8h at 50-70 DEG C, obtains super-hydrophobic oleophobic coating.
Preferably, in step 1), inorganic weak bases are one or more in sodium bicarbonate, saleratus and sodium carbonate；
Glycols homologue is one or more in ethylene glycol, propylene glycol and butanediol；
Alkyl phenol polyoxyethylene ether class emulsifier is octyl phenol polyoxyethylene ether and/or nonylphenol polyoxyethylene ether；
Sulfonate and/or sulfate type anion emulsifier are alkylbenzene sulfonate, alkylsulfonate, aliphatic alcohol sulfate With it is one or more in aralkyl phenol polyethenoxy ether sulfate；
Cross-linked evocating agent is one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
Preferably, in step 1),
Acrylic ester monomer is R1COOR2, R1For vinyl, methyl ethylene, dimethyl ethenyl or ethylethylene Base, R2For the alkyl of 1-10 carbon atom；
Hydroxyalkyl acrylates class monomer is R3COO-R4- OH, R3For vinyl, methyl ethylene, dimethyl ethenyl Or ethyl vinyl, R4For the alkyl of 1-10 carbon atom；
Acrylic monomer is acrylic acid, methacrylic acid, ethylacrylic acid or dimethacrylate；
Vinyl trialkyl oxysilane is vinyltrimethoxysilane or vinyltriethoxysilane.
Preferably, in step 1), according to quality meter, alkyl phenol polyoxyethylene ether class emulsifier：Sulfonate and/or sulfuric acid Salt form anion emulsifier=1:(1~9).
Preferably, in step 2), the initiation reaction at 40-75 DEG C of 10~20mL pre-emulsions is first taken, then at 75-90 DEG C It is lower to instill remaining pre-emulsion；After being added dropwise, reaction system keeps the temperature 1-8h at 60-90 DEG C.
Preferably, in step 3), alcohols solvent is one kind or more in isopropanol, methanol, ethyl alcohol, propyl alcohol and butanol Kind.
Preferably, in step 4), perfluoroalkyl triethoxysilane is 1H, 1H, 2H, 2H- perfluoroalkyl triethoxies Silane, perfluoroalkyl trimethoxy silane are 1H, 1H, 2H, and 2H- perfluoroalkyl trimethoxy silanes, the alkyl is 4~12 The alkyl of carbon atom；The quality of perfluoroalkyl triethoxysilane and/or perfluoroalkyl trimethoxy silane is cross-linking monomer matter The 0.1%-30% of amount.
Super-hydrophobic oleophobic coating prepared by the preparation method.
The super-hydrophobic oleophobic film of the super-hydrophobic oleophobic coating preparation.
Compared with prior art, the present invention has technique effect beneficial below：
The preparation method of super-hydrophobic oleophobic coating provided by the invention, respectively step reaction condition is mild, in step 2) and step It is rapid 3) in, reaction temperature is only up to 90 DEG C；Moreover, during preparing super-hydrophobic oleophobic coating, entire middle spacer step Suddenly it need not purify, enormously simplify synthetic method, large-scale industry is suitble to prepare.Coating synthesized by this method has good Good stability, storage stability is more than 2 years or more, and coating is stronger to the adhesion strength of base material, has good mechanical performance.
The preparation method of super-hydrophobic oleophobic coating provided by the invention is simple, and coating is at low cost；It is with good stabilization Property, storage stability is more than 2 years or more, and coating is stronger to the adhesion strength of base material, has good mechanical performance.
The adhesion strength of super-hydrophobic oleophobic film and base material provided by the invention is stronger, has good mechanical performance.
Description of the drawings
Fig. 1 is the synthetic route of the present invention.
Fig. 2 is the particle size distribution figure of silicone acrylic emulsion prepared by the present invention.
Fig. 3 is the IR Characterization figure of silicone acrylic emulsion and double thin coating, wherein a is silicone acrylic emulsion IR Characterization, is applied for double dredge Expect IR Characterization.
Fig. 4 is the thermal gravimetric analysis results figure of silicone acrylic emulsion and double thin coating, wherein a curves indicate silicone acrylic emulsion, b curves Indicate double thin coating.
Fig. 5-1 is the electron microscope that double thin films amplify 20k times, wherein prepares the positive silicic acid of double thin coating of double thin films Ethyl ester hydrolysis time is 40min.
Fig. 5-2 is the electron microscope that double thin films amplify 50k times, wherein prepares the positive silicic acid of double thin coating of double thin films Ethyl ester hydrolysis time is 40min.
Fig. 5-3 is the electron microscope that double thin films amplify 15k times, wherein prepares the positive silicic acid of double thin coating of double thin films Ethyl ester hydrolysis time is 150min.
Fig. 5-4 is the electron microscope that double thin films amplify 30k times, wherein prepares the positive silicic acid of double thin coating of double thin films Ethyl ester hydrolysis time is 150min.
Fig. 6 is to carry out analysis result figure to the surface chemistry composition of prepared double thin films by surface power spectrum.
Fig. 7 is increased PFTS amounts in raw material to the influence diagram of coating film coated surface fluorinated volume.
Fig. 8-1 is the hookup of silicon the third film and water prepared by silicone acrylic emulsion.
Fig. 8-2 is the hookup of silicon the third film and diiodomethane prepared by silicone acrylic emulsion.
Fig. 8-3 is the hookup of double thin films and water.
Fig. 8-4 is the hookup of double thin films and diiodomethane.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
As shown in Figure 1, the principle of the synthetic method of the present invention is, occurred first by silicon-containing monomer and acrylate monomer Free-radical emulsion polymerization synthesizes silicone acrylic emulsion, and then with ethyl orthosilicate (TEOS) cohydrolysis condensation occurs for silicone acrylic emulsion, is formed The reticular structure of hybrid inorganic-organic, finally in reticular structure surface modification perfluoro decyl trialkoxy silane (in such as Fig. 1 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane, PFTS).The silica that wherein ethyl orthosilicate (TEOS) hydrolysis generates Nano particle can provide the surface roughness of coating, and PFTS can reduce surface free energy, can generate double thin interfaces.And two The reticular structure that silica nano particle and silicone acrylic emulsion cohydrolysis are formed by hybrid inorganic-organic can greatly improve coating Wear-resisting property and adhesion property to base material.In particular, including step：
1. deionized water (about the 2/3 of total amount), inorganic weak bases are added in the preparation of pre-emulsion in three-necked flask successively (sodium bicarbonate in such as Fig. 1), glycols homologue (ethylene glycol solution in such as Fig. 1), the emulsification of alkyl phenol polyoxyethylene ether class Agent (polyoxethylene octylphenyl phenol ether -10, OP-10 in such as Fig. 1), sulfonate and/or sulfate type anion emulsifier are (as schemed Lauryl sodium sulfate in 1).After stirring, be added cross-linking monomer (methyl methacrylate MMA in such as Fig. 1, Butyl acrylate BA, acrylic acid AA, hydroxyethyl methacrylate HEMA) and the vinyl trialkyl oxysilane (ethylene in such as Fig. 1 Ethyl triethoxy silicane alkane), the cross-linked evocating agent (ammonium persulfate in such as Fig. 1) of 0.5% (accounting for monomer gross mass ratio), stirring is added Milky white colour-stable pre-emulsion is obtained, it is spare.
2. the synthesis of silicone acrylic emulsion takes 10~20mL pre-emulsions to be added in there-necked flask, under the conditions of 75 DEG C, reaction to breast There is blue light in liquid, continues to be heated to 80 DEG C to start that remaining pre-emulsion is added dropwise, and after being added dropwise after 120min, is further continued for keeping the temperature 90min, reaction was completed later, after emulsion temperature is cooled to room temperature, is adjusted pH within the scope of 7~8 with ammonium hydroxide, mistake Filter to obtain milky, the silicone acrylic emulsion of blueing light.
3. the preparation of pair thin coating, isopropanol is sequentially added in there-necked flask, ethyl orthosilicate, silicone acrylic emulsion, ammonium hydroxide stirs Mix to obtain uniform solution.60 DEG C are heated to, 100min is kept the temperature, PFTS is added dropwise and (explains principle as an example with PFTS, it may be used His raw material).After 60min, reaction was completed, obtains fluorine-containing Ludox composite material.
4, double thin coating are uniformly coated on base material and prepare double thin films
Embodiment 1：
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 12g, butyl acrylate 12.5g, propylene Sour 0.5g, hydroxyethyl methacrylate 0.5g, vinyltriethoxysilane 2.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 75 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 120min, is further continued for heat preservation 3h, reaction was completed later, and emulsion temperature is cold But to after room temperature, pH is adjusted within the scope of 7~8 (variable) with ammonium hydroxide, filters milky white using Buchner funnel decompression The silicone acrylic emulsion of color, blueing light.Take isopropanol 21mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g, room temperature Lower stirring 10min obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluors is added Ruthenium triethoxysilane 0.25g.After 2h, reaction was completed, obtains double thin coating.
Embodiment 2
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 12g, butyl acrylate 12.5g, propylene Sour 0.5g, hydroxyethyl methacrylate 0.5g, vinyltriethoxysilane 2.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Isopropanol 23mL, ethyl orthosilicate 2.7g, silicone acrylic emulsion 4.0g and ammonium hydroxide 0.91g are taken, is stirred at room temperature It mixes 10min and obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls is added Triethoxysilane 0.25g.After 2h, reaction was completed, obtains double thin coating.
Embodiment 3
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 12g, butyl acrylate 12.5g, propylene Sour 0.5g, hydroxyethyl methacrylate 0.5g, vinyltriethoxysilane 2.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Ethyl alcohol 25mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g are taken, is stirred at room temperature 10min obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls three is added Ethoxysilane 0.25g.After 0.5-8h, reaction was completed, obtains double thin coating.
Embodiment 4
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.05g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 11.5g, butyl acrylate 12.0g, third Olefin(e) acid 0.5g, hydroxyethyl methacrylate 0.5g, vinyltriethoxysilane 3.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Isopropanol 21mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g are taken, is stirred at room temperature It mixes 10min and obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls is added Triethoxysilane 0.25g.After 0.5-8h, reaction was completed, obtains double thin coating.
Embodiment 5：
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 12g, butyl acrylate 12.5g, propylene Sour 0.5g, hydroxyethyl methacrylate 0.5g, vinyltriethoxysilane 2.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Isopropanol 21mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g are taken, is stirred at room temperature It mixes 10min and obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls is added Trimethoxy silane 0.20g.After 1-4h, reaction was completed, obtains double thin coating.
Embodiment 6：
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.5248g, lauryl sodium sulfate 0.3165g, methyl methacrylate 12g, butyl acrylate 12.5g, propylene Sour 0.7g, vinyltriethoxysilane 2.5g and ammonium persulfate 0.084g mixing, stirring 30min (1000rpm) are obtained milky white Colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C and starts that remaining pre-emulsion is added dropwise, After being added dropwise after 90min, it is further continued for heat preservation 2h, reaction was completed later, will with ammonium hydroxide after emulsion temperature is cooled to room temperature PH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, blueing light silicone acrylic emulsion.It takes Isopropanol 21mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g stir 10min and obtain uniform solution at room temperature. 60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes 0.45g is added. After 0.5-8h, reaction was completed, obtains double thin coating.
Embodiment 7：
First by deionized water 46g, sodium bicarbonate 0.084g, ethylene glycol solution 0.01g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.1324g, lauryl sodium sulfate 0.3165g, methyl acrylate 12g, butyl acrylate 12.5g, ethoxy third Olefin(e) acid ester 4.1g, vinyltrimethoxysilane 4.2g and ammonium persulfate 0.013g mixing, stirring 30min (1000rpm) are obtained Milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C and starts that remaining pre-emulsion is added dropwise, After being added dropwise after 90min, it is further continued for heat preservation 2h, reaction was completed later, will with ammonium hydroxide after emulsion temperature is cooled to room temperature PH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, blueing light silicone acrylic emulsion.It takes Isopropanol 21mL, ethyl orthosilicate 2.0g, silicone acrylic emulsion 3.0g and ammonium hydroxide 0.89g stir 10min and obtain uniform solution at room temperature. 60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes 0.31g is added. After 6-8h, reaction was completed, obtains double thin coating.
Embodiment 8：
First by deionized water 46g, sodium bicarbonate 1.09g, ethylene glycol solution 0.81g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.6541g, lauryl sodium sulfate 0.1726g, methyl acrylate 28.4g, vinyltrimethoxysilane 8.5g It is mixed with ammonium persulfate 0.035g, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.15mL pre-emulsions are taken to add Enter in there-necked flask, be heated to 80 DEG C and start that remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, it Reaction was completed afterwards, after emulsion temperature is cooled to room temperature, adjusts within the scope of 7~8 (variable) pH with ammonium hydroxide, uses Buchner funnel decompression filter milky, blueing light silicone acrylic emulsion.Take isopropanol 21mL, ethyl orthosilicate 13.2.0g, silicon third Lotion 4.0g and ammonium hydroxide 0.71g stirs 10min and obtains uniform solution at room temperature.60 DEG C are heated to, whole process persistently stirs, and protects 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes 0.01g is added in warm 2h.After 6-8h, reaction was completed, obtains double thin coating.
Embodiment 9：
First by deionized water 46g, sodium bicarbonate 1.50g, ethylene glycol solution 1.41g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.1271g, lauryl sodium sulfate 0.1126g, methyl acrylate 15.3g, methacrylate butyl ester 6.4g, third Olefin(e) acid 4.2g, hydroxyethyl methacrylate 1.7g, vinyltrimethoxysilane 1.2g and ammonium persulfate 0.059g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Isopropanol 18mL, ethyl orthosilicate 0.5g, silicone acrylic emulsion 1.0g and ammonium hydroxide 0.1g are taken, is stirred at room temperature It mixes 10min and obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls is added Triethoxysilane 0.1g.After 6-8h, reaction was completed, obtains double thin coating.
Embodiment 10：
First by deionized water 46g, sodium bicarbonate 1.50g, ethylene glycol solution 1.41g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 0.1271g, lauryl sodium sulfate 0.1126g, methyl acrylate 15.3g, methacrylate butyl ester 6.4g, third Olefin(e) acid 4.2g, hydroxyethyl methacrylate 1.7g, vinyltrimethoxysilane 1.2g and ammonium persulfate 0.036g mixing, stirring 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C of beginnings Remaining pre-emulsion is added dropwise, after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled down To after room temperature, with ammonium hydroxide by pH adjust within the scope of 7~8 (variable), using Buchner funnel decompression filter milky, The silicone acrylic emulsion of blueing light.Isopropanol 18mL, ethyl orthosilicate 0.5g, silicone acrylic emulsion 1.0g and ammonium hydroxide 0.1g are taken, is stirred at room temperature It mixes 10min and obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls is added Triethoxysilane 0.15g.After 6-8h, reaction was completed, obtains double thin coating.
Embodiment 11：
First by deionized water 44g, sodium bicarbonate 0.91g, ethylene glycol solution 0.83g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) it is 1.02g, lauryl sodium sulfate 0.351g, ethyl methacrylate 11.0g, ethyl methacrylate 3.7g, double Butyl methacrylate 2.1g, acrylic acid 6.4g, hydroxy-ethyl acrylate 3.6g, vinyltrimethoxysilane 4.9g and persulfuric acid Ammonium 0.40g mixing, stirring 30min (1000rpm) obtain milky white colour-stable pre-emulsion.Take 15mL pre-emulsions that there-necked flask is added In, it is heated to 80 DEG C and starts that remaining pre-emulsion is added dropwise, after being added dropwise after 90min, be further continued for heat preservation 2h, terminate later anti- It answers, after emulsion temperature is cooled to room temperature, pH is adjusted within the scope of 7~8 (variable) with ammonium hydroxide, uses Buchner funnel Decompression filter milky, blueing light silicone acrylic emulsion.Take isopropanol 18mL, ethyl orthosilicate 0.5g, silicone acrylic emulsion 1.0g and Ammonium hydroxide 0.1g stirs 10min and obtains uniform solution at room temperature.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H is added, 1H, 2H, 2H- perfluoro decyl triethoxysilane 0.15g.After 6-8h, reaction was completed, obtains double thin coating.
Embodiment 12：
First by deionized water 44g, sodium bicarbonate 0.95g, ethylene glycol solution 0.82g, OP-10 (polyoxethylene octylphenyl benzene Phenolic ether -10) 1.13g, lauryl sodium sulfate 0.406g, ethyl acrylate 16.0g, butyl methacrylate 4.1g, acrylic acid 6.4g, hydroxy-ethyl acrylate 0.6g, vinyltrimethoxysilane 4.7g and ammonium persulfate 0.040g mixing, stir 30min (1000rpm) obtains milky white colour-stable pre-emulsion.It takes 15mL pre-emulsions to be added in there-necked flask, is heated to 80 DEG C and starts to be added dropwise Remaining pre-emulsion after being added dropwise after 90min, is further continued for heat preservation 2h, reaction was completed later, and emulsion temperature is cooled to room After temperature, pH is adjusted within the scope of 7~8 (variable) with ammonium hydroxide, milky, blueing are filtered to obtain using Buchner funnel decompression The silicone acrylic emulsion of light.Isopropanol 23mL, ethyl orthosilicate 3.7g, silicone acrylic emulsion 4.5g and ammonium hydroxide 0.9g are taken, is stirred at room temperature 10min obtains uniform solution.60 DEG C are heated to, whole process persistently stirs, and keeps the temperature 2h, and 1H, 1H, 2H, 2H- perfluoro decyls three is added Ethoxysilane 0.06g.After 6-8h, reaction was completed, obtains double thin coating.
Embodiment as above is only the section Example of the present invention in the course of the research；The present invention is sent out in the course of the research Existing, the parameter of preparation method of the invention is adjusted in a certain range in preparation process, can equally be prepared with good The product of good performance.Specifically, when preparing milky white colour-stable pre-emulsion, acrylic ester monomer：Hydroxyalkyl acrylates Class monomer：Acrylic monomer：Vinyl trialkyl oxysilane=(30~99)：(0~20)：(0~30)：(1~20)；It is inorganic The quality of weak base is the 0.05%~5% of cross-linking monomer quality, and the quality of glycols homologue is cross-linking monomer quality 0.01%-5%, the gross mass of emulsifier are the 0.1%-5% of cross-linking monomer quality, and the content of the water of addition is entire reactant The 50%~70% of system.When preparing cohydrolysis condensation suspension, silicone acrylic emulsion：Alcohols solvent：Ethyl orthosilicate=(1-30)： (40-98)：(1-30)；Ammonium hydroxide accounts for the 0.5%-10% of cohydrolysis condensation suspension gross mass.
The silicone acrylic emulsion and double thin coating emulsion property indices that the present invention prepares are as shown in table 1.Silicone acrylic emulsion and Coating emulsion performance of film on glass slide is as shown in table 2.
The indices of table 1 silicone acrylic emulsion and coating emulsion
Index Silicone acrylic emulsion Double thin coating emulsions
Appearance The lotion of milky blueing light Milky, finely dispersed lotion
Gel fraction 2.01% /
Solid content 30.96% 54.43%
Viscosity/mPas 31.5 96.2
Calcium ion stability Pass through Pass through
Storage stability 2 years or more 2 years or more
The indices of table 2 silicone acrylic emulsion film and coating film
Index Silicone acrylic emulsion film Coating emulsion film
Appearance Film uniform ground is transparent The smooth film of white uniformity
Adhesive force 0 grade 0 grade
Water absorption rate % 3.88 0.5
Pencil hardness 5B 6H
To the contact angle of water 35.63° 150.34°
To the contact angle of diiodomethane 56.03° 137.41°
As shown in Fig. 2, the Average Particle Diameters that inventor determines prepared silicone acrylic emulsion are 105.6nm, grain size Narrow distribution.
IR Characterization is carried out to silicone acrylic emulsion and double thin coating, characterization result is shown in figure 3, wherein a is silicone acrylic emulsion IR Characterization, b are double thin coating IR Characterizations.2955cm in figure-1The absorption peak at place is that the stretching vibration of methylene and methyl is drawn It rises, 1726cm-1The very strong big spike of absorption that place occurs is the C=O double bond vibration absorption peaks in ester group, mainly in monomer What ester group generated；C=C stretching vibration peaks are not occurred among 1695~1630, this shows the double bond for participating in the monomer of reaction It is basic to disappear, all carry out free radical polymerization, it can be determined that go out vinyltriethoxysilane and carried out with acrylate monomer Copolymerization.1449cm-1The absorption peak at place is-CH2Deformation vibration；1386cm in figure-1The absorption peak at place is-CH3Deformation vibration Caused by characteristic absorption peak；1240~1140cm-1Place occur absorption peak be C-O-C keys asymmetric stretching vibration absworption peak and C-C stretching vibrations；1064cm-1The absorption peak that place occurs is Si-O stretching vibrations；1200-900cm in figure-1Between absorption peak Reinforce mainly caused by introducing C-F keys in system than silicone acrylic emulsion；In 803cm-1Place occur one it is stronger new Absorption peak is the asymmetric vibration absorption peak of Si-O-Si in system.Infrared figure illustrates that PFTS has been wrapped up silica and receives Rice grain surface.
Thermogravimetric analysis is carried out to silicone acrylic emulsion and double thin coating, is as a result shown in Fig. 4.Wherein, a curves indicate the third breast of silicon Liquid, b curves indicate double thin coating.On the thermogravimetric curve of silicone acrylic emulsion, between 340 DEG C~420 DEG C, scission of link occur is mainly The c h bond and C-O keys of C-C keys, side chain in polyacrylate backbone.Weightlessness has reached 90% in this section, due to lotion Contain organosilicon in copolymer, with the raising of temperature, the larger Si-O keys of bond energy and Si-C keys are gradually broken, final to go back Remaining 4% participation amount.On the thermogravimetric curve of double thin coating, between 340 DEG C~420 DEG C, occur mainly poly- the third of scission of link The c h bond and C-O keys of C-C keys, side chain on olefin(e) acid ester main chain.Between 470 DEG C~530 DEG C, the mainly titanium dioxide of appearance The Si-C keys and F-C keys that silicon particle surface is connected, finally there remains 35% participation amount, be much larger than silicone acrylic emulsion (4%), this Cross-linked structure as-Si-O-Si- is mainly formd in reaction process, results in inorganic content increase.
By the double thin coating preparation thin films in pairs of gained, Electronic Speculum observation is carried out, electron microscope is illustrated in Fig. 5-1, Fig. 5-2, figure In 5-3 and Fig. 5-4.Double thin coating preparations prepared when being 150min that Fig. 5-3 and Fig. 5-4 is the teos hydrolysis time Double thin films, amplify 15k times in Fig. 5-3,30k times of amplification in Fig. 5-4.From Fig. 5-3 and Fig. 5-4, it will be seen that working as positive silicon When the hydrolysis of ethyl acetate time is 150min, double thin film coated surfaces are made of uniform spherical particle, and the diameter of particle is at 80 nanometers Left and right has a small amount of ball being relatively large in diameter interspersed wherein, and the diameter of larger ball is in 200 rans.Granular surface layer, Provide certain roughness, and build suitable roughness advantageously form it is super-hydrophobic or superoleophobic.Fig. 5-1 and Fig. 5-2 is Double thin films of teos hydrolysis time prepared double thin coating preparations when being 40min amplify 20k times in Fig. 5-1, scheme Amplify 50k times in 5-2.From Fig. 5-1 and Fig. 5-2 as can be seen that waiting (40min) when hydrolysis time is shorter, generated painting peplomer Diameter is smaller, so the hydrolysis time of ethyl orthosilicate has the microscopic appearance of film critically important influence.
The surface chemistry composition of prepared double thin films is analyzed by surface power spectrum, analysis result is illustrated in figure In 6.It is 1.0% in the fluorine-containing mass ratio of raw material addition, can be seen that fluorine is accounted in double thin film coated surfaces by surface power spectrum 13.70%, this fluorine-contained surface substance is more likely to surface migration.Increased PFTS amounts are fluorine-containing to coating film coated surface in raw material As shown in fig. 7, when finding that fluorine content in feeding intake is relatively low, fluorine-contained surface amount increases with the middle fluorine of feeding intake and increases rapidly for the influence of amount Add, with the increase of inventory, the pace of change of fluorine-contained surface amount reduces.
Double thin films of the third film of silicon and double thin coating preparations prepared by silicone acrylic emulsion are measured to water and diiodomethane Contact angle.Such as the hookup that Fig. 8-1 is silicon the third film and water, Fig. 8-2 is the hookup of silicon the third film and diiodomethane.According to figure Shown in 8-1 and Fig. 8-2, the third film of silicon Qinshui oleophylic.And double thin films reach 150.34 ° (such as Fig. 8-3 institutes to the contact angle of water Show), 137.41 ° (as shown in fig. 8-4) are reached to the contact angle of diiodomethane, which has reached super-hydrophobic, oleophobic.

Claims (9)

1. a kind of preparation method of super-hydrophobic oleophobic coating, which is characterized in that including step：
1) by water, inorganic weak bases, glycols homologue, alkyl phenol polyoxyethylene ether class emulsifier, sulfonate and/or sulfate type The mixture of anion emulsifier, cross-linking monomer and cross-linked evocating agent stirs to obtain milky white colour-stable pre-emulsion；
Wherein, the cross-linking monomer include acrylic ester monomer, hydroxyalkyl acrylates class monomer, acrylic monomer and Vinyl trialkyl oxysilane, according to quality meter, acrylic ester monomer：Hydroxyalkyl acrylates class monomer：Acrylic compounds Monomer：Vinyl trialkyl oxysilane=(30~99)：(0~20)：(0~30)：(1~20)；The quality of inorganic weak bases is to hand over The 0.05%~5% of receipts or other documents in duplicate weight, the quality of glycols homologue are the 0.01%-5% of cross-linking monomer quality, emulsifier Gross mass is the 0.1%-5% of cross-linking monomer quality；
2) milky white colour-stable pre-emulsion reacts 1-8h at 40~90 DEG C, adjusts pH value to 7~8 by ammonium hydroxide after cooling, obtains Silicone acrylic emulsion；
3) silicone acrylic emulsion, alcohols solvent, ethyl orthosilicate and ammonium hydroxide are stirred evenly, is heated to 40-80 DEG C of reaction 1-10h, obtains Cohydrolysis is condensed suspension；According to weight meter, silicone acrylic emulsion：Alcohols solvent：Ethyl orthosilicate=(1-30)：(40-98)：(1- 30)；Ammonium hydroxide accounts for the 0.5%-10% of cohydrolysis condensation suspension gross mass；
4) it is condensed in suspension to cohydrolysis and perfluoroalkyl triethoxysilane and/or perfluoroalkyl trimethoxy silane is added, 0.5-8h is reacted at 50-70 DEG C, obtains super-hydrophobic oleophobic coating.
2. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that inorganic weak in step 1) Alkali is one or more in sodium bicarbonate, saleratus and sodium carbonate；
Glycols homologue is one or more in ethylene glycol, propylene glycol and butanediol；
Alkyl phenol polyoxyethylene ether class emulsifier is octyl phenol polyoxyethylene ether and/or nonylphenol polyoxyethylene ether；
Sulfonate and/or sulfate type anion emulsifier are alkylbenzene sulfonate, alkylsulfonate, aliphatic alcohol sulfate and virtue It is one or more in alkyl phenol polyoxyethylene ether sulfate；
Cross-linked evocating agent is one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
3. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that in step 1),
Acrylic ester monomer is R1COOR2, R1For vinyl, methyl ethylene, dimethyl ethenyl or ethyl vinyl, R2For The alkyl of 1-10 carbon atom；
Hydroxyalkyl acrylates class monomer is R3COO-R4- OH, R3For vinyl, methyl ethylene, dimethyl ethenyl or second Base vinyl, R4For the alkyl of 1-10 carbon atom；
Acrylic monomer is acrylic acid, methacrylic acid, ethylacrylic acid or dimethacrylate；
Vinyl trialkyl oxysilane is vinyltrimethoxysilane or vinyltriethoxysilane.
4. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that in step 1), according to matter Gauge, alkyl phenol polyoxyethylene ether class emulsifier：Sulfonate and/or sulfate type anion emulsifier=1:(1~9).
5. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that in step 2), first take 10 The initiation reaction at 40-75 DEG C of~20mL pre-emulsions, then instills remaining pre-emulsion at 75-90 DEG C；After being added dropwise, instead System is answered to keep the temperature 1-8h at 60-90 DEG C.
6. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that in step 3), alcohols is molten Agent is one or more in isopropanol, methanol, ethyl alcohol, propyl alcohol and butanol.
7. the preparation method of super-hydrophobic oleophobic coating as described in claim 1, which is characterized in that in step 4), perfluor alkane Ethyl triethoxy silicane alkane be 1H, 1H, 2H, 2H- perfluoroalkyl triethoxysilanes, perfluoroalkyl trimethoxy silane be 1H, 1H, 2H, 2H- perfluoroalkyl trimethoxy silane, the alkyl are the alkyl of 4~12 carbon atoms；Perfluoroalkyl triethoxysilane And/or the 0.1%-30% that the quality of perfluoroalkyl trimethoxy silane is cross-linking monomer quality.
8. super-hydrophobic oleophobic coating prepared by claim 1~7 any one of them preparation method.
9. by the super-hydrophobic oleophobic film of super-hydrophobic oleophobic coating preparation according to any one of claims 8.
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