CN103709882B - A kind of super-double-hydrophobic surface and its preparation method with universality - Google Patents

A kind of super-double-hydrophobic surface and its preparation method with universality Download PDF

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CN103709882B
CN103709882B CN201310633591.1A CN201310633591A CN103709882B CN 103709882 B CN103709882 B CN 103709882B CN 201310633591 A CN201310633591 A CN 201310633591A CN 103709882 B CN103709882 B CN 103709882B
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super
epoxy resin
microballoon
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double
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CN103709882A (en
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胡继文
李妃
邹海良
林树东
刘国军
涂园园
齐健
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Guangzhou Chemical Co Ltd of CAS
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Guangzhou Chemical Co Ltd of CAS
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
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    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

Abstract

The invention belongs to super two thin material field, disclose a kind of super-double-hydrophobic surface and its preparation method with universality, this super-double-hydrophobic surface with universality is prepared by following method: by the N components dissolved of a kind of aqueous fluorine-containing epoxy resin in solvent P, obtain N solution; Again by the M component disperses of super for a kind of water dispersible two thin microballoon in N solution, add catalyst I subsequently, obtain a kind of super two hydrophobic coating; Finally super two hydrophobic coating is coated in through pretreated substrate material surface, dry, obtain having the super-double-hydrophobic surface of universality. The present invention has good scrubbing resistance and erosion resistance, and Bound moisture disperses super two thin microballoon and aqueous fluorine-containing epoxy resin advantage separately, gives substrate super-hydrophobic and super thin oil ability, and major part base material is feasible, has universality.

Description

A kind of super-double-hydrophobic surface and its preparation method with universality
Technical field
The invention belongs to super two thin material field, it is specifically related to a kind of super-double-hydrophobic surface and its preparation method with universality.
Background technology
Surface wettability is one of important feature of solid surface, wettability can be weighed with the contact angle of water on the surface, usually by water contact angle more than 150 ��, the roll angle surface that is less than 10 �� be called super hydrophobic surface, oil is had the contact angle being greater than 150 �� by surface, it will be recognized that be super oleophobic surface. If the static contact angle of the water on a certain surface and oil is all greater than 150 �� and its roll angle is all less than 5 ��, then this interface can be referred to as super two thin interface. Super hydrophobic surface and super-double-hydrophobic surface possess certain self-cleaning function, and the water droplet that namely surface contaminant can be tumbled such as dust etc. is taken away and do not leave any vestige. Automatic cleaning coating has the advantages such as water saving, energy-saving and environmental protection, more and more gets more and more people's extensive concerning, and is one of the focus of current material subject research.
Relative to constructing super-drainage interface, the preparation of super two thin material and construct and seem more difficult, the Science and Technology problem mainly related to is more, is therefore still in development in this respect, seldom has the report about super two thin material industrialization product to occur.
The roughness of solid surface and low surface energy prepare influence factor that is super-hydrophobic or super-double-hydrophobic surface most critical, and fluorochemicals and fluoropolymer are widely used in this field because of its low surface energy. In order to build super-hydrophobic or super-double-hydrophobic surface at the smooth surface such as glass, metal, the method that people commonly use is by inorganic nano/micron particle such as silicon-dioxide, titanium dioxide, Z 250s and fluoropolymer is blended or by Nano/micron level particle fluoride, is then coated onto material surface thus builds super-hydrophobic or super-double-hydrophobic surface by the Nano/micron level particle of fluoride. In these methods, being difficult to really be bonded together by chemical bonding effect between polymkeric substance, inorganic particulate and substrate, mainly by physical adsorption effect, therefore the weather resistance of super-double-hydrophobic surface is not fine. In addition, preparation fluoride inorganic particulate needs this kind of out-phase reaction that fluoropolymer is grafted to surface of inorganic particles, and major part report all needs surface of inorganic particles is carried out a series of process, and step is comparatively loaded down with trivial details causes very difficult large-scale industrialization.
Patent 201110131477.X proposes the preparation of a kind of fluorine-containing pair of functional microsphere and is applied to construct super-double-hydrophobic surface. Main method be preparation a kind of containing multiple functional group nanometer or micro-size particles, make its surface not only containing fluorochemicals, the group of covalent linkage can be formed in addition with substrate reaction, again this kind of surface grafting is had fluorochemicals and can with matrix carry out chemical bonding nanometer or a micron microballoon be sprayed on substrate surface, and construct super two thin interface with this. Coating prepared by this invention has excellent super two thin characteristics, and coating is bonded with substrate surface by covalent linkage, so that ultra-amphosphobic can have better weather resistance. But, the base material that this method can process has certain limitation, it is necessary to containing active group (such as hydroxyl, carboxyl, amino etc.), otherwise do not possess cohesiveness, and fluorine-containing microballoon needs to be dispersed in containing in fluorous solvent.
Patent 201110266897.9 propose a kind of utilize fluorine-containing silicon-containing copolymer and silicon-dioxide carry out blended after carry out assembling film forming on the surface containing active group, surface well ultra-amphosphobic energy can be given, this kind of method utilizes more fluorine-containing silicon-containing copolymer, cost is higher, and need blended assembling to react, technics comparing is complicated, and base material need to contain active group, does not have universality.
Patent 201110373304.9 proposes and utilizes atom transfer radical polymerization to obtain crosslinkable ultra-amphosphobic microballoon in amino modified inorganic microspheres surface grafting crosslinkable monomers and fluorochemical monomer, this fluorine-containing microballoon assembling film forming obtains super-double-hydrophobic surface excellent performance, not only there is good hydrophobic oleophobic contact angle, there is good resistance to acids and bases simultaneously, also have good weathering resistance. But the treating processes of the method is comparatively loaded down with trivial details, reagent, equipment requirements is higher, and fluorine-containing microballoon needs to be dispersed in containing, in fluorous solvent, surface does not have cohesiveness group yet, and therefore cementability neither be very strong.
In recent years, utilize document and the patent of the super oleophobic surface of fluoropolymer constructing super-drainage more, but also there is following problem in the major part of document report at present: (1) bonding force between fluoropolymer and substrate surface does not cause by force the rub resistance of coating, and washing fastness is not strong; (2) most methods condition harshness, complex steps, cost height, and do not possess universality; (3) fluoropolymer that the super thin oil of constructing super-drainage adopts is mainly oil-soluble, this kind of oil soluble fluoropolymer, it is necessary to use a large amount of organic solvents, not only expensive but also can be polluted by environment, is unfavorable for large-scale industrialization.
Therefore, develop a kind of simple and be easy to realize and the super oleophobic surface of method constructing super-drainage of environmental protection, become modern times coating and the growing demand of field of surface treatment.
Summary of the invention
In order to overcome the shortcoming of prior art and deficiency, the primary and foremost purpose of the present invention is to provide a kind of super-double-hydrophobic surface with universality;
Another object of the present invention is to provide the preparation method of above-mentioned super-double-hydrophobic surface;
The object of the present invention is achieved through the following technical solutions:
A super-double-hydrophobic surface with universality, be by N components dissolved in solvent P, obtain N solution; Again by M component disperses in N solution, add catalyst I subsequently, obtain a kind of super two hydrophobic coating; Finally super two hydrophobic coating is coated in substrate material surface, dry, namely obtain having the ultra-amphosphobic surface of universality; Described N component is a kind of aqueous fluorine-containing epoxy resin, and M component is a kind of super two thin microballoon of water dispersible.
Described M component is super two thin microballoons of water dispersible, particle diameter is 50-1000nm, this microballoon is by introducing one layer of epoxy resin A at substrate microsphere surface, the epoxide group ring-opening reaction grafting hydrophilic compounds B and fluorochemicals C on recycling epoxy resin A surface obtains, as shown in Figure 1, in formula, g represents grafting to its structural formula.
Described substrate microballoon is that silicon dioxide microsphere, aluminum oxide micro-sphere, titanium dioxide microballoon sphere, ferric oxide microballoon and surface are containing the one in the polymer microballoon of hydroxyl, it is preferable that silicon dioxide microsphere; Particle diameter is 50-1000nm.
Described epoxy resin A is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy, polymethyl acrylic acid glycidyl ether, more than one in polypropylene-base glycidyl ether, poly-adjacent toluene glycidyl ether and polyphenyl glycidyl ether, it is preferable that polymethyl acrylic acid glycidyl ether, more than one in poly-adjacent toluene glycidyl ether and polyphenyl glycidyl ether, its molecular weight is 1000-100000.
Described hydrophilic compounds B is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) amine, more than one in methoxy poly (ethylene glycol) mercapto alcohol, methoxy poly (ethylene glycol) carboxylic acid, polyoxyethylene glycol amine and polyoxyethylene glycol mercaptan, and molecular weight is 300-2000.
Described fluorochemicals C is 3-perfluoro capryl propyl alcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro hexyl ethanol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, 1H, 1H, 2H, own-1-the alcohol of 2H-perfluor, perfluorinated acid, perfluor caproic acid, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, 1H, 1H, 2H, 2H-perfluoro decyl mercaptan, 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, more than one in 4-perfluoro capryl aniline, 1H, 1H-perfluoro capryl amine and perfluoro octyl sulfonic acid amine.
The preparation method of the super two thin microballoon of described water dispersible, comprises the following steps:
(1) epoxy resin A is dissolved in solvent E and configures epoxy resin solution A, substrate microballoon is dispersed in solvent G, ultrasonic 1h, obtain microballoon dispersion liquid, continue ultrasonic limit, limit epoxy resin solution A to be added drop-wise in microballoon dispersion liquid with the speed of 0.2-5mL/min, then continue ultrasonic 30-180min, revolve and steam except desolventizing, thermal treatment, cooling, adds solvent E and heavily disperses, centrifuge washing, drying, obtains the coated microballoon of epoxy resin;
(2) the coated microballoon of epoxy resin prepared by step (1) is dispersed in solvent H1In, supersound process, then add catalyzer K and be heated to 60-120 DEG C, then successively add fluorochemicals C solution and hydrophilic compounds B when stirring, reaction 2-24h, finally remove the solvent in reaction system, obtain the super two thin microballoon of water dispersible.
Solvent E, G described in step (1) is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide.
Ultrasound condition described in step (1) is ultrasonic power is 300W, and temperature is 35 DEG C; Described heat-treat condition is thermal treatment 20-90min in 60-130 DEG C of vacuum drying oven; Described washing times is 4 times.
Epoxy resin solution A described in step (1) and microballoon dispersion liquid mass percentage concentration are respectively 1-10%, 0.2-5%, and the mass ratio of substrate microballoon and epoxy resin A is 1:2-10.
Catalyzer K described in step (2) is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine.
Solvent H described in step (2)1, solvent H2For more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide.
Fluorochemicals C solution described in step (2) is dissolved in solvent H by fluorochemicals C2Prepare; The coated microballoon of described epoxy resin, solvent H1, solvent H2, fluorochemicals C, hydrophilic compounds B and catalyzer K mass ratio be 1:(1-50): (1-50): (0.2-10): (0.2-10): (0.001-0.1).
Supersound process condition described in step (2) is ultrasonic power is 300W, and temperature is 35 DEG C, and the time is 30min.
Described N component is aqueous fluorine-containing epoxy resin, preparation method comprises the following steps: be dissolved in solvent by epoxy resin A, dripping the mixed solution adding finely dispersed hydrophilic compounds B, fluorochemicals C and catalyzer in advance at 60-120 DEG C while stirring, rate of addition is 0.1g/min-100g/min, drips after adding end, continue reaction 4-10 hour, it is cooled to room temperature, concentrated, then precipitate in solvent F, drying, obtains aqueous fluorine-containing epoxy resin.
Described epoxy resin A is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy, polymethyl acrylic acid glycidyl ether, polypropylene-base glycidyl ether, more than one in poly-adjacent toluene glycidyl ether and polyphenyl glycidyl ether, it is preferable that more than one in polymethyl acrylic acid glycidyl ether, poly-adjacent toluene glycidyl ether and polyphenyl glycidyl ether.
Described hydrophilic compounds B is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) amine, more than one in methoxy poly (ethylene glycol) mercapto alcohol, methoxy poly (ethylene glycol) carboxylic acid, polyoxyethylene glycol amine and polyoxyethylene glycol mercaptan, and molecular weight is 300-2000.
Described fluorochemicals C is 3-perfluoro capryl propyl alcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro hexyl ethanol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, 1H, 1H, 2H, own-1-the alcohol of 2H-perfluor, perfluorinated acid, perfluor caproic acid, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, 1H, 1H, 2H, 2H-perfluoro decyl mercaptan, 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, more than one in 4-perfluoro capryl aniline, 1H, 1H-perfluoro capryl amine and perfluoro octyl sulfonic acid amine.
Described solvent is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide.
Described catalyzer is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine.
Described solvent F is normal hexane, anhydrous diethyl ether, sherwood oil, ethyl acetate, methyl alcohol, more than one in second alcohol and water.
Mass ratio between described epoxy resin A, solvent, hydrophilic compounds B, fluorochemicals C and catalyzer is: 1:10-100:1-10:1-10:0.00001-0.0001.
Described catalyst I is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine.
Described solvent P is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone and phenylfluoroform.
The preparation method of above-mentioned super-double-hydrophobic surface comprises the following steps:
(1) substrate surface pre-treatment;
(2) by N components dissolved in solvent P, N solution is obtained; Again by M component disperses in N solution, stirring or supersound process make microballoon evenly disperse, then add catalyst I, obtain a kind of super two hydrophobic coating; Wherein, N component is aqueous fluorine-containing epoxy resin, and M component is the super two thin microballoon of water dispersible;
(3) super two hydrophobic coating prepared by step (2) is coated in substrate surface in step (1), film forming, then at 90-140 DEG C, it is cross-linked 2-24h, obtain the material of super-hydrophobic/thin oil, be a kind of ultra-amphosphobic surface.
Base material described in step (1) is sheet glass, cotton, filter paper, thin-film material, tinsel, plastic sheet, timber or cement matrix; Wherein the pretreatment process of filter paper, tinsel, plastic sheet, thin-film material, timber, cement matrix and cotton is: base material is successively with ethanol, water washing, then dry; The pretreatment process of sheet glass is: by sheet glass, at piranha solution, (volume ratio is the dense H of 7:32SO4And H2O2Mixed solution) middle immersion 5h, more successively with ethanol, water washing, then dry.
The M component of the super two thin microballoon of the water dispersible described in step (2), the N component of aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:5-100:0.001-0.01:10-200.
Coating method described in step (3) is applied by the mode of spraying or dip-coating; Film-forming temperature is 30 DEG C.
The described materials application with ultra-amphosphobic surface, in production life aspect, comprises the windshield glass of the outer protective of military industry equipment, the outer field water-tight corrosion-proof of oil pipeline, kitchen guarding's apparatus, automobile and aircraft.
The principle of the present invention: two important factors affecting solid surface wettability are surface microstructure and the surface only energy of solid, therefore to be prepared super two thin material and must meet two conditions, one is need the uneven surface constructing micro-nano rice, and another introduces low-surface energy substance molecular layer. The present invention is taking the super two thin microballoon of water dispersible as providing condition at surface construction coarse structure, then introduces aqueous fluorine-containing epoxy resin, makes the hydrophobic oleophobic performance of coating reach best by the ratio of both adjustment. Microballoon and epoxy resin are all hydrophilic, avoid the use constructing organic solvent in super-double-hydrophobic surface process, are conducive to environmental protection. In addition, a large amount of epoxide group in coating, be can be used for being cross-linked between base material and microballoon and is namely firmly combined by chemical bond, thus the weather resistance of the material that is improved.
Compared with prior art, the present invention has the following advantages and useful effect:
(1) the present invention adopts the method preparing super-double-hydrophobic surface of offer, and simple, cost is lower, is expected to scale operation;
(2) the two kinds of components preparing super-double-hydrophobic surface that the present invention relates to all have good water dispersible, can avoid using environmentally harmful organic solvent; Epoxide groups a large amount of in two components can realize between fluorine-containing microballoon and with base material by chemical bond mortise; Fluorochemicals can provide low surface interface, and gained super-double-hydrophobic surface has good scrubbing resistance and erosion resistance.
(3) when aqueous fluorine-containing epoxy resin and the super two thin microballoon of water dispersible are separately for constructing super-double-hydrophobic surface, there is respective shortcoming, aqueous fluorine-containing epoxy resin can provide low surface energy but can not provide roughness, therefore can only construct super-double-hydrophobic surface at coarse substrate surface, the Bound moisture of the present invention super two thin microballoon of dispersion and aqueous fluorine-containing epoxy resin advantage separately, the super two thin microballoon of water-dispersion can provide surfaceness, water fluoric resin can make up the low surface energy of the super two thin microballoon of water dispersible, thus give substrate super-hydrophobic and super thin oil ability, by arbitrarily adjusting epoxy component in the ratio of two components and each component, hydrophilic monomer and fluorine component according to needed for the base material that is applied to regulate flexibly, and base material is feasible (comprises yarn fabric to major part, polymkeric substance, pottery, buildings, metal base, the scraps of paper etc.), therefore there is universality.
Accompanying drawing explanation
Fig. 1 is the general structure of super two thin microballoons of water dispersible;
Fig. 2, Fig. 3 are respectively the silicon dioxide microsphere of embodiment 1 preparation and the TEM photo of the super two thin microballoon of water dispersible;
Fig. 4 is the SEM photograph of the super two thin microballoon of water-dispersion prepared by embodiment 1;
Fig. 5 is the Infrared Characterization figure of the super two thin microballoon of water dispersible that embodiment 1 prepares;
Fig. 6 is the SEM photograph of the super-double-hydrophobic surface that embodiment 8 is constructed in glass sheet surface;
Fig. 7 is the SEM photograph of the super-double-hydrophobic surface that embodiment 9 is constructed in glass sheet surface;
Fig. 8 is the SEM photograph of the super-double-hydrophobic surface that embodiment 10 is constructed at cotton surface;
Fig. 9 is the SEM photograph of the super-double-hydrophobic surface that embodiment 11 is constructed at wood surface.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation of super two thin microballoons of water dispersible:
(1) preparation of silicon dioxide microsphere: add 100ml dehydrated alcohol and 3mL ammoniacal liquor in the round-bottomed flask of 250mL, then drip and add 4mL tetraethyl orthosilicate, after reacting 24h at 35 DEG C, product dehydrated alcohol centrifuge washing three times, the silicon dioxide microsphere obtained carries out vacuum freezedrying, and final gained silicon dioxide microsphere particle diameter is 100 �� 5nm.
(2) preparation of the coated microballoon of epoxy resin: polymethyl acrylic acid glycidyl ether is dissolved in solvent E and configures epoxy resin solution, the substrate microballoon (silicon dioxide microsphere) step (1) prepared is dispersed in solvent G, supersound process 1h, obtain microballoon dispersion liquid, continuing ultrasonic limit, limit is added drop-wise in microballoon dispersion liquid by epoxy resin solution with the speed of 0.2mL/min, continue ultrasonic 30min again, revolve and after steaming removing major part solvent, product is placed in 60 DEG C of vacuum drying oven thermal treatment 90min, after product cools, add solvent E heavily disperse, centrifuge washing 4 times, product is dry at room temperature in vacuo, namely the coated microballoon of epoxy resin is obtained.
Solvent E, G are tetrahydrofuran (THF); Polymethyl acrylic acid Racemic glycidol ethereal solution and microballoon dispersion liquid mass percentage concentration are respectively 1%, 0.2%; The mass ratio of substrate microballoon and polymethyl acrylic acid glycidyl ether is 1:2.
(3) preparation of the super two thin microballoon of water dispersible: the coated microballoon of epoxy resin step (2) prepared is dispersed in solvent H1In, supersound process 30min, then add catalyzer K and be heated to 60 DEG C, then successively add when stirring and it is dissolved in solvent H2Fluorochemicals C solution and hydrophilic compounds B react 24h, finally remove the solvent in reaction system, obtain the super two thin microballoon of described water dispersible.
Solvent H1, solvent H2For tetrahydrofuran (THF), catalyzer K is triethylamine; Fluorochemicals C is 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, and hydrophilic compounds B is methoxy poly (ethylene glycol) mercapto alcohol, and molecular weight is 1000; Microballoon, solvent H1, solvent H2, fluorochemicals C, hydrophilic compounds B and catalyzer K mass ratio be 1:1:1:0.2:0.2:0.001.
Structural characterization such as Fig. 2, shown in 3,4,5:
Fig. 2 and 3 is respectively the silicon dioxide microsphere of embodiment 1 preparation and the TEM photo of the super two thin microballoon of water dispersible, and Fig. 4 is the SEM photograph of the super two thin microballoon of water-dispersion, and can obtain unmodified silicon-dioxide particle diameter by Fig. 2 is 100 �� 5nm, and size is more even. It is 130 �� 5nm that Fig. 3 can obtain the silicon-dioxide particle diameter after grafting polymkeric substance, in figure, high-visible silicon-dioxide shell has one layer of polymeric wall, same can also see that there is one layer of polymeric on the surface of the super two thin microballoon of water-dispersion in the diagram, so smoothless, particle diameter is at about 130nm, and the result of TEM is just corresponding.
Fig. 5 is the Infrared Characterization figure of the super two thin microballoon of water dispersible that embodiment 1 prepares, 3483cm-1The wider absorption peak that place occurs, corresponding to the antisymmetric stretching vibration of-OH base and the symmetrical stretching vibration of silica sphere; 2968cm-1The wide peak at place is methoxy poly (ethylene glycol) mercapto alcohol, perfluor spicy thioalcohol, the C-H stretching vibration of-CH3 in polymethyl acrylic acid glycidyl ether; 1726cm-1For the stretching vibration absorption peak of the C=O of polymethyl acrylic acid glycidyl ether; 1104cm-1, 1222cm-1The strong absorption peak that place occurs is attributed to together with-C-F stretching vibration overlaps with the antisymmetric stretching vibration absorption peak of Si-O-Si; 804cm-1Place is the characteristic peak of silicon-dioxide; 935cm-1Place is the characteristic peak of ring oxygen, is the ring oxygen in polymethyl acrylic acid glycidyl ether.
Embodiment 2
The preparation of super two thin microballoons of water dispersible:
(1) preparation of silicon dioxide microsphere: add 50ml dehydrated alcohol, 3ml deionized water and 3ml ammoniacal liquor in the round-bottomed flask of 100ml, then drip and add 2ml tetraethyl orthosilicate, after reacting 24 at 25 DEG C, product dehydrated alcohol centrifuge washing three times, the silicon dioxide microsphere obtained carries out vacuum freezedrying, and final gained silicon dioxide microsphere particle diameter is 350 �� 5nm.
(2) preparation of the coated microballoon of epoxy resin: poly-adjacent toluene glycidyl ether is dissolved in solvent E and configures epoxy resin solution, silicon dioxide microsphere is dispersed in solvent G, supersound process 1h, obtain microballoon dispersion liquid, continuing ultrasonic limit, limit is added drop-wise in microballoon dispersion liquid by epoxy resin solution with the speed of 3mL/min, continue ultrasonic 100min again, revolve and after steaming removing major part solvent, product is placed in 90 DEG C of vacuum drying oven thermal treatment 40min, after product cools, add solvent E heavily disperse, centrifuge washing 4 times, product is dry at room temperature in vacuo, the coated microballoon of epoxy resin can be obtained.
Solvent E, G are dimethyl formamide; Poly-adjacent toluene Racemic glycidol ethereal solution and dispersion liquid microspheres quality percentage concentration are respectively 3%, 2%; The mass ratio of substrate microballoon (silicon dioxide microsphere) and poly-adjacent toluene glycidyl ether is 1:6.
(3) preparation of the super two thin microballoon of water dispersible: the coated microballoon of epoxy resin step (2) prepared is dispersed in solvent H1In, supersound process 30min, then add catalyzer K and be heated to 80 DEG C, then successively add when stirring and it is dissolved in solvent H2Fluorochemicals C solution and hydrophilic compounds B react 8h, finally remove the solvent in reaction system, obtain the super two thin microballoon of described water-dispersion.
Solvent H1, solvent H2For dimethyl formamide, catalyzer K is triethylamine; Fluorochemicals C is perfluorobutyric acid, and hydrophilic compounds B is methoxy poly (ethylene glycol) mercaptan, and molecular weight is 1000; Microballoon, solvent H1, solvent H2, fluorochemicals C, the mass ratio of hydrophilic compounds B and catalyzer K is 1:10:20:3:2:0.01.
The Spectrum Analysis of product is as follows: FT-IR:3453cm-1The wider absorption peak that place occurs, corresponding to the antisymmetric stretching vibration of-OH base and the symmetrical stretching vibration of silica sphere; 2920cm-1The wide peak at place is methoxy poly (ethylene glycol) mercapto alcohol, perfluorobutyric acid, the C-H stretching vibration of-CH3 in poly-adjacent toluene glycidyl ether; 1745cm-1The peak of the wide a little point at place is the stretching vibration absorption peak of the C=O stayed after poly-adjacent toluene glycidyl ether and perfluorobutyric acid react; 1231cm-1, 1305cm-1The strong absorption peak that place occurs is attributed to together with-C-F stretching vibration overlaps with the antisymmetric stretching vibration absorption peak of Si-O-Si; 824cm-1Place is the characteristic peak of silicon-dioxide; 915cm-1Place is the characteristic peak of ring oxygen, is the ring oxygen in poly-adjacent toluene glycidyl ether; 860cm-1The C-H charateristic avsorption band on phenyl ring that place is poly-adjacent toluene glycidyl ether.
Embodiment 3
The preparation of super two thin microballoons of water dispersible:
(1) preparation of the polymer microballoon of hydroxyl is contained on surface: progressively add 130mL distilled water under stirring in the there-necked flask of 500mL, the mixture of 4.80g methyl methacrylate and 0.4g Ethylene glycol dimethacrylate, and 41mg peroxy-disulfuric acid aqueous solutions of potassium (5mL), reaction system rouses nitrogen 30min with the oxygen in removal system at 25 DEG C, it is placed in the oil bath resume reaction 2h being preheating to 90 DEG C again, reaction is centrifugal after terminating, priority water and methyl alcohol heavily disperse centrifuge washing, product room temperature dried in vacuo overnight, the polyalcohol microspherulite diameter obtained is 220 �� 5nm.
(2) preparation of the coated microballoon of epoxy resin: polyphenyl glycidyl ether is dissolved in solvent E and configures epoxy resin solution, the substrate microballoon (polymer microballoon) step (1) prepared is dispersed in solvent G, supersound process 1h, obtain microballoon dispersion liquid, continuing ultrasonic limit, limit is added drop-wise in microballoon dispersion liquid by epoxy resin solution with the speed of 5mL/min, continue ultrasonic 180min again, revolve and after steaming removing major part solvent, product is placed in 130 DEG C of vacuum drying oven thermal treatment 20min, after product cools, add solvent E heavily disperse, centrifuge washing 4 times, product is dry at room temperature in vacuo, the coated microballoon of epoxy resin can be obtained.
Solvent E, G are N-Methyl pyrrolidone; Polyphenyl glycidyl ether solution and microballoon dispersion liquid mass percentage concentration are respectively 10%, 5%; The mass ratio of substrate microballoon (polymer microballoon) and polyphenyl glycidyl ether is 1:10.
(3) preparation of the super two thin microballoon of water dispersible: the coated microballoon of epoxy resin step (2) prepared is dispersed in solvent H1In, supersound process 30min, then add catalyzer K and be heated to 120 DEG C, then successively add when stirring and it is dissolved in solvent H2Fluorochemicals C solution and hydrophilic compounds B react 2h, finally remove the solvent in reaction system, obtain the super two thin microballoon of water dispersible.
Solvent H1, solvent H2For N-Methyl pyrrolidone, catalyzer K is N, N-diisopropyl ethyl amine; Fluorochemicals C is 1H, 1H-perfluoro capryl amine, and hydrophilic compounds B is methoxy poly (ethylene glycol) carboxylic acid, and molecular weight is 1500; Microballoon, solvent H1, solvent H2, fluorochemicals C, hydrophilic compounds B and catalyzer K mass ratio be 1:50:50:10:10:0.1.
The Spectrum Analysis of product is as follows: the wider absorption peak that FT-IR:3452cm-1 place occurs, corresponding to the antisymmetric stretching vibration of-OH base and the symmetrical stretching vibration on polymer microballoon surface; The N-H stretching vibration that the weak absorbing peak at 3321cm-1 place is remaining after perfluoro capryl amine reacts absorbs; 2931cm-1The wide peak at place is methoxy poly (ethylene glycol) carboxylic acid, perfluoro capryl amine, the C-H stretching vibration of-CH3 in polyphenyl glycidyl ether; 1725cm-1Place is the stretching vibration absorption peak of the C=O stayed after polyphenyl glycidyl ether and methoxy poly (ethylene glycol) carboxylic acid reaction; 1300cm-1The strong wide absorption peak that place occurs is attributed to-C-F stretching vibration absorption peak; 922cm-1Place is the characteristic peak of ring oxygen, is the ring oxygen in polyphenyl glycidyl ether; 890cm-1The C-H charateristic avsorption band on phenyl ring that place is polyphenyl glycidyl ether.
Embodiment 4
The preparation of aqueous fluorine-containing epoxy resin: epoxy resin A is dissolved in solvent, the mixed solution adding hydrophilic compounds B scattered in advance, fluoropolymer C and catalyzer is dripped while stirring at 120 DEG C, rate of addition is 100g/min, drip after adding end, after continuing reaction 4h, after being cooled to room temperature, concentrated, redeposition is to, in solvent F, obtaining aqueous fluorine-containing epoxy resin after dry; Mass ratio between its epoxy resin A, solvent, hydrophilic compounds B, fluoropolymer C and catalyzer is 1:100:10:10:0.0001; Epoxy resin A is poly-adjacent toluene glycidyl ether, and solvent E is pimelinketone, and hydrophilic compounds B is polyoxyethylene glycol amine (molecular weight is 300), and fluoropolymer C is perfluoro hexyl ethanol, and catalyzer is 1-propyl imidazole, and solvent F is normal hexane.
The Spectrum Analysis of product is as follows: 1H-NMR (CDCl3 makees solvent): 3.75ppm and 4.25ppm is two absorption peaks of-CH2-between oxirane ring and ester bond in poly-adjacent toluene glycidyl ether monomers, 2.57ppm and 2.85ppm is two absorption peaks of-CH2-in oxirane ring, 3.2ppm is the absorption peak of methyne (-CH-) in oxirane ring, a series of absorption peaks between 3.4-3.ppm are then the absorption peak of-CH2 in polyoxyethylene glycol amine, can obviously see the methylene radical (-CH of perfluoro hexyl ethanol2-) absorption peak, respectively at 4.77ppm and 2.33ppm place, can show that polyoxyethylene glycol amine and perfluoro hexyl ethanol have been bonded on the poly-adjacent toluene glycidyl ether of main chain, and remain the ring oxygen of a part.
Embodiment 5
The preparation of aqueous fluorine-containing epoxy resin: epoxy resin A is dissolved in solvent, the mixed solution adding hydroaropic substance B scattered in advance, fluoropolymer C and catalyzer is dripped while stirring at 60 DEG C, rate of addition is 0.1g/min, drip after adding end, after continuing reaction 10h, after being cooled to room temperature, concentrated, redeposition is to, in solvent F, obtaining aqueous fluorine-containing epoxy resin after dry; Mass ratio between its epoxy resin A, solvent E, hydroaropic substance B, fluoropolymer C and catalyzer is 1:10:1:1:0.00001; Epoxy resin A is polyphenyl glycidyl ether, and solvent is dioxane, and hydrophilic compounds B is methoxy poly (ethylene glycol) mercaptan (molecular weight is 500), fluoropolymer C is 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, catalyzer is benzyltriethylammoinium chloride, and solvent F is sherwood oil.
The Spectrum Analysis of product is as follows: 1H-NMR (CDCl3 makees solvent): 3.69ppm and 4.31ppm is two absorption peaks of polyphenyl glycidyl ether-CH2-between oxirane ring and ester bond, 2.62ppm and 2.95ppm is two absorption peaks of-CH2-in oxirane ring, 3.32ppm is the absorption peak of methyne (-CH-) in oxirane ring, a series of absorption peaks between 3.4-3.65ppm are then the absorption peak of-CH2 in methoxy poly (ethylene glycol) mercaptan, 4.89ppm and 2.51ppm is two on perfluor spicy thioalcohol-CH2 absorption peaks, can show that methoxy poly (ethylene glycol) mercaptan and perfluor spicy thioalcohol have been bonded on main chain polyphenyl glycidyl ether, and remain the ring oxygen of a part.
Embodiment 6
The preparation of aqueous fluorine-containing epoxy resin: epoxy resin A is dissolved in solvent, the mixed solution adding hydroaropic substance B scattered in advance, fluoropolymer C and catalyzer is dripped while stirring at 100 DEG C, rate of addition is 50g/min, drip after adding end, after continuing reaction 7h, after being cooled to room temperature, concentrated, redeposition is to, in solvent F, obtaining aqueous fluorine-containing epoxy resin after dry; Its epoxy resin A, mass ratio between solvent, hydroaropic substance B, fluoropolymer C and catalyzer is 1:60:5:5:0.00008, epoxy resin A is polymethyl acrylic acid glycidyl ether, solvent is tetrahydrofuran (THF), and hydrophilic compounds B is methoxy poly (ethylene glycol) carboxylic acid (molecular weight is 2000), and fluoropolymer C is 1H, 1H-perfluoro capryl amine, catalyzer is N, N-diisopropyl ethyl amine, and solvent F is methyl alcohol.
The Spectrum Analysis of product is as follows: 1H-NMR (CDCl3 makees solvent): 3.52ppm and 4.26ppm is two absorption peaks of polymethyl acrylic acid glycidyl ether-CH2-between oxirane ring and ester bond, 2.60ppm and 2.92ppm is two absorption peaks of-CH2-in oxirane ring, 3.2ppm is the absorption peak of methyne (-CH-) in oxirane ring, a series of absorption peaks between 3.5-3.85ppm are then the absorption peak of-CH2 in methoxy poly (ethylene glycol) carboxylic acid, 4.65ppm and 2.67ppm is two on perfluoro capryl amine-CH2 absorption peaks, can show that methoxy poly (ethylene glycol) carboxylic acid and perfluoro capryl amine have been bonded on main chain polymethyl acrylic acid glycidyl ether, and remain the ring oxygen of a part.
Embodiment 7(comparative example)
A kind of super-double-hydrophobic surface, is prepared by following method:
(1) by sheet glass, at piranha solution, (volume ratio is the dense H of 7:32SO4And H2O2Mixed solution) middle immersion 5h, more successively with ethanol, water washing, then dry;
(2) being dissolved in solvent P by aqueous fluorine-containing epoxy resin prepared by embodiment 4, add catalyst I, can obtain a kind of super two hydrophobic coating, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 5:0.001:10; Solvent P is phenylfluoroform, and catalyst I is triethylamine;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 90 DEG C of baking ovens to be cross-linked 24h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
Embodiment 8
A kind of super-double-hydrophobic surface, is prepared by following method:
(1) by sheet glass, at piranha solution, (volume ratio is the dense H of 7:32SO4And H2O2Mixed solution) middle immersion 5h, more successively with ethanol, water washing, then dry;
(2) aqueous fluorine-containing epoxy resin prepared by embodiment 4 is dissolved in solvent P, obtain aqueous fluorine-containing epoxy resin solution, the super two thin microballoon of water dispersible embodiment 1 prepared again is dispersed in aqueous fluorine-containing epoxy resin solution, stirring or supersound process make microballoon evenly disperse, add catalyst I again, a kind of super two hydrophobic coating can be obtained; The super two thin microballoon of water-based, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:5:0.001:10; Solvent P is phenylfluoroform, and catalyst I is triethylamine;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 90 DEG C of baking ovens to be cross-linked 24h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
Structural characterization is as shown in Figure 6:
Fig. 6 is the super-double-hydrophobic surface that embodiment 8 is constructed in glass sheet surface, it is fewer that aqueous fluorine-containing epoxy resin adds, the structure of microballoon look at also more clear, and the ring oxygen of microsphere surface has small part to be cross-linked, and the nanostructure of microballoon provides constructs the required roughness of super-double-hydrophobic surface.
Embodiment 9
A kind of super-double-hydrophobic surface, is prepared by following method:
(1) by sheet glass, at piranha solution, (volume ratio is the dense H of 7:32SO4And H2O2Mixed solution) middle immersion 5h, more successively with ethanol, water washing, then dry;
(2) aqueous fluorine-containing epoxy resin prepared by embodiment 4 is dissolved in solvent P, obtain aqueous fluorine-containing epoxy resin solution, the super two thin microballoon of water dispersible embodiment 1 prepared again is dispersed in aqueous fluorine-containing epoxy resin solution, stirring or supersound process make microballoon evenly disperse, add catalyst I again, a kind of super two hydrophobic coating can be obtained; The super two thin microballoon of water dispersible, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:10:0.003:20; Solvent P is dioxane, and catalyst I is N, N-diisopropyl ethyl amine;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 100 DEG C of baking ovens to be cross-linked 10h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
Structural characterization is as shown in Figure 7:
Fig. 7 is the SEM photograph of the super-double-hydrophobic surface that embodiment 9 is constructed in glass sheet surface, as can be seen from Figure, super two thin microballoon part is overmolding to one by aqueous fluorine-containing epoxy resin, cohesiveness is better, coatingsurface defines the micro nano structure of multilayer in film process, adding the participation of aqueous fluorine-containing epoxy resin, hydrophobic oleophobic performance is improved.
Embodiment 10
A ultra-amphosphobic surface, is prepared by following method:
(1) cotton is successively with ethanol, water washing, then dry;
(2) aqueous fluorine-containing epoxy resin prepared by embodiment 6 is dissolved in solvent P, obtain aqueous fluorine-containing epoxy resin solution, the super two thin microballoon of water dispersible embodiment 2 prepared again is dispersed in aqueous fluorine-containing epoxy resin solution, stirring or supersound process make microballoon evenly disperse, add catalyst I again, a kind of super two hydrophobic coating can be obtained; The super two thin microballoon of water dispersible, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:100:0.01:200; Solvent P is butanone, and catalyst I is tetrabutyl ammonium fluoride;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 140 DEG C of baking ovens to be cross-linked 2h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
Structural characterization is as shown in Figure 8:
Fig. 8 is the SEM photograph of the super-double-hydrophobic surface that embodiment 10 is constructed at cotton surface.
Embodiment 11
A ultra-amphosphobic surface, is prepared by following method:
(1) timber is successively with ethanol, water washing, then dry;
(2) the aqueous fluorine-containing epoxy resin implementing 5 preparations is dissolved in solvent P, obtain aqueous fluorine-containing epoxy resin solution, again the super two thin microballoon of water dispersible implementing 3 preparations is dispersed in aqueous fluorine-containing epoxy resin solution, stirring or supersound process make microballoon evenly disperse, add catalyst I again, a kind of super two hydrophobic coating can be obtained; The super two thin microballoon of water dispersible, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:50:0.005:50; Solvent P is N,N-DIMETHYLACETAMIDE, and catalyst I is benzyltriethylammoinium chloride;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 120 DEG C of baking ovens to be cross-linked 8h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
Structural characterization is as shown in Figure 9:
Fig. 9 is the SEM photograph of the super-double-hydrophobic surface that embodiment 11 is constructed at wood surface, aqueous fluorine-containing epoxy resin ratio owing to adding is higher, the super two thin microballoon of major part is all covered by inside polymkeric substance, the roughness making coating is not fine, but the fluorine-containing groups in aqueous fluorine-containing epoxy resin compensate for the defect of roughness to a certain extent, therefore the hydrophobic oleophobic performance of this coating also can manage it.
Embodiment 12
A ultra-amphosphobic surface, is prepared by following method:
(1) tinsel is successively with ethanol, water washing, then dry;
(2) aqueous fluorine-containing epoxy resin prepared by embodiment 6 is dissolved in solvent P, obtain aqueous fluorine-containing epoxy resin solution, the super two thin microballoon of water dispersible embodiment 3 prepared again is dispersed in aqueous fluorine-containing epoxy resin solution, stirring or supersound process make microballoon evenly disperse, add catalyst I again, a kind of super two hydrophobic coating can be obtained; The super two thin microballoon of water dispersible, aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:20:0.008:100; Solvent P is N-Methyl pyrrolidone, and catalyst I is N-benzyl imidazole;
(3) the super two hydrophobic coating prepared in step 2 is coated in substrate surface, film forming at 30 DEG C by the mode of spraying or dip-coating, then it is placed in 130 DEG C of baking ovens to be cross-linked 5h, obtain the material of a kind of super-hydrophobic/thin oil, i.e. super-double-hydrophobic surface.
The performance perameter of super-double-hydrophobic surface prepared by this embodiment is as shown in table 1.
The performance perameter of super-double-hydrophobic surface prepared by table 1 embodiment 7-12
In table 1, WCA is water contact angle, OCA is oil contact angle, SA1 is water roll angle, SA2 is that oil roll angle is all according to document (DeanXiongandGuojunLiu.Diblock-copolymer-coatedWater-andO il-RepellentCottonFabrics.Langmuir2012, the method mentioned in 28,6911-6918) is tested.
Table 1 characterizes the bonding force of super-double-hydrophobic surface on base material by indexs such as resistance to acids and bases, washing fastness, resistance to ultrasonic property.
Wherein the testing method of resistance to acids and bases is reference literature (GuangLi, HaitingZheng, YanxueWang, HuWang, QibaoDong, RukeBai.Afacilestrategyforthefabricationofhighlystablesu perhydrophobiccottonfabricusingamphiphilicfluorinatedtri blockazidecopolymers.Polymer2010, 51, the method mentioned in 1940-1946), that is: the super-double-hydrophobic surface prepared is immersed in respectively in the solvent of different pH value, then sample is taken out at set intervals, after washing the soda acid on surface with water, again with its contact angle of contact angle instrument test, when the contact angle of water or oil is greater than 150 ��, represent that the hydrophobic of this material or oleophobic property can not declines. until its contact angle is less than 150 ��, represent that the hydrophobic of its surface or oleophobic property can have dropped. record this time, by comparing the length of this time, characterize its resistance to acids and bases.
The testing method of washing fastness is reference literature (DeanXiongandGuojunLiu.Diblock-copolymer-coatedWater-andO il-RepellentCottonFabrics.Langmuir2012, the method mentioned in 28,6911-6918).
The testing method of resistance to ultrasonic property: super-double-hydrophobic surface is immersed in THF, because THF has good solubility for above-mentioned super-double-hydrophobic surface, then adopt KQ-218 type ultrasonic cleaner (ultrasonic instrument company limited of city of Kunshan) ultrasonic, measure the contact angle after different ultrasonic time, when the contact angle of water or oil is greater than 150 ��, represent that the hydrophobic of this material or oleophobic property can not declines. Until its contact angle is less than 150 ��, represent that the hydrophobic of its surface or oleophobic property can have dropped. Record this time, by comparing the length of this time, characterize its resistance to ultrasonic property.
As can be seen from Table 1: that the super-double-hydrophobic surface of embodiment 7-12 is bonded with base material is firm, cohesive force strong, rub resistance, wash resistant; Compared with adding the super-double-hydrophobic surface prepared by water fluoric resin separately, by the super-double-hydrophobic surface better effects if prepared by the super two thin microballoon of water dispersible and water fluoric resin.
Above-described embodiment is that the present invention preferably implements mode; but embodiments of the present invention are not restricted to the described embodiments; the change done under the spirit of other any the present invention of not deviating from and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, it is included within protection scope of the present invention.

Claims (7)

1. one kind has the super-double-hydrophobic surface of universality, it is characterised in that: be by N components dissolved in solvent P, obtain N solution; Again by M component disperses in N solution, add catalyst I subsequently, obtain a kind of super two hydrophobic coating; Finally super two hydrophobic coating is coated in substrate material surface, dry, namely obtain having the super-double-hydrophobic surface of universality; Described N component is aqueous fluorine-containing epoxy resin; Described M component is the super two thin microballoon of water dispersible, and this microballoon is by introducing one layer of epoxy resin A at substrate microsphere surface, and the epoxide group ring-opening reaction grafting hydrophilic compounds B and fluorochemicals C on recycling epoxy resin A surface obtains;
Described substrate microballoon is silicon dioxide microsphere, aluminum oxide micro-sphere, titanium dioxide microballoon sphere, ferric oxide microballoon or the surface polymer microballoon containing hydroxyl;
Described epoxy resin A is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy, polymethyl acrylic acid glycidyl ether, polypropylene-base glycidyl ether, gathers more than one in adjacent toluene glycidyl ether and polyphenyl glycidyl ether;
Described hydrophilic compounds B is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) amine, more than one in methoxy poly (ethylene glycol) mercapto alcohol, methoxy poly (ethylene glycol) carboxylic acid, polyoxyethylene glycol amine and polyoxyethylene glycol mercaptan;
Described fluorochemicals C is 3-perfluoro capryl propyl alcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro hexyl ethanol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, 1H, 1H, 2H, own-1-the alcohol of 2H-perfluor, perfluorinated acid, perfluor caproic acid, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, 1H, 1H, 2H, 2H-perfluoro decyl mercaptan, 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, more than one in 4-perfluoro capryl aniline, 1H, 1H-perfluoro capryl amine and perfluoro octyl sulfonic acid amine;
Described catalyst I is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine;
Described solvent P is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone and phenylfluoroform.
2. there is the super-double-hydrophobic surface of universality according to claim 1, it is characterised in that: the preparation method of the super two thin microballoon of described water dispersible, comprises the following steps:
(1) epoxy resin A is dissolved in solvent E and configures epoxy resin solution A, substrate microballoon is dispersed in solvent G, ultrasonic 1h, obtain microballoon dispersion liquid, continue ultrasonic limit, limit epoxy resin solution A to be added drop-wise in microballoon dispersion liquid with the speed of 0.2-5mL/min, then continue ultrasonic 30-180min, revolve and steam except desolventizing, thermal treatment, cooling, adds solvent E and heavily disperses, centrifuge washing, drying, obtains the coated microballoon of epoxy resin;
(2) the coated microballoon of epoxy resin prepared by step (1) is dispersed in solvent H1In, supersound process, then add catalyzer K and be heated to 60-120 DEG C, then successively add fluorochemicals C solution and hydrophilic compounds B when stirring, reaction 2-24h, finally remove the solvent in reaction system, obtain the super two thin microballoon of water dispersible; Described fluorochemicals C solution is that fluorochemicals C is dissolved in solvent H2Prepare;
Solvent E, G described in step (1) is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide;
Catalyzer K described in step (2) is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine;
Solvent H described in step (2)1��H2For more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide.
3. there is the super-double-hydrophobic surface of universality according to claim 2, it is characterised in that:
Supersound process condition described in step (1) is ultrasonic power is 300W, and temperature is 35 DEG C; Described heat-treat condition is thermal treatment 20-90min in 60-130 DEG C of vacuum drying oven; Described washing times is 4 times;
Epoxy resin solution A described in step (1) and microballoon dispersion liquid mass percentage concentration are respectively 1-10%, 0.2-5%, and the mass ratio of substrate microballoon and epoxy resin A is 1:2-10;
Supersound process condition described in step (2) is ultrasonic power is 300W, and temperature is 35 DEG C, and the time is 30min;
The coated microballoon of epoxy resin described in step (2), solvent H1, solvent H2, fluorochemicals C, the mass ratio of hydrophilic compounds B and catalyzer K is 1:(1-50): (1-50): (0.2-10): (0.2-10): (0.001-0.1).
4. there is the super-double-hydrophobic surface of universality according to claim 1, it is characterized in that: described N component is aqueous fluorine-containing epoxy resin, preparation method comprises the following steps: be dissolved in solvent by epoxy resin A, the mixed solution adding finely dispersed hydrophilic compounds B, fluorochemicals C and catalyzer in advance is dripped while stirring at 60-120 DEG C, rate of addition is 0.1g/min-100g/min, drip after adding end, continue reaction 4-10 hour, it is cooled to room temperature, concentrated, precipitate in solvent F again, dry, obtain aqueous fluorine-containing epoxy resin;
Described solvent F is normal hexane, anhydrous diethyl ether, sherwood oil, ethyl acetate, methyl alcohol, more than one in second alcohol and water.
5. there is the super-double-hydrophobic surface of universality according to claim 4, it is characterized in that: described epoxy resin A is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy, polymethyl acrylic acid glycidyl ether, more than one in polypropylene-base glycidyl ether, poly-adjacent toluene glycidyl ether and polyphenyl glycidyl ether;
Described hydrophilic compounds B is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) amine, more than one in methoxy poly (ethylene glycol) mercapto alcohol, methoxy poly (ethylene glycol) carboxylic acid, polyoxyethylene glycol amine and polyoxyethylene glycol mercaptan;
Described fluorochemicals C is 3-perfluoro capryl propyl alcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro hexyl ethanol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, 1H, 1H, 2H, own-1-the alcohol of 2H-perfluor, perfluorinated acid, perfluor caproic acid, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, 1H, 1H, 2H, 2H-perfluoro decyl mercaptan, 1H, 1H, 2H, 2H-perfluor spicy thioalcohol, 1H, 1H, 2H, 2H-perfluor dodecyl mercaptans, more than one in 4-perfluoro capryl aniline, 1H, 1H-perfluoro capryl amine and perfluoro octyl sulfonic acid amine;
Described catalyzer is triethylamine, Trimethylamine 99, tetrabutyl ammonium fluoride, N, N-diisopropyl ethyl amine, benzyltriethylammoinium chloride, imidazoles, 1-propyl imidazole, N-benzyl imidazole, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, benzyltriethylammoinium chloride, trolamine, tri-isopropanolamine and N, more than one in N-diethylethanolamine;
Described solvent is more than one in tetrahydrofuran (THF), dimethyl formamide, dioxane, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, butanone, pimelinketone, phenyl ether and methyl-phenoxide;
Mass ratio between described epoxy resin A, solvent, hydrophilic compounds B, fluorochemicals C and catalyzer is: 1:10-100:1-10:1-10:0.00001-0.0001.
6. the preparation method of the super-double-hydrophobic surface with universality according to claim 1, it is characterised in that: comprise the following steps:
(1) substrate surface pre-treatment;
(2) by N components dissolved in solvent P, N solution is obtained; Again by M component disperses in N solution, stirring or supersound process make microballoon evenly disperse, then add catalyst I, obtain a kind of super two hydrophobic coating; Described N component is aquosity fluorine-containing epoxy resin, and described M component is the super two thin microballoon of water dispersible;
(3) super two hydrophobic coating prepared by step (2) is coated in substrate surface in step (1), film forming, then at 90-140 DEG C, it is cross-linked 2-24h, obtain the material of super-hydrophobic/thin oil, be a kind of super-double-hydrophobic surface;
Base material described in step (1) is sheet glass, cotton, filter paper, thin-film material, tinsel, plastic sheet, timber or cement matrix;
The pretreatment process of described filter paper, tinsel, plastic sheet, thin-film material, timber, cement matrix and cotton is: by each base material successively with ethanol, water washing, then dry;
The pretreatment process of sheet glass is: in piranha solution, sheet glass is soaked 5h, more successively with ethanol, water washing, then dry;
The M component of the super two thin microballoon of the water dispersible described in step (2), the N component of aqueous fluorine-containing epoxy resin, the mass ratio of catalyst I and solvent P is 1:5-100:0.001-0.01:10-200;
Coating method described in step (3) is applied by the mode of spraying or dip-coating; Film-forming temperature is 30 DEG C.
7. the application of the super-double-hydrophobic surface with universality according to claim 1, it is characterized in that: the described materials application with ultra-amphosphobic surface, in production life aspect, comprises the windshield glass of the outer protective of military industry equipment, the outer field water-tight corrosion-proof of oil pipeline, kitchen guarding's apparatus, automobile and aircraft.
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