CN103554353B - A kind of Cross-linkable fluoropolymer Nano microsphere and preparation method thereof and application - Google Patents
A kind of Cross-linkable fluoropolymer Nano microsphere and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of Cross-linkable fluoropolymer Nano microsphere and preparation method thereof and application.Described preparation method comprises the following steps: be dispersed in by epoxy cross-linking Nano microsphere in solvent orange 2 A 1, add catalyzer again and be heated to 60 ~ 120 DEG C, then under the condition stirred, the fluorochemicals solution being dissolved in solvent orange 2 A 2 is added, reaction 2 ~ 24h, finally remove the solvent in reaction system, obtain described cross-linking type fluorine-containing polymer nano-microspheres.The polymer nano-microspheres of the present invention's synthesis, both containing epoxide group, contains fluorine-containing groups again, and size tunable; Synthesized polymer nano-microspheres utilizes fluoro-containing group to construct low surface energy interface, utilizes polymer microballoon to build coarse structure, therefore can realize the effective combination between ultra-amphosphobic polymer microballoon and substrate surface, thus improve the weather resistance of material.And synthesize fluoropolymer Nano microsphere in the present invention and prepare super two thin material technology simple, do not need main equipment.
Description
Technical field
The invention belongs to super two thin Material Field, be specifically related to a kind of Cross-linkable fluoropolymer Nano microsphere and preparation method thereof and application.
Background technology
The topmost characterization parameter of moistened surface behavior is contact angle, if the static contact angle of surface to water is less than 10 °, is referred to as ultra-hydrophilic surface, if surface has the contact angle being greater than 150 °, is referred to as super hydrophobic surface.If surface has the contact angle being greater than 150 ° to oil, super oleophobic surface can be thought.If surface both had super-hydrophobicity, there is again super oleophobic performance, be then referred to as super-double-hydrophobic surface.
Super-double-hydrophobic surface, due to the hydrophobic oleophobic performance of its uniqueness, can be applicable to a lot of aspect.Super-double-hydrophobic surface has self-cleaning function and can be used for the minute surface that sun power electroplax or some needs keep clean, the surface of such as gas kitchen ranges.Moreover metallic surface forms the corrosion resistance that super-double-hydrophobic surface also can improve metallic surface greatly.If construct super-double-hydrophobic surface in addition on electric wire or high-voltage fence, electric wire can be avoided to form cryosphere at ice storm or Character of Snowstorm surface, thus cause short circuit to cause power-off plant downtime on a large scale, even cause the interruption of the communications and transportation circuits such as railway.
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.Plating one deck fluorochemicals film at material surface is the comparatively cost-effective method preparing fluorine surface, fluorochemicals can form fluorine-containing thin layer at substrate surface, even be combined in substrate surface by chemical bonding mode, but this thin layer is easy to owing to being unimolecular layer be polluted or damage, be unfavorable for forming multistage coarse structure, therefore the coarse structure on starting material surface also had higher requirements.For overcoming the defect of the method and super-hydrophobic or super-double-hydrophobic surface can being built 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 fluoridized by Nano/micron level particle, then the Nano/micron level particle fluoridized is coated onto material surface thus builds super-hydrophobic or super-double-hydrophobic surface.The uneven surface that inorganic particulate is formed and fluoropolymer low surface energy provide good condition for building super-hydrophobic or super-double-hydrophobic surface.When but these methods build super-double-hydrophobic surface, polymkeric substance, be difficult between inorganic particulate and substrate be really bonded together by chemical bonding effect, and mainly physisorption, therefore, under outer field action, easily lose established super-double-hydrophobic surface.And prepare this out-phase reaction that fluorinated inorganic particle needs fluoropolymer to be grafted to surface of inorganic particles, need to carry out a series of process to surface of inorganic particles, step is comparatively loaded down with trivial details, and fluoropolymer utilization ratio is also lower.
If a kind of micro-and nano-particles containing active function groups can be prepared, make its surface not only be easy to grafted fluoropolymer compound, can also react with base material and form the group of firm covalent linkage, just can well overcome above defect.
Chinese patent 201110131477.X proposes a kind of preparation of fluorine-containing difunctional microballoon and is applied to and constructs super-double-hydrophobic surface.But fluorine-contained surface part is unit molecule thin layer, be therefore easy to be polluted or damage.Patent 201110090620.5 proposes a kind of preparation of two fluorine-containing crosslinkable block copolymers of thin property and form fluorine-containing Nano microsphere after silica sphere assembling, and is applied to and constructs super-double-hydrophobic surface.This method needs the preparation of the segmented copolymer of complex process, needs harsh assembling condition simultaneously.
Chinese patent CN101748461A propose a kind of aluminium or aluminum alloy sheet are carried out two-step electrochemical process after obtain with perfluor chain alkyl trichlorosilane or the process of perfluor polymethacrylate the surface that surface has super-double-thinning property again.This method exist equally cohesive strength not or surface hold flimsy problem.Patent CN1379128A proposes the array structure thin film that the preparation of a kind of chemical gaseous phase depositing process has ultra-amphosphobic energy, but technics comparing is harsh, is not easy to suitability for industrialized production application.
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 method utilizes more fluorine-containing silicon-containing copolymer, and need blended assembling to react when using, technics comparing is complicated.
In recent years, utilize fluoropolymer constructing super-drainage to surpass the document at oleophobic interface and patent more, but the bonding force between most of fluoropolymer of current bibliographical information and substrate surface is not strong, thus cause constructed super-hydrophobic/super oleophobic interface to exist insecure, rub resistance, the shortcomings such as washing fastness is not strong, and for the smooth surface of glass and so on for base material builds super-double-hydrophobic surface less effective especially.Therefore, develop a kind of simple and method that is that be easy to realize prepares a kind of micro-and nano-particles containing active function groups, make its surface be easy to a large amount of fluorochemicals of grafting or fluoropolymer, and containing the group of firm covalent linkage can be formed with various substrate surface, just can solve above problem.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of Cross-linkable fluoropolymer Nano microsphere.
Another object of the present invention is to the Cross-linkable fluoropolymer Nano microsphere providing above-mentioned preparation method to obtain.
Another object of the present invention is that the Cross-linkable fluoropolymer Nano microsphere providing above-mentioned preparation method to obtain is constructing the application in super-double-hydrophobic surface.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of Cross-linkable fluoropolymer Nano microsphere, comprise the following steps: epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add catalyzer again and be heated to 60 ~ 120 DEG C, then under the condition stirred, the fluorochemicals F solution being dissolved in solvent orange 2 A 2 is added, reaction 2 ~ 24h, finally remove the solvent in reaction system, obtain described cross-linking type fluorine-containing polymer nano-microspheres.
Preferably, the mass ratio of described epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, fluorochemicals F and catalyzer is 1:(1 ~ 50): (1 ~ 50): (0.2 ~ 10): (0.001 ~ 0.1).
Preferably, the structural formula of described fluorochemicals F is such as formula shown in (a):
wherein n=0,1,2,3,4,5,6,7,8,9 or 10; M=0,1,2,3,4,5,6,7,8,9 or 10; X is hydroxyl, amino, carboxyl or sulfydryl;
Described catalyzer is more than one in triethylamine, diethylene diamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine and benzyltriethylammoinium chloride;
Described solvent orange 2 A 1 and solvent orange 2 A 2 are more than one in tetrahydrofuran (THF), dimethyl fumarate, Isosorbide-5-Nitrae-dioxane, pimelinketone, two butanone, p-Xylol, phenylfluoroform, phenyl ether and methyl-phenoxide;
The size of described epoxy cross-linking Nano microsphere is 50 ~ 1000 nanometers, and its structural formula is such as formula shown in (b):
Preferred, described fluorochemicals F is 3-perfluoro capryl propyl alcohol, perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, perfluor-2, more than one in 5-dimethyl-3,6-dioxanonanoic acid, 11 fluorine caproic acids, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, perfluoro decyl mercaptan, perfluor spicy thioalcohol, perfluor dodecyl mercaptans, perfluoro capryl aniline and perfluoro octyl sulfonic acid amine.
Preferably, described epoxy cross-linking Nano microsphere prepares gained by the following method: initiator, stablizer and emulsifying agent are joined in solvent B, 50 ~ 80 DEG C are warming up to after passing into rare gas element deoxygenation, and then the mixed solution of the double bond monomer H added containing epoxide group and linking agent, reaction 3 ~ 10h, by product successively successively with the washing of methyl alcohol, water and tetrahydrofuran (THF), then centrifugal, heavily dispersion and vacuum-drying, obtains described epoxy cross-linking Nano microsphere.
Preferred, the mass ratio of described solvent B, initiator, stablizer, emulsifying agent, double bond monomer H containing epoxide group and linking agent is 1:(0.002 ~ 0.01): (0.01 ~ 0.2): (0 ~ 0.2): (0.1 ~ 50): (0.1 ~ 50).
Preferred, the structural formula of the described double bond monomer H containing epoxide group is such as formula shown in (c):
wherein, R
1for hydrogen atom or methyl; R
3for CH
2, O, COOCH
2or C
6h
6; Z=0,1,2,3,4,5,6,7,8,9 or 10; Y=0 or 1; X is epoxide group;
Described linking agent is the monomer with two or more double bonds, and its structural formula is such as formula shown in (d):
Wherein, m=1,2,3,4,5,6,7,8,9 or 10; R is (C
6h
4) t, (CH
2) t or CO (OCH
2cH
2o) tOC, t=1,2,3,4,5,6,7,8,9 or 10; R
2for hydrogen atom or methyl; R
4for hydrogen atom or methyl;
Described solvent B is methyl alcohol, ethanol, n-propyl alcohol, Virahol or water; Described initiator is more than one in isobutyl miaow hydrochloride of Potassium Persulphate, ammonium persulphate, azo isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo two; Described stablizer is polyvinylpyrrolidone, polyoxyethylene glycol or polyvinyl alcohol; Emulsifying agent is sodium lauryl sulphate, Dodecyl trimethyl ammonium chloride, polyethenoxy ether class or Sodium dodecylbenzene sulfonate; Described rare gas element is nitrogen or helium.
Most preferred, the described double bond monomer H containing epoxide group is more than one in methacryloxyethyl acid glycidyl ether, propenyl glycidyl ether and 1,2-epoxy group(ing)-5-hexene;
Described linking agent is more than one in vinyl hexanediacetate, 1,4 cyclohexane dimethanol divinyl ether, Ethylene glycol dimethacrylate, TEGDMA, triethylene glycol diacrylate, Vinylstyrene and TEG dimethacrylate.
The Cross-linkable fluoropolymer Nano microsphere that above-mentioned preparation method obtains; Its structural formula is such as formula shown in (e):
in formula, g represents grafting, and F is fluorochemicals.
The Cross-linkable fluoropolymer Nano microsphere of above-mentioned preparation method's gained is applied to constructs super-double-hydrophobic surface; Described concrete steps of constructing super-double-hydrophobic surface are as follows:
(1) substrate surface pre-treatment;
(2) the Cross-linkable fluoropolymer Nano microsphere will prepared, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, the mass ratio of epoxy resin and solvent M is 1:(0.002 ~ 0.5): (0.1 ~ 0.4): (1 ~ 50);
(3) coating liquid step (2) prepared is coated in substrate surface by spraying or the mode of dip-coating, after 20 ~ 30 DEG C of film forming, then be positioned over 80 ~ 120 DEG C crosslinked 2 ~ 24 hours, obtain described super-double-hydrophobic surface;
Base material described in step (1) is sheet glass, cotton, filter paper, timber or cement matrix;
Described solvent M is more than one in tetrahydrofuran (THF), dimethyl fumarate, dioxy six alkane, pimelinketone, two butanone, p-Xylol, phenylfluoroform, phenyl ether and methyl-phenoxide;
Described solidifying agent is triethylamine, diethylenetriamine, tetraethylene pentamine, Tetra hydro Phthalic anhydride, glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole;
Described epoxy resin is vinyl cyclohexene dioxide, bisphenol A type epoxy resin, 2,3-epoxypropyl butyl ether, glycidyl ether type epoxy resin, glycidyl ester epoxy resin, molecular weight are the polymethyl acrylic acid glycidyl ether of 500 ~ 100000 or molecular weight is one in the polypropylene-base glycidyl ether of 500 ~ 100000.
Wherein the pre-treatment of filter paper, timber, cement matrix and cotton is: use ethanol, water washing successively, then dry; The pre-treatment of sheet glass is: sheet glass is soaked for some time in piranha solution, then uses ethanol, water washing successively, then dry; The dense H of described piranha solution to be volume ratio be 7:3
2sO
4and H
2o
2mixed solution.
Above-mentioned super two thin material can be applicable to the hydrophobic oleophobic modification of most substrate surface such as self-cleaning coating, the outer protective of military industry equipment, the outer field water-tight corrosion-proof of oil pipeline, the non-resistance coating of oleophobic pipeline lining, the yarn fabric of hydrophobic oleophobic type of water proof anti-corrosive paint, steel surface process, the hydrophobic oleophobic coating of windshield, exterior wall self-cleaning coating, sculpture.
Principle of the present invention is: the present invention can prepare the epoxy cross-linking Nano microsphere of size tunable by emulsion polymerization, this polymer microballoon surface is containing a large amount of epoxide groups, utilize the active function groups of some of epoxide group and fluorochemicals as amino, carboxyl, sulfydryl or hydroxyl reaction, fluorochemicals is grafted to epoxy cross-linking microsphere surface, it is crosslinked that remaining epoxide group can be used for epoxy resin and base material, makes this super-hydrophobic/oleophobic coating pass through firmly chemical bonds with substrate surface.
Polymer nano-microspheres crosslinkable synthesized by the present invention, be attached to surface containing fluorochemicals again simultaneously, utilize epoxide group mutually bonding with base material, fluoro-containing group is utilized to construct low surface energy interface, polymer microballoon is utilized to build coarse structure, therefore can realize the effective combination between ultra-amphosphobic polymer microballoon and substrate surface, thus improve the weather resistance of material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) polymer nano-microspheres of the present invention's synthesis is both containing epoxide group, simultaneously again containing fluorine-containing groups, and size tunable;
(2) due in the polymer nano-microspheres prepared in the present invention containing epoxide group again containing fluorine-containing groups, not only meet and build super two two prerequisites (coarse surface and low surface energy interface) of dredging, avoid and adopt inorganic particulate etc. again to construct uneven surface, and the epoxide group of microsphere surface and most substrate surface have the advantage of bonding force, thus can directly realize most substrate surface particularly smooth surface super-hydrophobic/oleophobic performance;
(3) the fluorochemicals part in the fluoropolymer Nano microsphere prepared of the present invention, can according to the hydro-oleophobicity on the wherein number controlled material surface of fluorine atom, if only need hydrophobic, then low fluorine-containing then can, if need oleophobic, then need high fluorine-containing;
(4) synthesize fluoropolymer Nano microsphere in the present invention and prepare super two thin material technology simple, not needing main equipment, is therefore a kind of preparation method of super two thin materials of simple possible.
Accompanying drawing explanation
Fig. 1 is the TEM test pattern of the Cross-linkable fluoropolymer Nano microsphere that embodiment 3 obtains;
AFM bis-bit plan of Fig. 2 super two open coat that to be the obtained Cross-linkable fluoropolymer Nano microsphere of embodiment 3 prepare in glass sheet surface;
The AFM three-dimensional plot of Fig. 3 super two open coat that to be the obtained Cross-linkable fluoropolymer Nano microsphere of embodiment 3 prepare in glass sheet surface;
Fig. 4 is the epoxy cross-linking Nano microsphere prepared of embodiment 3 and Cross-linkable fluoropolymer Nano microsphere
1h NMR spectrogram.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) synthesis of epoxy cross-linking Nano microsphere: in solvent B, add initiator, stablizer and emulsifying agent, be warming up to 50 DEG C after logical nitrogen deoxygenation 30min, more slowly drip containing the double bond monomer H of epoxide group and the mixed solution of linking agent, continue reaction 3h, reaction terminate rear cool to room temperature, product with methylalcohol, water, tetrahydrofuran (THF) (THF) washing, centrifugal, heavily disperse 4 times, be placed in vacuum 40 DEG C of dried overnight, product is white powder, is required epoxy cross-linking Nano microsphere.Wherein solvent B, initiator, stablizer, emulsifying agent, the double bond monomer H containing epoxide group, the mass ratio of linking agent is 1:0.002:0.1:0.1:0.1:0.1;
The size of this epoxy cross-linking Nano microsphere is 50nm;
Double bond monomer H wherein containing epoxide group is methyl propenoic acid glycidyl ether; Linking agent is vinyl hexanediacetate; Solvent B is methyl alcohol; Initiator is Potassium Persulphate;
Described stablizer is polyvinylpyrrolidone; Emulsifying agent is sodium lauryl sulphate.
(2) synthesis of Cross-linkable fluoropolymer Nano microsphere: above-mentioned epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add at catalyzer increases the temperature to 60 DEG C again, slowly drip the fluorochemicals F solution being dissolved in solvent orange 2 A 2 while stirring, after dropping terminates, temperature of reaction is kept to continue reaction 2h.Again the solvent in this system is eliminated, obtain white powder, be required Cross-linkable fluoropolymer Nano microsphere.The structural formula of this cross-linking type fluorine-containing polymer nano-microspheres is as follows:
Wherein epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, the mass ratio of fluorine-containing material compound F 17-hydroxy-corticosterone and catalyzer is 1:1:1:0.2:0.001; Wherein fluorochemicals F is perfluor dodecyl mercaptans; Catalyzer is diethylene diamine; Solvent orange 2 A 1, A2 is all the mixing of THF and pimelinketone.
As follows to the Spectrum Analysis of product:
1h-NMR (CDCl
3make solvent): 3.69ppm, the 4.31ppm(-CH between oxirane ring and ester bond
2-two absorption peaks) ,-CH in 2.57ppm, 2.85ppm(oxirane ring
2-two absorption peaks), the absorption peak of-CH-in 3.2ppm(oxirane ring), two methylene radical absorption peaks on 4.89ppm, 2.51ppm(perfluor dodecyl mercaptans).
(3) above-mentioned fluorine-containing bi-functional microspheres is used for carry out modification to its surface, prepares hydrophobic/oleophobic coating, comprise following operation steps:
A () filter paper uses ethanol, water washing successively, then dry;
B Cross-linkable ultra-amphosphobic epoxy cross-linking microballoon that () will prepare, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, epoxy resin, the mass ratio of solvent M is 1:0.002:0.1:10; Solvent M is THF; Solidifying agent is tetraethylene pentamine, Tetra hydro Phthalic anhydride; Epoxy resin is vinyl cyclohexene dioxide.
C the coating liquid prepared in step (b) is coated in substrate surface by spraying or the mode of dip-coating by (), after 20 ~ 30 DEG C of film forming, then be placed on 80 DEG C of crosslinked 24h, can obtain a kind of super-hydrophobic/material of oleophobic.
Embodiment 2
(1) synthesis of epoxy cross-linking Nano microsphere: in solvent B, add initiator, stablizer and emulsifying agent, be warming up to 60 DEG C after logical nitrogen deoxygenation 30min, more slowly drip containing the double bond monomer H of epoxide group and the mixed solution of linking agent, continue reaction 6h, reaction terminates rear cool to room temperature, and product with methylalcohol, water, THF wash centrifugal heavy dispersion 5 times, are placed in vacuum 40 DEG C of dried overnight, product is white powder, is required epoxy cross-linking Nano microsphere.Wherein solvent B, initiator, stablizer, emulsifying agent, the double bond monomer H containing epoxide group, the mass ratio of linking agent is 1:0.004:0.05:0:1:0.5;
The size of this epoxy cross-linking Nano microsphere is 100nm;
Double bond monomer H wherein containing epoxide group is 1,2-epoxy group(ing)-5-hexene; Linking agent is Ethylene glycol dimethacrylate; Solvent B ethanol; Initiator is azo isobutyronitrile; Stablizer is polyvinyl alcohol; Emulsifying agent is Sodium dodecylbenzene sulfonate.
(2) synthesis of Cross-linkable fluoropolymer Nano microsphere: above-mentioned epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add at catalyzer increases the temperature to 80 DEG C again, slowly drip the fluorochemicals F solution being dissolved in solvent orange 2 A 2 while stirring, after dropping terminates, temperature of reaction is kept to continue reaction 6h.Again the solvent in this system is eliminated, obtain white powder, be required Cross-linkable fluoropolymer Nano microsphere.The structural formula of this cross-linking type fluorine-containing polymer nano-microspheres is as follows:
Wherein epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, the mass ratio of fluorine-containing material compound F 17-hydroxy-corticosterone and catalyzer is 1:5:10:0.8:0.005; Wherein fluorochemicals F is perfluoro octyl ethanol; Catalyzer can be triethylamine; Solvent orange 2 A 1, A2 is all phenylfluoroform.
As follows to the Spectrum Analysis of product: 1H-NMR (CDCl
3make solvent) :-CH of the contiguous oxirane ring of 3.52-4.47ppm(
2-multi-absorption peak) ,-CH of the contiguous double bond of 1.7-2.15ppm(
2-multi-absorption peak)-CH in 2.32ppm, 2.55ppm(oxirane ring
2-two absorption peaks), the absorption peak of-CH-in 3.15ppm(oxirane ring), two methylene radical absorption peaks on 4.53ppm, 2.17ppm(perfluor perfluoro octyl ethanol).
(3) above-mentioned Cross-linkable fluoropolymer Nano microsphere is used for carrying out modification to glass sheet surface, prepares hydrophobic/oleophobic coating, comprise following operation steps:
A () at piranha solution, (volume ratio is the dense H of 7:3 by sheet glass
2sO
4and H
2o
2mixed solution) middle immersion for some time, then use ethanol, water washing successively, then dry;
B Cross-linkable fluoropolymer Nano microsphere that () will prepare, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, epoxy resin, the mass ratio of solvent M is: 1:0.5:0.15:10; Solvent M is pimelinketone; Solidifying agent is glyoxal ethyline; Epoxy resin is bisphenol A type epoxy resin;
C the coating liquid prepared in step (b) is coated in substrate surface by spraying or the mode of dip-coating by (), at 20 ~ 30 DEG C after film forming, then be placed on 100 DEG C of crosslinked 8h, can obtain a kind of super-hydrophobic/material of oleophobic.
Embodiment 3
(1) synthesis of epoxy cross-linking Nano microsphere: in solvent B, add initiator, stablizer and emulsifying agent, be warming up to 70 DEG C after logical nitrogen deoxygenation 30min, more slowly drip containing the double bond monomer H of epoxide group and the mixed solution of linking agent, continue reaction 5h, reaction terminates rear cool to room temperature, and product with methylalcohol, water, THF wash centrifugal heavy dispersion 4 ~ 5 times, are placed in vacuum 40 DEG C of dried overnight, product is white powder, is required epoxy cross-linking Nano microsphere.Wherein solvent B, initiator, stablizer, emulsifying agent, the double bond monomer H containing epoxide group, the mass ratio of linking agent is 1:0.005:0.11:0.05:10:6;
The size of this epoxy cross-linking Nano microsphere is 160nm; Double bond monomer H wherein containing epoxide group is propenyl glycidyl ether; Linking agent is TEGDMA; Solvent B is methanol-water; Initiator is azo two isobutyl miaow hydrochloride; Stablizer is polyoxyethylene glycol; Emulsifying agent is Dodecyl trimethyl ammonium chloride;
(2) synthesis of Cross-linkable fluoropolymer Nano microsphere: above-mentioned epoxy cross-linking microballoon is dispersed in solvent orange 2 A 1, add catalyzer again and increase the temperature to 70 DEG C, slowly drip the fluorochemicals F solution being dissolved in solvent orange 2 A 2 while stirring, after dropping terminates, temperature of reaction is kept to continue reaction 4h.Again the solvent in this system is eliminated, obtain white powder, be required Cross-linkable fluoropolymer Nano microsphere.The structural formula of this cross-linking type fluorine-containing polymer nano-microspheres is as follows:
Wherein epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, the mass ratio of fluorine-containing material compound F 17-hydroxy-corticosterone and catalyzer is 1:10:15:3:0.01; Fluorochemicals F is perfluor decyl mercaptan;
Catalyzer is benzyltriethylammoinium chloride; Solvent orange 2 A 1, A2 is the mixing of DMF and phenyl ether;
(3) above-mentioned Cross-linkable fluoropolymer Nano microsphere is used for carrying out modification to glass sheet surface, prepares hydrophobic/oleophobic coating, comprise following operation steps:
A () at piranha solution, (volume ratio is the dense H of 7:3 by sheet glass
2sO
4and H
2o
2mixed solution) middle immersion for some time, then use ethanol, water washing successively, then dry;
B Cross-linkable fluoropolymer Nano microsphere that () will prepare, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, epoxy resin, the mass ratio of solvent M is 1:0.3:0.25:30; Solvent M is methyl-phenoxide; Solidifying agent is triethylamine; Epoxy resin is ethylene glycol diglycidylether;
C the coating liquid prepared in step (b) is coated in substrate surface by spraying or the mode of dip-coating by (), after 20 ~ 30 DEG C of film forming, then be placed on 80 DEG C of crosslinked 24h, can obtain a kind of super-hydrophobic/material of oleophobic.
The TEM test pattern of the Cross-linkable fluoropolymer Nano microsphere that accompanying drawing 1 is prepared for the present embodiment, size is at about 150nm as can be seen from FIG..
AFM bis-bit plan of super two open coat that the Cross-linkable fluoropolymer Nano microsphere prepared for the present embodiment of accompanying drawing 2 is prepared in glass sheet surface, microspherulite diameter is at about 150nm as can be seen from FIG., substantially identical with TEM result, more even in glass sheet surface film forming.
The AFM three-dimensional plot of super two open coat that the Cross-linkable fluoropolymer Nano microsphere prepared for the present embodiment of accompanying drawing 3 is prepared in glass sheet surface, coating has certain roughness as can be seen from Figure, for super two dredging provides condition.
The epoxy cross-linking Nano microsphere that accompanying drawing 4 is prepared for the present embodiment and Cross-linkable fluoropolymer Nano microsphere
1h NMR spectrogram, wherein (a) is epoxy cross-linking Nano microsphere
1h NMR spectrogram, in (a), can see 3.75ppm and 4.25ppm-CH between oxirane ring and ester bond
2two absorption peaks of-(c position) ,-CH in oxirane ring
2two absorption peaks of-(e position) respectively at 2.62ppm and 2.82ppm place ,-CH-(d the position in oxirane ring) absorption peak then at 3.2ppm place.B () is Cross-linkable fluoropolymer Nano microsphere
1h NMR spectrogram, in (b), perfluor decyl mercaptan with containing after epoxy cross-linking microsphere surface PART EPOXY carries out ring-opening reaction, the chemical shift at c and e place moves forward to f and h position a little, but change is not clearly comparatively speaking, therefore in crosslinkable polymer microballoon collection of illustrative plates, visibility point does not change, and just peak type has broadened a bit.And two methylene radical absorption peaks on former perfluor decyl mercaptan are respectively in 4.77ppm(i position) and 2.33ppm(j position) place.The above results shows that perfluor decyl mercaptan has been bonded to containing epoxy cross-linking microsphere surface.
Embodiment 4
(1) synthesis of epoxy cross-linking Nano microsphere: in solvent B, add initiator, stablizer and emulsifying agent, be warming up to 75 DEG C after logical nitrogen deoxygenation 30min, more slowly drip containing the double bond monomer H of epoxide group and the mixed solution of linking agent, continue reaction 8h, reaction terminates rear cool to room temperature, and product with methylalcohol, water, THF wash centrifugal heavy dispersion 4 ~ 5 times, are placed in vacuum 40 DEG C of dried overnight, product is white powder, is required epoxy cross-linking Nano microsphere.Wherein solvent B, initiator, stablizer, emulsifying agent, the double bond monomer H containing epoxide group, the mass ratio of linking agent is 1:0.008:0.08:0.05:15:30;
The size of this epoxy cross-linking Nano microsphere is 200nm; Double bond monomer H wherein containing epoxide group is 1,2-epoxy group(ing)-5-hexene; Linking agent is Vinylstyrene; Solvent B is water; Initiator is ammonium persulphate; Stablizer is polyvinyl alcohol; Emulsifying agent is polyethoxylated fatty alcohols (n=30);
(2) synthesis of Cross-linkable fluoropolymer Nano microsphere: above-mentioned epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add catalyzer again and increase the temperature to 80 DEG C, slowly drip the fluorochemicals F solution being dissolved in solvent orange 2 A 2 while stirring, after dropping terminates, temperature of reaction is kept to continue reaction 24h.Again the solvent in this system is eliminated, obtain white powder, be required Cross-linkable fluoropolymer Nano microsphere.The structural formula of this cross-linking type fluorine-containing polymer nano-microspheres is as follows:
Wherein epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, the mass ratio of fluorine-containing material compound F 17-hydroxy-corticosterone and catalyzer is 1:40:30:8:0.08; Fluorochemicals F is perfluorobutyric acid; Catalyzer is diethylene diamine; Solvent orange 2 A 1, A2 is all the mixing of THF and methyl-phenoxide.
As follows to the Spectrum Analysis of product: FT-IR:3441cm
-1the wider absorption peak that place occurs, corresponding to antisymmetric stretching vibration and the symmetrical stretching vibration of the-OH base generated after epoxy addition; 1735cm
-1locate the stretching vibration absorption peak that strong absorption peak is C=O in perfluorobutyric acid; 1254cm
-1the strong absorption peak that place occurs is attributed to-C-F stretching vibration; 930cm
-1place is the characteristic peak of epoxy.
(3) above-mentioned fluorine-containing bi-functional microspheres is used for carry out modification to wood surface, prepares hydrophobic/oleophobic coating, comprise following operation steps:
A () timber uses ethanol, water washing successively, then dry;
B Cross-linkable fluoropolymer Nano microsphere that () will prepare, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, epoxy resin, the mass ratio of solvent M is 1:0.1:0.2:15; Solvent M is phenyl ether; Solidifying agent is Tetra hydro Phthalic anhydride; Epoxy resin is epoxypropyl butyl ether;
C the coating liquid prepared in step (b) is coated in substrate surface by spraying or the mode of dip-coating by (), after 20 ~ 30 DEG C of film forming, then be placed on 100 DEG C of crosslinked 10h, can obtain a kind of super-hydrophobic/material of oleophobic.
Embodiment 5
(1) synthesis of epoxy cross-linking Nano microsphere: in solvent B, add initiator, stablizer and emulsifying agent, be warming up to 80 DEG C after logical nitrogen deoxygenation 30min, more slowly drip containing the double bond monomer H of epoxide group and the mixed solution of linking agent, continue reaction 10h, reaction terminates rear cool to room temperature, and product with methylalcohol, water, THF wash centrifugal heavy dispersion 4 ~ 5 times, are placed in vacuum 40 DEG C of dried overnight, product is white powder, is required epoxy cross-linking Nano microsphere.Wherein solvent B, initiator, stablizer, emulsifying agent, the double bond monomer H containing epoxide group, the mass ratio of linking agent is 1:0.01:0.1:0.2:20:50;
The size of this epoxy cross-linking Nano microsphere is 1000nm; Double bond monomer H wherein containing epoxide group is propenyl glycidyl ether; Linking agent is TEG dimethacrylate; Solvent B is Virahol; Initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile); Stablizer is polyvinylpyrrolidone; Emulsifying agent is sodium lauryl sulphate;
(2) synthesis of Cross-linkable fluoropolymer Nano microsphere: above-mentioned epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add catalyzer again and increase the temperature to 120 DEG C, slowly drip the fluorochemicals F solution being dissolved in solvent orange 2 A 2 while stirring, after dropping terminates, temperature of reaction is kept to continue reaction 10h.Again the solvent in this system is eliminated, obtain white powder, be required Cross-linkable fluoropolymer Nano microsphere.The structural formula of this cross-linking type fluorine-containing polymer nano-microspheres is as follows:
Wherein epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, the mass ratio of fluorine-containing material compound F 17-hydroxy-corticosterone and catalyzer is 1:50:50:10:0.1; Fluorochemicals F is perfluoro octyl sulfonic acid amine; Catalyzer is diisopropyl ethyl amine; Solvent orange 2 A 1, A2 is all the mixing of DMF and dioxy six alkane;
As follows to the Spectrum Analysis of product: FT-IR:3450cm
-1the wider absorption peak that place occurs, corresponding to antisymmetric stretching vibration and the symmetrical stretching vibration of the-OH base generated after epoxy addition; 1758cm
-1locate the stretching vibration absorption peak that strong absorption peak is C=O in propenyl glycidyl ether; 1320cm
-1the strong absorption peak that place occurs is attributed to-C-F stretching vibration; 1037cm
-1place is the charateristic avsorption band of O=S=O; 938cm
-1place is the characteristic peak of epoxy.
(3) above-mentioned Cross-linkable fluoropolymer Nano microsphere is used for carrying out modification to its surface, prepares hydrophobic/oleophobic coating, comprise following operation steps:
A () filter paper uses ethanol, water washing successively, then dry;
B Cross-linkable fluoropolymer Nano microsphere that () will prepare, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, epoxy resin, the mass ratio of solvent M is 1:0.5:0.4:50; Solvent M is dioxy six alkane; Solidifying agent is 2-ethyl-4-methylimidazole; Epoxy resin is o-phthalic acid diglycidyl ester;
C the coating liquid prepared in step (b) is coated in substrate surface by spraying or the mode of dip-coating by (), after 20 ~ 30 DEG C of film forming, then be placed on 120 DEG C of crosslinked 12h, can obtain a kind of super-hydrophobic/material of oleophobic.
The performance perameter of super-double-hydrophobic surface prepared by table 1 embodiment 1 ~ 5
In table 1, WCA is water contact angle, OCA is oily contact angle, SA is water roll angle, all according to document (Dean Xiong and Guojun Liu.Diblock-copolymer-coated Water-andOil-Repellent Cotton Fabrics.Langmuir2012,28,6911-6918) in the method mentioned test.
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 (Guang Li, Haiting Zheng, Yanxue Wang, Hu Wang, Qibao Dong, Ruke Bai.A facile strategy for the fabrication of highly stablesuperhydrophobic cotton fabric using amphiphilic fluorinated triblock azidecopolymers.Polymer2010, 51, the method mentioned 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, use its contact angle of contact angle instrument test again, when the contact angle of water or oil is greater than 150 °, represent that the hydrophobic of this material or oleophobic performance do not decline.Until its contact angle is less than 150 °, represent that the hydrophobic of its surface or oleophobic performance have dropped.Recording this time, by comparing the length of this time, characterizing its resistance to acids and bases.
The testing method of washing fastness is reference literature (Dean Xiong and Guojun Liu.Diblock-copolymer-coated Water-and Oil-Repellent Cotton Fabrics.Langmuir2012,28,6911-6918) in the method mentioned.
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 (Kunshan Ultrasonic Instruments Co., Ltd.) 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 performance do not decline.Until its contact angle is less than 150 °, represent that the hydrophobic of its surface or oleophobic performance have dropped.Recording this time, by comparing the length of this time, characterizing its resistance to ultrasonic property.
As can be seen from Table 1: super-double-hydrophobic surface and the base material bonding of embodiment 1 ~ 5 are firm, cohesive force strong, rub resistance, wash resistant.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a Cross-linkable fluoropolymer Nano microsphere, it is characterized in that, comprise the following steps: epoxy cross-linking Nano microsphere is dispersed in solvent orange 2 A 1, add catalyzer again and be heated to 60 ~ 120 DEG C, then under the condition stirred, the fluorochemicals F solution being dissolved in solvent orange 2 A 2 is added, reaction 2 ~ 24h, finally removes the solvent in reaction system, obtains described cross-linking type fluorine-containing polymer nano-microspheres;
The structural formula of described fluorochemicals F is such as formula shown in (a):
(a), wherein n=0,1,2,3,4,5,6,7,8,9 or 10; M=0,1,2,3,4,5,6,7,8,9 or 10; X is hydroxyl, amino, carboxyl or sulfydryl;
The size of described epoxy cross-linking Nano microsphere is 50 ~ 1000 nanometers, and its structural formula is such as formula shown in (b):
(b)。
2. preparation method according to claim 1, it is characterized in that, the mass ratio of described epoxy cross-linking Nano microsphere, solvent orange 2 A 1, solvent orange 2 A 2, fluorochemicals F and catalyzer is 1:(1 ~ 50): (1 ~ 50): (0.2 ~ 10): (0.001 ~ 0.1).
3. preparation method according to claim 1, is characterized in that,
Described catalyzer is more than one in triethylamine, diethylene diamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine and benzyltriethylammoinium chloride;
Described solvent orange 2 A 1 and solvent orange 2 A 2 are more than one in tetrahydrofuran (THF), dimethyl fumarate, Isosorbide-5-Nitrae-dioxane, pimelinketone, two butanone, p-Xylol, phenylfluoroform, phenyl ether and methyl-phenoxide
。
4. preparation method according to claim 1, it is characterized in that, described fluorochemicals F is 3-perfluoro capryl propyl alcohol, perfluor dodecyl mercaptans, 3-perfluoro hexyl propyl alcohol, perfluoro octyl ethanol, the perfluor trimethyl carbinol, perfluor-2, more than one in 5-dimethyl-3,6-dioxanonanoic acid, 11 fluorine caproic acids, Perfluorocaprylic Acid, perfluorobutyric acid, perfluoro-heptanoic acid, perfluoro decyl mercaptan, perfluor spicy thioalcohol, perfluor dodecyl mercaptans, perfluoro capryl aniline and perfluoro octyl sulfonic acid amine;
Described epoxy cross-linking Nano microsphere prepares gained by the following method: initiator, stablizer and emulsifying agent are joined in solvent B, 50 ~ 80 DEG C are warming up to after passing into rare gas element deoxygenation, and then the mixed solution of the double bond monomer H added containing epoxide group and linking agent, reaction 3 ~ 10h, by product successively successively with the washing of methyl alcohol, water and tetrahydrofuran (THF), then centrifugal, heavily dispersion and vacuum-drying, obtains described epoxy cross-linking Nano microsphere.
5. preparation method according to claim 4, it is characterized in that, the mass ratio of described solvent B, initiator, stablizer, emulsifying agent, double bond monomer H containing epoxide group and linking agent is 1:(0.002 ~ 0.01): (0.01 ~ 0.2): (0 ~ 0.2): (0.1 ~ 50): (0.1 ~ 50).
6. preparation method according to claim 4, is characterized in that, the structural formula of the described double bond monomer H containing epoxide group is such as formula shown in (c):
(c); Wherein, R
1for hydrogen atom or methyl; R
3for CH
2, O, COOCH
2or C
6h
6; Z=0,1,2,3,4,5,6,7,8,9 or 10; Y=0 or 1; X is epoxide group;
Described linking agent is the monomer with two or more double bonds, and its structural formula is such as formula shown in (d):
(d)
Wherein, m=1,2,3,4,5,6,7,8,9 or 10; R is (C
6h
4) t, (CH
2) t or CO (OCH
2cH
2o) tOC, t=1,2,3,4,5,6,7,8,9 or 10; R
2for hydrogen atom or methyl; R
4for hydrogen atom or methyl;
Described solvent B is methyl alcohol, ethanol, n-propyl alcohol, Virahol or water; Described initiator is more than one in isobutyl miaow hydrochloride of Potassium Persulphate, ammonium persulphate, azo isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo two; Described stablizer is polyvinylpyrrolidone, polyoxyethylene glycol or polyvinyl alcohol; Emulsifying agent is sodium lauryl sulphate, Dodecyl trimethyl ammonium chloride, polyethenoxy ether class or Sodium dodecylbenzene sulfonate; Described rare gas element is nitrogen or helium.
7. preparation method according to claim 4, is characterized in that, the described double bond monomer H containing epoxide group is more than one in methacryloxyethyl acid glycidyl ether, propenyl glycidyl ether and 1,2-epoxy group(ing)-5-hexene;
Described linking agent is more than one in vinyl hexanediacetate, 1,4 cyclohexane dimethanol divinyl ether, Ethylene glycol dimethacrylate, TEGDMA, triethylene glycol diacrylate, Vinylstyrene and TEG dimethacrylate.
8. the Cross-linkable fluoropolymer Nano microsphere that obtains of preparation method described in any one of claim 1 ~ 7, it is characterized in that, Cross-linkable fluoropolymer Nano microsphere structural formula is such as formula shown in (e):
(e); In formula, g represents grafting, and F is fluorochemicals.
9. the Cross-linkable fluoropolymer Nano microsphere that preparation method described in any one of claim 1 ~ 7 obtains is applied to constructs super-double-hydrophobic surface; It is characterized in that, described in construct the concrete steps of super-double-hydrophobic surface as follows:
(1) substrate surface pre-treatment;
(2) the Cross-linkable fluoropolymer Nano microsphere will prepared, solidifying agent and epoxy resin are dispersed in solvent M, obtain coating liquid; Wherein Cross-linkable fluoropolymer Nano microsphere, solidifying agent, the mass ratio of epoxy resin and solvent M is 1:(0.002 ~ 0.5): (0.1 ~ 0.4): (1 ~ 50);
(3) coating liquid step (2) prepared is coated in substrate surface by spraying or the mode of dip-coating, after 20 ~ 30 DEG C of film forming, then be positioned over 80 ~ 120 DEG C crosslinked 2 ~ 24 hours, obtain described super-double-hydrophobic surface.
10. Cross-linkable fluoropolymer Nano microsphere application according to claim 9, it is characterized in that, the base material described in step (1) is sheet glass, cotton, filter paper, timber or cement matrix;
Described solvent M is more than one in tetrahydrofuran (THF), dimethyl fumarate, dioxy six alkane, pimelinketone, two butanone, p-Xylol, phenylfluoroform, phenyl ether and methyl-phenoxide;
Described solidifying agent is triethylamine, diethylenetriamine, tetraethylene pentamine, Tetra hydro Phthalic anhydride, glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole;
Described epoxy resin is vinyl cyclohexene dioxide, bisphenol A type epoxy resin, 2,3-epoxypropyl butyl ether, molecular weight are the polymethyl acrylic acid glycidyl ether of 500 ~ 100000 or molecular weight is one in the polypropylene-base glycidyl ether of 500 ~ 100000.
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